Non-fullerene acceptor material and application thereof

Abstract

The invention relates to the technical field of organic photovoltaic cell materials, in particular to a non-fullerene acceptor material and application thereof. The non-fullerene acceptor material provided by the invention has a structure as shown in a formula (I), and a dicyano structure is introduced into a large fused ring core of the non-fullerene acceptor material, so that the non-fullerene acceptor material is applied to a two-component system as a third component, and the photoelectric conversion efficiency of a device is effectively improved.

Description

Technical Field

[0001] The present invention relates to the technical field of organic photovoltaic cell materials, and in particular to a non-fullerene acceptor material and applications thereof. Background Art

[0002] With the development of efficient non-fullerene acceptor materials and the optimization of device structure and process, the photoelectric performance of organic solar cells has rapidly improved, with the power conversion efficiency (PCE) of single-junction devices exceeding 20%. Compared with fullerene materials and their derivatives, non-fullerene acceptor materials have advantages in light absorption, energy level tunability, high solubility, and crystallinity. Among them, efficient photogenerated carrier generation and low energy loss are the main reasons for the higher PCE of organic solar cells based on non-fullerene acceptor materials. Currently, the active layer in commonly used organic solar cells adopts a bulk heterojunction (BHJ) structure, that is, the donor and acceptor materials are blended and dissolved and then spin-coated into a film. However, to further overcome the inherent limitations of binary systems in terms of phase separation control, exciton recombination suppression, and carrier mobility, and achieve higher power conversion efficiency and device stability, we can often achieve performance improvements of the binary host by rationally designing the third component and synergistically optimizing the active layer morphology, energy level matching, and charge transfer dynamics. Summary of the Invention

[0003] In view of this, the present invention aims to develop a new type of non-fullerene acceptor material and apply it as the third component in a binary organic solar cell system, thereby improving the photoelectric conversion efficiency of the organic solar cell.

[0004] To achieve the above objectives, the first aspect of the present invention provides a non-fullerene acceptor material having a structure as shown in the general formula (I):

[0005]

[0006] in:

[0007] Each occurrence of Z is independently selected from S or Se;

[0008] Each occurrence of R1 is independently selected from -H, -D, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, a a A substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or R a a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms;

[0009] Each occurrence of R2 is independently selected from R b a substituted or unsubstituted alkyl group having 8 to 30 carbon atoms;

[0010] Each occurrence is independently selected from wherein each occurrence of M is independently selected from O or C(CN)2; Each occurrence is independently selected from the c A substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or R c A substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms; * indicates the attachment site;

[0011] R a each occurrence is independently selected from alkyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, or alkylthio having 1 to 20 carbon atoms;

[0012] R b Each occurrence is independently selected from -D (deuterium), -F, -Cl, an aromatic group having 6-10 carbon atoms, or a heteroaromatic group having 5-10 ring atoms, or a group formed by a combination of the foregoing groups;

[0013] R c Each occurrence is independently selected from -D (deuterium), -F, -Cl, -Br, -I, -CF3, -CN, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms, a straight-chain alkoxy group having 1 to 10 carbon atoms, a branched-chain alkoxy group having 3 to 10 carbon atoms, or a group formed by a combination of the foregoing groups.

[0014] In one embodiment, the Selected from

[0015] Furthermore, the Each occurrence is independently selected from the following groups:

[0016]

[0017] in:

[0018] m1 is selected from 0, 1, 2, 3 or 4; m2 is selected from 0, 1, 2, 3, 4, 5 or 6; m2 is selected from 0, 1 or 2;

[0019] # represents a fusion site, which is selected from carbon atoms.

[0020] In an optional embodiment, the R c Each occurrence is independently selected from -D (deuterium), -F, -Cl, -Br, -I, -CF3, -CN, methyl or methoxy.

[0021] Specifically, the Selected from any of the following groups:

[0022]

[0023]

[0024] In one embodiment, Each occurrence is selected from the same group.

[0025] In one embodiment, each occurrence of R1 is independently selected from -H, -D, a linear alkyl group having 1 to 20 carbon atoms, a branched alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, a linear alkoxy group having 1 to 20 carbon atoms, a branched alkoxy group having 3 to 20 carbon atoms, a cyclic alkoxy group having 3 to 20 carbon atoms, a linear alkylthio group having 1 to 20 carbon atoms, a branched alkylthio group having 3 to 20 carbon atoms, a cyclic alkylthio group having 3 to 20 carbon atoms, a substituted R a A substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or R a A substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms.

[0026] Furthermore, R a Each occurrence is independently selected from a straight chain alkyl group having 1 to 10 carbon atoms, a branched chain alkyl group having 3 to 10 carbon atoms, a straight chain alkoxy group having 1 to 10 carbon atoms, a branched chain alkoxy group having 3 to 10 carbon atoms, a straight chain alkylthio group having 1 to 10 carbon atoms, or a branched chain alkylthio group having 3 to 10 carbon atoms.

[0027] In one embodiment, each occurrence of R1 is independently selected from -H, -D, or the following groups:

[0028] *-C8H 17 、*-C9H 19 、*-C 11 H 23 、 *-OC 11 H 23 、*--OC 10 H 21 、*-OC 12 H 25 、*-OC9H 19 、 *-SC 11 H 23 、*-SC 10 H 21 、*-SC 12 H 25 、*-SC9H 19 、

[0029]

[0030] Furthermore, each occurrence of R1 is selected from the same group.

[0031] In an alternative embodiment, each occurrence of R2 is independently selected from b a substituted or unsubstituted alkyl group having 8 to 30 carbon atoms; said R b is selected from phenyl, or phenyl substituted by one or more Fs.

[0032] In another alternative embodiment, each occurrence of R2 is independently selected from R b a substituted or unsubstituted branched alkyl group having 8 to 20 carbon atoms; said R b is selected from phenyl, or phenyl substituted by one or more Fs.

[0033] In one embodiment, each occurrence of R2 is independently selected from the following groups:

[0034]

[0035] Furthermore, each occurrence of R2 is selected from the same group.

[0036] In one embodiment, each occurrence of Z is selected from S.

[0037] In another embodiment, each occurrence of Z is the same and is selected from Se.

[0038] Specifically, the non-fullerene acceptor material according to the present invention is selected from the following structures but is not limited thereto:

[0039]

[0040]

[0041]

[0042]

[0043] The second aspect of the present invention provides an organic compound as shown in the general formula (II):

[0044]

[0045] in:

[0046] Each occurrence of Z is independently selected from S or Se;

[0047] Each occurrence of R1 is independently selected from -H, -D, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, a a A substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or R a a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms;

[0048] Each occurrence of R2 is independently selected from R b a substituted or unsubstituted alkyl group having 8 to 20 carbon atoms;

[0049] R a Each occurrence is independently selected from alkyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, or alkylthio having 3 to 20 carbon atoms;

[0050] R b Each occurrence is independently selected from -D (deuterium), -F, -Cl, an aromatic group having 6-10 carbon atoms, or a heteroaromatic group having 5-10 ring atoms, or a group formed by a combination of the above groups.

[0051] The further definitions of R1 and R2 are the same as those described above.

[0052] In a specific embodiment, the organic compound represented by the general formula (II) is selected from the following structures, but is not limited thereto:

[0053]

[0054]

[0055]

[0056] The third aspect of the present invention relates to a mixture, comprising the non-fullerene acceptor material according to the first aspect.

[0057] Furthermore, according to the mixture of the present invention, the mixture comprises a first compound and a second compound, the first compound is selected from the non-fullerene acceptor material as described in the first aspect, and the second compound is selected from the structure described in formula (III):

[0058]

[0059] in:

[0060] Each occurrence of Y is independently selected from S or Se;

[0061] Each occurrence of W is independently selected from S or Se;

[0062] Each occurrence of R3 is independently selected from -H, -D, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a d A substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or R d a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms;

[0063] R d Each occurrence is independently selected from alkyl having 3 to 20 carbon atoms, alkoxy having 3 to 20 carbon atoms, alkylthio having 3 to 20 carbon atoms;

[0064] R4, at each occurrence, is independently selected from an alkyl group having 8 to 20 carbon atoms;

[0065] Each occurrence of R5 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, -CN, a straight-chain alkyl group having 1 to 10 carbon atoms, a branched-chain alkyl group having 3 to 10 carbon atoms, a straight-chain alkoxy group having 1 to 10 carbon atoms, a branched-chain alkoxy group having 3 to 10 carbon atoms, or a group formed by a combination of the foregoing groups.

[0066] In an alternative embodiment, each occurrence of R3 is independently selected from -H, -D, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 3 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a branched-chain alkoxy group having 3 to 20 carbon atoms, a straight-chain alkylthio group having 1 to 20 carbon atoms, a branched-chain alkylthio ... straight-chain alkylthio group having 3 to 20 carbon atoms, a straight-chain alkylthio group having 1 to 20 carbon atoms, a straight-chain alkylthio group having 3 to 20 carbon atoms, a straight-chain alkylthio group d Substituted or unsubstituted phenyl, or R d Substituted or unsubstituted thienyl; said R d Each occurrence is independently selected from -D, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 3 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a branched-chain alkoxy group having 3 to 20 carbon atoms, a straight-chain alkylthio group having 1 to 20 carbon atoms, and a branched-chain alkylthio group having 3 to 20 carbon atoms.

[0067] Each occurrence of R4 is independently selected from a straight chain alkyl group having 8 to 20 carbon atoms, or a branched chain alkyl group having 8 to 20 carbon atoms.

[0068] In a specific embodiment, the second compound is selected from the following structures, but is not limited thereto:

[0069]

[0070] In one embodiment, the mass ratio of the first compound to the second compound in the mixture is selected from 0 to 20%.

[0071] Furthermore, the mass ratio of the first compound to the second compound in the mixture is selected from 5 to 10%.

[0072] In a specific embodiment, the mass ratio of the first compound to the second compound in the mixture is selected from 0.1:1.1 or 0.2:1.

[0073] The fourth aspect of the present invention relates to an organic photovoltaic device, comprising a cathode, an anode, and a photoactive layer located between the cathode and the anode, wherein the photoactive layer acceptor material comprises the non-fullerene acceptor material as described in the first aspect or the mixture as described in the third aspect.

[0074] Furthermore, the photoactive layer of the organic photovoltaic device according to the present invention further comprises a photoactive layer donor material. Preferably, the photoactive layer donor material is selected from polymer donor materials.

[0075] In a specific embodiment, the polymer donor material is selected from one, two, or more of PBDB-T, PM6, PM7, D18, D18-Cl, PTO2, PB2, PB2F, PTVT-BT, PTQ10, PTQ11, PBQx-TC1, PBQx-TF, and PTB7-TH, but is not limited thereto. For further information on the selection of active layer donor materials, see Progress in Polymer Science, 143 (2023), 101711.

[0076] The photoactive layer preparation method comprises: dissolving the photoactive layer donor material and the acceptor material in an organic solvent according to a certain mass ratio, stirring and uniformly dissolving the material to obtain a photoactive layer solution.

[0077] The organic solvent is preferably selected from tetralin, 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, methyl chloride, dichloromethane, chloroform, dichloroethylene, trichloroethylene, 1,2-trimethylbenzene, Chlorotrifluoroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, carbon tetrachloride, tetrahydrofuran, anisole, 2,4-dimethylanisole, 1-methylnaphthalene, morpholine, 1,4-dioxane, N-methylpyrrolidone, acetone, cyclopentanone, cyclohexanone, methyl ethyl ketone, ethyl acetate, n-butyl acetate, carbon disulfide, carbon tetrachloride, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, indane, methyl benzoate, ethyl benzoate, acetonitrile, hexamethylphosphoramide, or a mixture of two or more thereof.

[0078] The above solution is used to prepare the photoactive layer by a printing or coating method. The printing or coating method may include, but is not limited to, inkjet printing, gravure printing, spray printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, rotary roller printing, lithographic printing, flexographic printing, rotary printing, spray coating, brush coating, pad printing, and slot die coating. Slot coating, spin coating, and inkjet printing are preferred.

[0079] The mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is preferably: 1:0.8 to 1:1.5; further, the mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is preferably: 1:1 to 1:1.5; the mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is preferably: 1:1 to 1:1.2.

[0080] 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 6 to 10 mg / mL.

[0081] In one embodiment, the organic photovoltaic device according to the present invention comprises an anode, an anode buffer layer, a photoactive layer, a cathode buffer layer, and a cathode layer stacked from bottom to top.

[0082] At least one of the anode and cathode is transparent or translucent to facilitate light incidence. The materials used to prepare the electrodes can be selected from metals such as vanadium (V), chromium (Cr), zinc (Zn), silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), palladium (Pd), or alloys of the above metals; conductive nanomaterials such as metal nanowires, nanoparticle pastes, graphene, carbon nanotubes, etc.; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc.; combinations of metals and oxides such as ZnO:Al or SnO2:Sb; 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, etc., but are not limited thereto.

[0083] Preferably, the cathode buffer layer material can be selected from metal complexes, metal oxides, metal salts, etc. with low work function, such as metal complexes of 8-hydroxyquinoline, complexes containing Alq3, metal complexes containing Liq, LiF, Ca, titanium oxide (TiO x ), zinc oxide (ZnO), cesium carbonate (Cs2CO3), etc.; it can also be a polymer material, such as PFN-Br or PFN or PDINN or PDINO or PNDIT-F3N-Br or PNDIT-F3N, etc., but not limited to this.

[0084] The anode buffer layer material is selected from PEDOT:PSS, molybdenum oxide (MoO x ), vanadium oxide (V2O5), nickel oxide (NiO), tungsten oxide (WO x , preferably, x is selected from 2 or 3), small molecule self-assembly materials such as 2PACz, MeO-2PACz, etc., but not limited thereto.

[0085] It should be noted that, in order to improve the performance of the organic photovoltaic cell device, the organic photovoltaic cell may further comprise other functional layers, including but not limited to a charge blocking layer, a charge transport layer and a passivation layer.

[0086] The organic photovoltaic cell according to the present invention is mainly used in indoor photovoltaics, wearable devices, smart Internet of Things, smart homes, smart agriculture, building photovoltaics, new energy vehicles and other fields.

[0087] Beneficial effects of the present invention:

[0088] The present invention provides a non-fullerene acceptor material having a structure as shown in formula (I). By introducing a dicyano structure into the large condensed ring core of the non-fullerene acceptor material, when it is used as a third component in a binary device system, on the one hand, the phase separation behavior of the active layer is precisely regulated, inducing the formation of a nano-interpenetrating network structure with high crystallinity and optimized molecular orientation, thereby improving the charge transfer efficiency; on the other hand, the third component has a relatively wide bandgap, and the introduction of a suitable proportion will reduce the energy loss of the device. When applied to an organic photovoltaic device, the photoelectric conversion efficiency of the device is effectively improved. BRIEF DESCRIPTION OF THE DRAWINGS

[0089] In order to more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the specific embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0090] Figure 1 is a schematic structural diagram of a device embodiment of the present invention;

[0091] Reference numerals: 101, substrate; 102, anode layer; 103, anode buffer layer; 104, photoactive layer; 105, cathode buffer layer; 106, cathode layer. DETAILED DESCRIPTION

[0092] The following examples are provided for a better understanding of the present invention and are not intended to limit the best mode of implementation. They do not limit the content and scope of protection of the present invention. Any product identical or similar to the present invention obtained by anyone under the guidance of the present invention or by combining the features of the present invention with other prior arts shall fall within the scope of protection of the present invention.

[0093] 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").

[0094] In the present invention, organic photovoltaic device, organic photovoltaic cell, organic solar cell, OPV, and OSC have the same meaning and can be interchanged.

[0095] In the present invention, photoactive layer and active layer have the same meaning and can be interchanged.

[0096] In the present invention, when a group contains multiple substituents with the same symbol, the substituents may be the same or different from each other, for example The six Rs on the benzene ring may be the same as or different from each other.

[0097] In the present invention, "substituted" means that one or more hydrogen atoms in a substituted group are replaced by a substituent.

[0098] 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 same applies to the "number of ring atoms" described below unless otherwise specified. In an aromatic group, the number of ring atoms is the same as the number of carbon atoms; in a heteroaromatic group, the number of ring atoms is the number of carbon atoms plus the number of heteroatoms; for example, the number of ring atoms of a benzene ring is 6, the number of ring atoms of a naphthalene ring is 10, the number of ring atoms of 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.

[0099] In the present invention, "aromatic group" refers to an optional functional group or substituent derived from an aromatic carbocyclic ring. The aromatic group can be a monocyclic aromatic group (e.g., phenyl) or a polycyclic aromatic group. In other words, the aromatic group can be a monocyclic aromatic group, a condensed ring aromatic group, two or more monocyclic aromatic groups connected by carbon-carbon conjugation, a monocyclic aromatic group and a condensed ring aromatic group connected by carbon-carbon conjugation, or two or more condensed ring aromatic groups connected by carbon-carbon conjugation. That is, unless otherwise indicated, two or more aromatic groups connected by carbon-carbon conjugation can also be considered as aromatic groups of the present application. Aromatic groups include, but are not limited to, phenyl, biphenyl, terphenyl, naphthyl, and derivatives thereof.

[0100] In the present invention, "heteroaromatic group" refers to a monovalent heteroaromatic ring or derivative thereof containing 1, 2, 3, 4, 5, 6 or more heteroatoms in the ring, wherein the heteroatom can be at least one of B, O, N, P, Si, Se and S. The heteroaromatic group can be a monocyclic heteroaromatic group or a polycyclic heteroaromatic group. In other words, the heteroaromatic group can be a single heteroaromatic ring system or multiple heteroaromatic ring systems connected by carbon-carbon bonds, and any heteroaromatic ring system is a heteroaromatic monocyclic ring or a heteroaromatic fused ring. Heteroaromatic groups include, but are not limited to, thienyl, furyl, selenophenyl, thienothiphenyl, thienoselenophenyl, pyridyl, pyrimidinyl, triazinyl and their derivatives.

[0101] In the present invention, alkyl comprises straight chain alkyl, branched chain alkyl, cyclic alkyl and combination thereof. The carbon number of straight chain alkyl can be with 1 to 30 carbon atoms, with 1 to 20 carbon atoms, with 1 to 16 carbon atoms, with 1 to 10 carbon atoms or with 1 to 6 carbon atoms. The carbon number of branched chain alkyl can be with 3 to 30 carbon atoms, with 3 to 20 carbon atoms, with 3 to 16 carbon atoms, with 3 to 10 carbon atoms or with 3 to 6 carbon atoms. The carbon number of cycloalkyl can be with 3 to 30 carbon atoms, with 3 to 20 carbon atoms, with 3 to 16 carbon atoms, with 3 to 10 carbon atoms or with 3 to 6 carbon atoms. The non-limiting examples of straight chain alkyl include methyl (-CH ), ethyl (-C H ), n-propyl (-C H ), n-butyl (-C H ), n-pentyl (-C H 11 ), n-hexyl (-C6H 13 ), n-heptyl (-C7H 15 ), n-octyl (-C8H 17 ), n-nonyl (-C9H 19 ),-C 10 H 21 、-C 11 H 23 、-C 12 H 25 、-C13 H 27 、-C 14 H 29 、-C 15 H 31 、-C 16 H 33 Non-limiting examples of branched alkyl groups include isopropyl, branched alkyl groups containing 4 carbon atoms, branched alkyl groups containing 5 carbon atoms, branched alkyl groups containing 6 carbon atoms, branched alkyl groups containing 7 carbon atoms, branched alkyl groups containing 8 carbon atoms, branched alkyl groups containing 9 carbon atoms, branched alkyl groups containing 10 carbon atoms, branched alkyl groups containing 11 carbon atoms, branched alkyl groups containing 12 carbon atoms, branched alkyl groups containing 13 carbon atoms, branched alkyl groups containing 14 carbon atoms, branched alkyl groups containing 15 carbon atoms, and branched alkyl groups containing 16 carbon atoms. Non-limiting examples of cycloalkyl groups include: cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloalkyl groups containing 7 carbon atoms, cycloalkyl groups containing 8 carbon atoms, cycloalkyl groups containing 9 carbon atoms, cycloalkyl groups containing 10 carbon atoms (such as adamantyl), cycloalkyl groups containing 11 carbon atoms, cycloalkyl groups containing 12 carbon atoms, cycloalkyl groups containing 13 carbon atoms, cycloalkyl groups containing 14 carbon atoms, cycloalkyl groups containing 15 carbon atoms, and cycloalkyl groups containing 16 carbon atoms.

[0102] The term "alkoxy" refers to a group having the structure "-O-alkyl," i.e., an alkyl group as defined above attached to another group via an oxygen atom. A straight-chain alkoxy group means that the alkyl group in "-O-alkyl" is selected from a straight-chain alkyl group, where the definition of straight-chain alkyl is the same as above; a branched-chain alkoxy group means that the alkyl group in "-O-alkyl" is selected from a branched-chain alkyl group, where the definition of branched-chain alkyl is the same as above.

[0103] The term "alkylthio" refers to a group having the structure "-S-alkyl," i.e., an alkyl group as defined above attached via a sulfur atom to another group. A straight-chain alkylthio group means that the alkyl group in "-S-alkyl" is selected from a straight-chain alkyl group, where the definition of straight-chain alkyl is as described above; a branched-chain alkylthio group means that the alkyl group in "-S-alkyl" is selected from a branched-chain alkyl group, where the definition of branched-chain alkyl is as described above.

[0104] In the present invention, when a linking site is not specified in a group, it means that any linking site in the group can be used as the linking site.

[0105] 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.

[0106] In the present invention, the single bond connecting the substituent runs through the corresponding ring, indicating that the substituent can be connected to any position of the ring, for example R is connected to any substitutable position of the benzene ring.

[0107] In the present invention, taking 3 to 20 carbon atoms as an example, it means containing 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms.

[0108] In the present invention, having 3 to 10 carbon atoms means containing 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms.

[0109] In the present invention, taking having 1 to 20 carbon atoms as an example, it means containing 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20 carbon atoms.

[0110] In the present invention, the term "having 1 to 10 carbon atoms" is taken as an example, which means containing 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10 carbon atoms.

[0111] In the process of describing the structural elements of the present invention, the words "include" or "comprises" and the like used in the present invention mean that the devices or materials preceding the word include the devices or materials listed after the word and their equivalents, without excluding other devices or materials.

[0112] 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.

[0113] The terms "combination thereof", "any combination thereof", "any combination thereof", "combination" and the like used in the present invention include all suitable combinations of any two, any three or more of the listed groups.

[0114] 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.

[0115] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in this field can be used. If the manufacturer of the reagents or instruments is not specified, they are all commercially available conventional reagents.

[0116] Synthesis Example of Non-Fullerene Acceptor Material

[0117] The following examples are provided to facilitate a better understanding of the disclosure of the present invention and are not intended to limit the present invention in any way. The experimental methods used in the following examples are conventional methods unless otherwise specified, and the materials and reagents used are all prior art and can be obtained from commercial sources unless otherwise specified.

[0118] Synthesis Example 1: Synthesis of Compound (1)

[0119]

[0120] Synthesis of compound 1-2:

[0121] Compound 1-1 (2.4 g, 2.40 mmol) was added to a 100 mL three-necked flask, and 20 mL of tetrahydrofuran was added with stirring to dissolve. The nitrogen atmosphere was replaced three times, and the temperature was lowered to 0°C. 16 mL of lithium aluminum hydride (2.5 M) was added, and the temperature was raised to 80°C for 18 h. The mixture was then extracted with water and dichloromethane, dried over Na2SO4, and concentrated to afford compound 1-2 (1.97 g, 84.5% yield, MS: 971.85).

[0122] Synthesis of compound 1-3:

[0123] Compound 1-2 (1.9 g, 1.95 mmol) and urea (0.35 g, 5.85 mmol) were added to a 100 mL round-bottom flask. A 25% THF / water solution was added and stirred thoroughly. One to two drops of acetic acid were then added as a catalyst. The reaction mixture was heated to 120°C for 4.5 hours and then to 135°C for 0.5 hours to remove any remaining ammonia. After the reaction, the resulting precipitate was filtered, rinsed three times with ethanol, and then recrystallized from methanol. The precipitate was filtered and dried to yield compound 1-3 (1.81 g, 93.3% yield, MS: 995.12).

[0124] Synthesis of compound 1-4:

[0125] Compound 1-3 (1.79 g, 1.80 mmol), malononitrile (0.24 g, 3.60 mmol) and sodium acetate (0.30 g, 3.60 mmol) were added to a 100 mL round-bottom flask, the nitrogen was replaced three times, 30 mL of ethanol was added, and the mixture was heated to 40°C for 4 h. Concentrated hydrochloric acid was added to precipitate the solid, and the precipitate was filtered, washed three times with deionized water and three times with petroleum ether, and purified by column chromatography (DCM as eluent) to obtain compound 1-4 (1.35 g, 71.9% yield, MS: 1043.49).

[0126] Synthesis of compound 1-5:

[0127] Compound 1-4 (1.2 g, 1.15 mmol) was weighed into a 100 mL three-necked flask. 15 mL of 1,2-dichloroethane was added, the atmosphere was replaced with nitrogen three times, and the mixture was cooled to approximately 0°C in an ice-water bath. Separately, 20 mL of DMF and 3 mL of phosphorus oxychloride were thoroughly mixed in a 100 mL beaker and slowly added dropwise to the reaction flask under nitrogen. After the addition was complete, the mixture was heated to 90°C and reacted for 2 h. After the reaction was completed, the mixture was cooled to room temperature and then poured into icy NaOH solution. Extraction was performed with DCM and dried over anhydrous Na2SO4. The solvent was removed and the product was purified by column chromatography using a PE:DCM ratio of 2:1 (volume ratio) to afford compound 1-5 (0.92 g, 72.7% yield, MS: 1099.74).

[0128] Synthesis of compound (1):

[0129] Compound 1-5 (100 mg, 0.091 mmol), compound A1 (104 mg, 0.454 mmol), and dry toluene (8 mL) were added to a two-necked flask. After nitrogen was replaced three times, boron trifluoride etherate (0.3 mL) and acetic anhydride (0.3 mL) were added and reacted at room temperature for 20 min. After the reaction, the reaction solution was added dropwise to methanol for precipitation, and the crude product was filtered to obtain a crude product. The crude product was purified by column chromatography using a 1:1 (volume ratio) eluent of PE:DCM to obtain compound (1) (102 mg, 73.6% yield, MALDI-TOF-MS: 1523.86).

[0130] Synthesis Example 2: Synthesis of Compound (5)

[0131]

[0132] Compound 1-5 (100 mg, 0.091 mmol), compound A2 (120 mg, 0.454 mmol), and dry toluene (8 mL) were added to a two-necked flask. After nitrogen was replaced three times, boron trifluoride etherate (0.3 mL) and acetic anhydride (0.3 mL) were added and reacted at room temperature for 20 min. After the reaction, the reaction solution was added dropwise to methanol for precipitation, and the crude product was filtered to obtain a crude product. The crude product was purified by column chromatography using a PE:DCM = 1:1 (volume ratio) eluent to obtain compound (5) (100 mg, 69.1% yield, MALDI-TOF-MS: 1589.53).

[0133] Synthesis Example 3: Synthesis of Compound (15)

[0134]

[0135] Synthesis of compound 15-2:

[0136] Compound 15-1 (2.1 g, 2.04 mmol) was added to a 100 mL three-necked flask, and 20 mL of tetrahydrofuran was added with stirring to dissolve. The nitrogen atmosphere was replaced three times, and the temperature was lowered to 0°C. 14 mL of lithium aluminum hydride (2.5 M) was added, and the temperature was raised to 80°C for 18 h. The mixture was then extracted with water and dichloromethane, dried over Na2SO4, and concentrated to afford compound 15-2 (1.86 g, 91.2% yield, MS: 1000.02).

[0137] Synthesis of compound 15-3:

[0138] Compound 15-2 (1.80 g, 1.80 mmol) and urea (0.32 g, 5.4 mmol) were added to a 100 mL round-bottom flask. A 25% THF / water solution was added and stirred thoroughly. One to two drops of acetic acid were then added as a catalyst. The reaction mixture was heated to 120°C for 4.5 hours and then to 135°C for 0.5 hours to remove any remaining ammonia. After completion of the reaction, the resulting precipitate was filtered and rinsed three times with ethanol, then recrystallized from methanol. The precipitate was filtered and dried to afford compound 15-3 (1.66 g, 90.1% yield, MS: 1023.65).

[0139] Synthesis of compound 15-4:

[0140] Compound 15-3 (1.60 g, 1.56 mmol), malononitrile (0.21 g, 3.12 mmol) and sodium acetate (0.26 g, 3.12 mmol) were added to a 100 mL round-bottom flask, the nitrogen atmosphere was replaced three times, 30 mL of ethanol was added, and the mixture was heated to 40°C for 4 h. Concentrated hydrochloric acid was added to precipitate the solid, and the precipitate was filtered, washed three times with deionized water and three times with petroleum ether, and purified by column chromatography (DCM as eluent) to obtain compound 15-4 (1.31 g, 78.3% yield, MS: 1071.84).

[0141] Synthesis of compound 15-5:

[0142] Compound 15-4 (1.10 g, 1.03 mmol) was weighed into a 100 mL three-necked flask. 15 mL of 1,2-dichloroethane was added, the atmosphere was replaced with nitrogen three times, and the mixture was cooled to approximately 0°C in an ice-water bath. Separately, 20 mL of DMF and 3 mL of phosphorus oxychloride were thoroughly mixed in a 100 mL beaker and slowly added dropwise to the reaction flask under nitrogen. After the addition was complete, the mixture was heated to 90°C for 2 h. After the reaction was complete, the mixture was cooled to room temperature and then poured into icy NaOH solution. The mixture was extracted with DCM and dried over anhydrous Na2SO4. The solvent was removed and the mixture was purified by column chromatography using a PE:DCM ratio of 2:1 (volume ratio) to afford compound 15-5 (0.85 g, 73.2% yield, MALDI-TOF-MS: 1127.55).

[0143] Synthesis of compound (15):

[0144] Compound 15-5 (110 mg, 0.098 mmol), compound A2 (117 mg, 0.443 mmol), and dry toluene (8 mL) were dissolved in a two-necked flask. After nitrogen was replaced three times, boron trifluoride etherate (0.3 mL) and acetic anhydride (0.3 mL) were added and reacted at room temperature for 20 min. After the reaction, the mixture was added dropwise to methanol to precipitate. The crude product was filtered and purified by column chromatography using a 1:1 (volume ratio) eluent to afford compound (15) (118 mg, 74.4% yield, MALDI-TOF-MS: 1617.82).

[0145] Synthesis Example 4: Synthesis of Compound (17)

[0146]

[0147] Synthesis of compound 17-2:

[0148] Compound 17-1 (3.0 g, 3.09 mmol) was added to a 100 mL three-necked flask, and 20 mL of tetrahydrofuran was added with stirring to dissolve. The nitrogen atmosphere was replaced three times, and the temperature was lowered to 0°C. 16 mL of lithium aluminum hydride (2.5 M) was added, and the temperature was raised to 80°C for 18 h. The mixture was then extracted with water and dichloromethane, dried over Na2SO4, and concentrated to afford compound 17-2 (2.59 g, 88.8% yield, MS: 943.82).

[0149] Synthesis of compound 17-3:

[0150] Compound 17-2 (2.50 g, 2.64 mmol) and urea (0.32 g, 5.39 mmol) were added to a 100 mL round-bottom flask. A 25% THF / water solution was added and stirred thoroughly. One to two drops of acetic acid were then added as a catalyst. The reaction mixture was heated to 120°C for 4.5 hours and then to 135°C for 0.5 hours to remove any remaining ammonia. After completion of the reaction, the resulting precipitate was filtered and rinsed three times with ethanol, then recrystallized from methanol. The precipitate was filtered and dried to afford compound 17-3 (2.13 g, 83.4% yield, MS: 967.18).

[0151] Synthesis of compound 17-4:

[0152] Compound 17-3 (2.10 g, 2.17 mmol), malononitrile (0.29 g, 4.34 mmol) and sodium acetate (0.36 g, 4.34 mmol) were added to a 100 mL round-bottom flask, the nitrogen was replaced three times, 30 mL of ethanol was added, and the mixture was heated to 40°C for 4 h. Concentrated hydrochloric acid was added to precipitate the solid, and the precipitate was filtered, washed three times with deionized water and three times with petroleum ether, and purified by column chromatography (DCM as eluent) to obtain compound 17-4 (1.36 g, 61.7% yield, MS: 1015.41).

[0153] Synthesis of compound 17-5:

[0154] Compound 17-4 (1.10 g, 1.08 mmol) was weighed into a 100 mL three-necked flask. 15 mL of 1,2-dichloroethane was added, the atmosphere was replaced with nitrogen three times, and the mixture was cooled to approximately 0°C in an ice-water bath. Separately, 20 mL of DMF and 3 mL of phosphorus oxychloride were thoroughly mixed in a 100 mL beaker and slowly added dropwise to the reaction flask under nitrogen. After the addition was complete, the mixture was heated to 90°C and reacted for 2 h. After the reaction was completed, the mixture was cooled to room temperature and then poured into icy NaOH solution. Extraction was performed with DCM and dried over anhydrous Na2SO4. The solvent was removed and the product was purified by column chromatography using a PE:DCM ratio of 2:1 (volume ratio) to afford compound 17-5 (0.96 g, 82.9% yield, MS: 1071.64).

[0155] Synthesis steps of compound 17:

[0156] Compound 17-5 (100 mg, 0.093 mmol), compound A1 (107 mg, 0.466 mmol), and dry toluene (8 mL) were dissolved in a two-necked flask. After nitrogen was replaced three times, boron trifluoride etherate (0.3 mL) and acetic anhydride (0.3 mL) were added and reacted at room temperature for 20 min. After the reaction, the mixture was added dropwise to methanol for precipitation. The crude product was filtered and purified by column chromatography using a 1:1 (volume ratio) eluent to afford compound (17) (98 mg, 70.5% yield, MALDI-TOF-MS: 1495.72).

[0157] Synthesis Example 5: Synthesis of Compound (20)

[0158]

[0159] Compound 17-5 (100 mg, 0.093 mmol), compound A3 (109 mg, 0.465 mmol), and dry toluene (8 mL) were dissolved in a two-necked flask. After nitrogen was replaced three times, boron trifluoride etherate (0.3 mL) and acetic anhydride (0.3 mL) were added and reacted at room temperature for 20 min. After the reaction, the mixture was added dropwise to methanol for precipitation. The crude product was filtered and purified by column chromatography using a 1:1 (volume ratio) eluent of PE:DCM to obtain compound (20) (92 mg, 65.7% yield, MALDI-TOF-MS: 1504.87).

[0160] Synthesis Example 6: Synthesis of Compound (21)

[0161]

[0162] Compound 1-5 (93 mg, 0.084 mmol), compound A4 (118 mg, 0.422 mmol), and dry toluene (8 mL) were dissolved in a two-necked flask. After nitrogen was replaced three times, boron trifluoride etherate (0.3 mL) and acetic anhydride (0.3 mL) were added and reacted at room temperature for 20 min. After the reaction, the mixture was added dropwise to methanol to precipitate. The crude product was filtered and purified by column chromatography using a 1:1 (volume ratio) eluent to obtain compound (21) (103 mg, 75.5% yield, MALDI-TOF-MS: 1623.90).

[0163] Synthesis Example 7: Synthesis of Compound (23)

[0164]

[0165] Synthesis of compound 23-2:

[0166] Compound 23-1 (2.5 g, 2.17 mmol) was added to a 100 mL three-necked flask, followed by the addition of 20 mL of tetrahydrofuran and stirring to dissolve. The nitrogen atmosphere was replaced three times, the temperature was lowered to 0°C, and 14 mL of lithium aluminum hydride (2.5 M) was added. The reaction temperature was raised to 80°C and allowed to react for 18 h. The mixture was then extracted with water and dichloromethane, dried over Na2SO4, and concentrated to afford compound 23-2 (1.99 g, 81.6% yield, MALDI-TOF-MS: 1123.65).

[0167] Synthesis of compound 23-3:

[0168] Compound 23-2 (1.80 g, 1.60 mmol) and urea (0.29 g, 4.79 mmol) were added to a 100 mL round-bottom flask. A 25% THF / water solution was added and stirred thoroughly. One to two drops of acetic acid were then added as a catalyst. The reaction mixture was heated to 120°C for 4.5 hours and then to 135°C for 0.5 hours to remove any remaining ammonia. After completion of the reaction, the resulting precipitate was filtered and rinsed three times with ethanol, then recrystallized from methanol. The precipitate was filtered and dried to yield compound 23-3 (1.40 g, 76.2% yield, MALDI-TOF-MS: 1147.91).

[0169] Synthesis of compound 23-4:

[0170] Compound 23-3 (1.30 g, 1.13 mmol), malononitrile (0.15 g, 2.27 mmol) and sodium acetate (0.19 g, 2.27 mmol) were added to a 100 mL round-bottom flask, the nitrogen atmosphere was replaced three times, 30 mL of ethanol was added, and the mixture was heated to 40°C for 4 h. Concentrated hydrochloric acid was added to precipitate the solid, and the precipitate was filtered, washed three times with deionized water and three times with petroleum ether, and purified by column chromatography (DCM as eluent) to give compound 23-4 (0.92 g, 68.1% yield, MALDI-TOF-MS: 1195.62).

[0171] Synthesis of compound 23-5:

[0172] Compound 23-4 (800 mg, 0.67 mmol) was weighed into a 100 mL three-necked flask. 15 mL of 1,2-dichloroethane was added, the atmosphere was replaced with nitrogen three times, and the mixture was cooled to approximately 0°C in an ice-water bath. Separately, 20 mL of DMF and 3 mL of phosphorus oxychloride were thoroughly mixed in a 100 mL beaker and slowly added dropwise to the reaction flask under nitrogen. After the addition was complete, the mixture was heated to 90°C and reacted for 2 h. After the reaction was completed, the mixture was cooled to room temperature and then poured into ice-cold NaOH solution. Extraction was performed with DCM and dried over anhydrous Na2SO4. The solvent was removed and the mixture was purified by column chromatography using a PE:DCM ratio of 2:1 (volume ratio) to afford compound 23-5 (0.69 g, 82.3% yield, MALDI-TOF-MS: 1251.83).

[0173] Synthesis of compound (23):

[0174] Compound 23-5 (100 mg, 0.080 mmol), compound A1 (92 mg, 0.399 mmol), and dry toluene (8 mL) were dissolved in a two-necked flask. After nitrogen was replaced three times, boron trifluoride etherate (0.3 mL) and acetic anhydride (0.3 mL) were added and reacted at room temperature for 20 min. After the reaction, the mixture was added dropwise to methanol for precipitation. The crude product was filtered and purified by column chromatography using a 1:1 (volume ratio) eluent of PE:DCM to obtain compound (23) (91 mg, 67.8% yield, MALDI-TOF-MS: 1676.35).

[0175] Synthesis Example 8: Synthesis of Compound (25)

[0176]

[0177] Compound 23-5 (100 mg, 0.080 mmol), compound A5 (125 mg, 0.399 mmol), and dry toluene (8 mL) were dissolved in a two-necked flask. After nitrogen was replaced three times, boron trifluoride etherate (0.3 mL) and acetic anhydride (0.3 mL) were added and reacted at room temperature for 20 min. After the reaction, the mixture was added dropwise to methanol for precipitation. The crude product was filtered and purified by column chromatography using a 1:1 (volume ratio) eluent to afford compound (25) (108 mg, 73.3% yield, MALDI-TOF-MS: 1841.97).

[0178] Synthesis Example 9: Synthesis of Compound (40)

[0179]

[0180] Synthesis of compound 40-2:

[0181] Compound 40-1 (2.40 g, 2.97 mmol), K2CO3 (4.1 g, 29.7 mmol), and KI (4.9 g, 29.7 mmol) were dissolved in 30 mL of DMF and purged three times. (3-(Bromomethyl)hexane-1,7-diyl)diphenyl (9.23 g, 26.73 mmol) was then added, and the mixture was heated to 110°C and stirred overnight. After completion of the reaction, the mixture was extracted with DCM, the DMF was washed off with multiple extractions, and the mixture was dried over anhydrous Na2SO4. Purification by column chromatography with PE:DCM = 10:1 (volume ratio) afforded compound 40-2 (2.26 g, 58.2% yield, MALDI-TOF-MS: 1335.98).

[0182] Synthesis of compound 40-3:

[0183] Compound 40-2 (2.0 g, 1.5 mmol) was added to a 100 mL three-necked flask, and 20 mL of tetrahydrofuran was added with stirring to dissolve. The nitrogen atmosphere was replaced three times, and the temperature was lowered to 0°C. 14 mL of lithium aluminum hydride (2.5 M) was added, and the temperature was raised to 80°C for 18 h. The mixture was then extracted with water and dichloromethane, dried over Na2SO4, and concentrated to afford compound 40-3 (1.52 g, 77.5% yield, MALDI-TOF-MS: 1308.75).

[0184] Synthesis of compound 40-4:

[0185] Compound 40-3 (1.50 g, 1.15 mmol) and urea (0.21 g, 3.51 mmol) were added to a 100 mL round-bottom flask, dissolved in a 25% THF / water solution, and stirred vigorously. One to two drops of acetic acid were then added as a catalyst. The reaction mixture was heated to 120°C for 4.5 hours, then to 135°C for 0.5 hours to remove any remaining ammonia. After completion of the reaction, the resulting precipitate was filtered, rinsed three times with ethanol, and then recrystallized from methanol. The precipitate was filtered and dried to afford compound 40-4 (1.32 g, 86.2% yield, MALDI-TOF-MS: 1331.87).

[0186] Synthesis of compound 40-5:

[0187] Compound 40-4 (1.30 g, 0.97 mmol), malononitrile (0.13 g, 2.00 mmol), and sodium acetate (0.16 g, 2.00 mmol) were added to a 100 mL round-bottom flask. The atmosphere was purged with nitrogen three times, and 30 mL of ethanol was added. The mixture was heated to 40°C and reacted for 4 h. Concentrated hydrochloric acid was added to precipitate a solid. The precipitate was filtered, washed three times with deionized water and three times with petroleum ether, and purified by column chromatography (DCM as eluent) to afford compound 40-5 (0.95 g, 71.7% yield, MALDI-TOF-MS: 1366.64).

[0188] Synthesis of compound 40-6:

[0189] Compound 40-5 (800 mg, 0.59 mmol) was weighed into a 100 mL three-necked flask. 15 mL of 1,2-dichloroethane was added, the atmosphere was replaced with nitrogen three times, and the mixture was cooled to approximately 0°C in an ice-water bath. Separately, 20 mL of DMF and 3 mL of phosphorus oxychloride were thoroughly mixed in a 100 mL beaker and slowly added dropwise to the reaction flask under nitrogen. After the addition was complete, the mixture was heated to 90°C and reacted for 2 h. After the reaction was completed, the mixture was cooled to room temperature and then poured into ice-cold NaOH solution. Extraction was performed with DCM and dried over anhydrous Na2SO4. The solvent was removed and the mixture was purified by column chromatography using a PE:DCM ratio of 2:1 (volume ratio) to afford compound 40-6 (0.64 g, 77.0% yield, MALDI-TOF-MS: 1436.22).

[0190] Synthesis of compound (40):

[0191] Compound 40-6 (100 mg, 0.07 mmol), compound A1 (82 mg, 0.355 mmol), and dry toluene (8 mL) were dissolved in a two-necked flask. After nitrogen was replaced three times, boron trifluoride etherate (0.3 mL) and acetic anhydride (0.3 mL) were added and reacted at room temperature for 20 min. After the reaction, the mixture was added dropwise to methanol for precipitation. The crude product was filtered and purified by column chromatography using a PE:DCM = 1:1 (volume ratio) eluent to obtain compound (40) (71 mg, 54.6% yield, MALDI-TOF-MS: 1860.46).

[0192] Organic Photovoltaic Cell (OPV) Device Examples

[0193] refer to Figure 1 Device embodiment 1 includes a substrate 101, an anode layer 102, an anode buffer layer 103, a photoactive layer 104, a cathode buffer layer 105, and a cathode layer 106 stacked in sequence; wherein the materials of the anode layer 102, the anode buffer layer 103, the photoactive layer 104, the cathode buffer layer 105, and the cathode layer 106 are, in sequence: indium tin oxide ITO / CBz-2Ph / photoactive layer material / PNDIT-F3N / Ag

[0194] Device Example 1

[0195] The preparation method comprises the following steps:

[0196] 1) ITO substrate cleaning

[0197] 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.

[0198] 2) Preparation of anode buffer layer 103

[0199] Subsequently, an anode buffer layer material CBz-2Ph (0.5 mg / mL, isopropyl alcohol solution) was spin-coated on the ITO substrate at a rotation speed of 3000 rpm for 30 seconds, and then annealed at 100° C. for 5 minutes to obtain the anode buffer layer 103 .

[0200] 3) Preparation of Photoactive Layer 104

[0201] In a glove box (inert gas atmosphere), the photoactive layer material solvent is evenly spin-coated on the anode buffer layer 103 at a rotation speed of 1800-4000 rpm to obtain a photoactive layer 104 with a total thickness of about 100 nm.

[0202] The photoactive layer material solvent is prepared by dissolving a donor material and an acceptor material in chloroform to a total concentration of 11 mg / mL, and adding 0.5% by volume of DIO as an additive. The donor material in the photoactive layer material is selected from polymer D18, and the acceptor material is selected from compound (H-4) and compound (1). The mass ratio of D18:compound (H-4):compound (1) is 1:1.1:0.1.

[0203] 4) Preparation of cathode buffer layer 105

[0204] After thermal annealing 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 0.5 mg / mL) was evenly spin-coated on the photoactive layer 104 at a spin coating speed of 3000 rpm for 30 seconds to obtain the cathode buffer layer 105.

[0205] 5) Preparation of cathode layer 106

[0206] In high vacuum (1×10 -6 Ag was evaporated onto the cathode buffer layer 105 at a pressure of 100 mbar to form a cathode layer 106 with a thickness of about 100 nm.

[0207] 6) Packaging

[0208] The devices were encapsulated with UV-curable resin in a nitrogen glove box.

[0209]

[0210] Device Examples 2-9

[0211] The preparation methods of device examples 2-9 are the same as those of device example 1, except that the choice of acceptor material in the photoactive layer is different. Specifically, the acceptor material compound (1) in device example 1 is replaced by compound (5), compound (15), compound (17), compound (20), compound (21), compound (23), compound (25), and compound (40), respectively. See Table 1 for details.

[0212] Device Comparative Example 1

[0213] The preparation method of device comparative example 1 is the same as that of device example 1, except that the preparation method of the photoactive layer is different, as follows:

[0214] In a glove box (inert gas atmosphere), the photoactive layer material solvent is evenly spin-coated on the anode buffer layer 103 at a rotation speed of 1800-4000 rpm to obtain a photoactive layer 104 with a total thickness of about 100 nm.

[0215] The photoactive layer material solvent is prepared by dissolving the donor material and the acceptor material in chloroform to a total concentration of 11 mg / mL and adding 0.5% by volume of DIO as an additive. The donor material in the photoactive layer material is selected from polymer D18, and the acceptor material is selected from compound (H-4). The mass ratio of D18 to compound (H-4) is 1:1.2.

[0216] The performance of the prepared organic photovoltaic device was tested. Under the irradiation of standard light from a solar simulator (AM 1.5G), the battery current-voltage curve was tested and the photoelectric conversion efficiency was calculated; as shown in Table 1.

[0217] Table 1

[0218]

[0219] As can be seen from the data in Table 1, compared to the comparative examples of devices that do not include the acceptor material described in the present invention, adding the non-fullerene acceptor material of the present invention to the D18 and compound (H-4) system can effectively improve the device's photoelectric conversion efficiency. The reason is that the cyano group can effectively regulate the molecular stacking and molecular energy levels of the non-fullerene acceptor material. By introducing a dicyano structure into the large fused ring core of the non-fullerene acceptor material, the present invention, when used as a third component in a binary device system, can achieve material interaction, construct an ideal bicontinuous phase separation network structure, and achieve efficient charge transfer. On the other hand, it can reduce the energy loss of the system and increase the open-circuit voltage of the device. Therefore, its application in organic photovoltaic devices can effectively improve the device's photoelectric conversion efficiency.

[0220] Furthermore, it can be seen from the data in Table 1 that the photoelectric conversion efficiency of device examples 1-4 and device example 6 exceeds 19%, which is much better than that of the binary system, indicating that compound (1), compound (5), compound (15), compound (17) and compound (21) and the binary device system D18 and compound (H-4) can form a better synergistic effect, thereby achieving better device photoelectric performance.

[0221] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will appreciate that other variations or modifications can be made based on the above description. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.

Claims

1. A non-fullerene acceptor material, characterized in that: It has the structure shown in the following formula (I): in: Each occurrence of Z is independently selected from S or Se; Each occurrence of R1 is independently selected from -H, -D, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, a a A substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or R a a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms; Each occurrence of R2 is independently selected from R b a substituted or unsubstituted alkyl group having 8 to 30 carbon atoms; Each occurrence is independently selected from wherein each occurrence of M is independently selected from O or C(CN)2; Each occurrence is independently selected from the c A substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or R c A substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms; * indicates the attachment site; R a each occurrence is independently selected from alkyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, or alkylthio having 1 to 20 carbon atoms; R b Each occurrence is independently selected from one or a combination of at least two of -D, -F, -Cl, an aromatic group having 6 to 10 carbon atoms, or a heteroaromatic group having 5 to 10 ring atoms; R c Each occurrence is independently selected from -D, -F, -Cl, -Br, -I, -CF3, -CN, a straight chain alkyl group having 1 to 10 carbon atoms, a branched chain alkyl group having 3 to 10 carbon atoms, a straight chain alkoxy group having 1 to 10 carbon atoms, or a branched chain alkoxy group having 3 to 10 carbon atoms.

2. The non-fullerene acceptor material according to claim 1, characterized in that described Each occurrence is independently selected from the following groups: in: m1 is selected from 0, 1, 2, 3 or 4; m2 is selected from 0, 1, 2, 3, 4, 5 or 6; m2 is selected from 0, 1 or 2; # represents a fusion site, which is selected from carbon atoms.

3. The non-fullerene acceptor material according to claim 1, characterized in that described Selected from any of the following groups:

4. The non-fullerene acceptor material according to any one of claims 1 to 3, characterized in that: Each occurrence of R1 is independently selected from -H, -D, a straight-chain alkyl group having 1 to 20 carbon atoms, a branched-chain alkyl group having 3 to 20 carbon atoms, a cyclic alkyl group having 3 to 20 carbon atoms, a straight-chain alkoxy group having 1 to 20 carbon atoms, a branched-chain alkoxy group having 3 to 20 carbon atoms, a cyclic alkoxy group having 3 to 20 carbon atoms, a straight-chain alkylthio group having 1 to 20 carbon atoms, a branched-chain alkylthio group having 3 to 20 carbon atoms, a cyclic alkylthio ... straight-chain alkylthio group having 3 to 20 carbon atoms, a branched-chain alkylthio group having 3 to 20 carbon atoms, a straight-chain alkylthio group having 3 to 20 carbon atoms, a branched-chain alkylthio group having 3 to 20 carbon atoms, a branched-chain alkylthio group having 3 to 20 carbon atoms, a branched-chain alkylthio group having 3 to 20 carbon atoms, a branched-chain a A substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or R a a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms; Preferably, R a Each occurrence is independently selected from a straight chain alkyl group having 1 to 10 carbon atoms, a branched chain alkyl group having 3 to 10 carbon atoms, a straight chain alkoxy group having 1 to 10 carbon atoms, a branched chain alkoxy group having 3 to 10 carbon atoms, a straight chain alkylthio group having 1 to 10 carbon atoms, or a branched chain alkylthio group having 3 to 10 carbon atoms.

5. The non-fullerene acceptor material according to claim 1, characterized in that Each occurrence of R1 is independently selected from -H, -D, or the following groups: *-C8H 17 、*-C9H 19 、*-C 11 H 23 、 *-OC 11 H 23 、*-OC 10 H 21 、*-OC 12 H 25 、*-OC9H 19 、 *-SC 11 H 23 、*-SC 10 H 21 、*-SC 12 H 25 、*-SC9H 19 、 6. The non-fullerene acceptor material according to claim 1, characterized in that Each occurrence of R2 is independently selected from R b a substituted or unsubstituted alkyl group having 8 to 30 carbon atoms; said R b is selected from phenyl, phenyl substituted by one or more Fs.

7. The non-fullerene acceptor material according to claim 1, characterized in that The non-fullerene acceptor material is selected from any of the following structures:

8. An organic compound, characterized in that: Contains an organic compound represented by general formula (II): in: Each occurrence of Z is independently selected from S or Se; Each occurrence of R1 is independently selected from -H, -D, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylthio group having 1 to 30 carbon atoms, a a A substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or R a a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms; Each occurrence of R2 is independently selected from R b a substituted or unsubstituted alkyl group having 8 to 30 carbon atoms; R a Each occurrence is independently selected from alkyl having 1 to 20 carbon atoms, alkoxy having 1 to 20 carbon atoms, or alkylthio having 1 to 20 carbon atoms; R b Each occurrence is independently selected from one or a combination of at least two of -D, -F, -Cl, an aromatic group having 6 to 10 carbon atoms, or a heteroaromatic group having 5 to 10 ring atoms.

9. A mixture, characterized in that The mixture comprises the non-fullerene acceptor material according to any one of claims 1 to 7.

10. The mixture according to claim 9, characterized in that The mixture comprises a first compound and a second compound, wherein the first compound is selected from the non-fullerene acceptor material according to any one of claims 1 to 7, and the second compound is selected from the structure described in formula (III): in: Each occurrence of Y is independently selected from S or Se; Each occurrence of W is independently selected from S or Se; Each occurrence of R3 is independently selected from -H, -D, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkylthio group having 1 to 20 carbon atoms, a d A substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or R d a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms; R d Each occurrence is independently selected from an alkyl group having 3 to 20 carbon atoms, an alkoxy group having 3 to 20 carbon atoms, or an alkylthio group having 3 to 20 carbon atoms; R4, at each occurrence, is independently selected from an alkyl group having 8 to 20 carbon atoms; Each occurrence of R5 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CF3, -CN, a straight chain alkyl group having 1 to 10 carbon atoms, a branched chain alkyl group having 3 to 10 carbon atoms, a straight chain alkoxy group having 1 to 10 carbon atoms, or a branched chain alkoxy group having 3 to 10 carbon atoms.

11. An organic photovoltaic device, characterized in that The organic photovoltaic device comprises a cathode, an anode, and a photoactive layer located between the cathode and the anode. The acceptor material of the photoactive layer comprises the non-fullerene acceptor material according to any one of claims 1 to 7 or the mixture according to claim 9 or 10.

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