Organic compound and organic electronic device thereof

Abstract

The invention relates to the field of organic photoelectric materials, in particular to an organic compound and an organic electronic device thereof. The organic compound provided by the invention has a structure as shown in a general formula (I), can be applied to organic electronic devices as an acceptor material, and shows efficient photoelectric properties when being matched with a proper donor material.

Description

Technical Field

[0001] This invention relates to the field of organic optoelectronic materials, specifically to an organic compound and its organic electronic device. Background Technology

[0002] Organic photovoltaics have attracted widespread attention from researchers due to their advantages such as light weight, solution-processability, low cost, and easy adjustment of material energy levels and band gaps. Semi-transparent organic photovoltaic devices (STOPVs) are functional devices that integrate both photoelectric conversion and photon transmission. They can absorb near-infrared photons and convert them into electrical energy, while also transmitting visible light photons, achieving a visible effect. Furthermore, due to the absorption of near-infrared sunlight, STOPVs can also achieve special functions such as heat insulation, and have potential applications in vehicles, buildings, and agricultural greenhouses.

[0003] The working principle of STOPV consists of two parts: 1) absorbing photons and converting them into electrical energy; 2) transmitting some visible light to achieve semi-transparent properties. The process of absorbing photons and converting them into electrical energy is as follows: a) the active layer absorbs photons and generates excitons; b) the excitons diffuse to the donor / acceptor material interface; c) the energy level difference between the donor / acceptor materials provides the driving force for exciton dissociation, causing the excitons to dissociate into free charges (holes and electrons) at the donor / acceptor interface; d) under the action of the built-in electric field, the free electrons and free holes move towards the anode and cathode of the battery, respectively, and are collected by the corresponding electrodes, thereby forming a photocurrent.

[0004] The donor and acceptor materials for the STOPV active layer mainly focus on polymer donor-small molecule acceptor blends, with small molecule acceptors comprising two main categories: fullerenes and non-fullerene acceptor molecules. Since its development in 2007, the photoelectric conversion efficiency of semi-transparent organic photovoltaic cells using fullerene acceptors has been only around 7%. This is because fullerenes exhibit weak absorption in the visible and near-infrared regions, preventing an increase in short-circuit current. Secondly, organic photovoltaic cells based on fullerene acceptors suffer from significant non-radiative losses, resulting in excessive open-circuit voltage losses. Furthermore, the energy levels and chemical structures of fullerene molecules are difficult to control, and their strong aggregation characteristics greatly limit the development of semi-transparent organic solar cells based on fullerenes. In contrast, non-fullerene acceptors have the following advantages: 1) flexible and diverse molecular structure design; 2) easily tunable molecular orbital energy levels; 3) absorption spectra covering the visible to near-infrared regions. These characteristics enable continuous color adjustment in non-fullerene acceptor semi-transparent organic photovoltaic cells, playing a crucial role in promoting the development of semi-transparent organic photovoltaic cell technology. However, the performance of current semi-transparent organic photovoltaic cell devices is still relatively low. Therefore, it is necessary to continuously develop materials for each functional layer to promote the development and industrialization of semi-transparent organic photovoltaic technology. Summary of the Invention

[0005] Based on this, the present invention aims to provide a novel active layer acceptor material that can be used in semi-transparent organic photovoltaic devices to achieve high photoelectric conversion efficiency of organic photovoltaic cells.

[0006] This invention provides an organic compound having a structure as shown in general formula (I):

[0007]

[0008] in:

[0009] Y is selected from O, S, or Se;

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

[0011] W is selected from O, S, or Se;

[0012] Each time R1 appears, it is independently selected from a straight-chain alkyl group having 1-30 carbon atoms, or a branched alkyl group having 3-30 carbon atoms;

[0013] Each time R2 appears, it is independently selected from a straight-chain alkoxy group having 1-30 carbon atoms, or a branched-chain alkoxy group having 3-30 carbon atoms;

[0014] Each time R3 appears, it is independently selected from a straight-chain alkyl group having 1-30 carbon atoms, or a branched alkyl group having 3-30 carbon atoms;

[0015] Each occurrence of R4 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, or -CF3;

[0016] Each time M appears, it is independently selected from O or C(CN)2;

[0017] Ar1 and Ar2 each time they appear, they are independently selected from substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms, or substituted or unsubstituted aromatic groups having 6-20 carbon atoms.

[0018] The term "substituted or unsubstituted" means that the defined group is not substituted, or is substituted by one or more substituents R, wherein R is selected from -D, -F, -Cl, -Br, -I, -CF3, -CN, straight-chain alkyl having 1 to 10 carbon atoms, branched-chain alkyl having 3 to 10 carbon atoms, straight-chain alkoxy having 1 to 10 carbon atoms, or branched-chain alkoxy having 3 to 10 carbon atoms.

[0019] The present invention further provides a mixture comprising the organic compound as described above.

[0020] The present invention further provides an organic electronic device that protects a cathode, an anode, and an active layer located between the cathode and the anode, the active layer comprising the organic compound or mixture described above, or prepared from the composition described above.

[0021] Beneficial effects:

[0022] This invention provides an organic compound based on the A-π-D'AD'-π-A configuration, wherein by introducing This effectively improved the molecular absorption spectrum, energy levels, and molecular morphology. Specifically, the introduction of π units extended the conjugation length of the compound, thereby broadening its absorption wavelength; furthermore, The energy levels of the compound can be tuned, thereby enhancing the dissociation of excitons in the active layer. Furthermore, the non-covalent interactions (O-S, F-S, etc.) between adjacent groups of the compound improve the planar configuration of the molecule, resulting in suitable nanoscale phase separation dimensions in the blend film. Particularly when paired with the polymer donor material PCE10, the shared functional groups enhance miscibility, promoting effective charge transport in the blend. In summary, the organic compounds described in this invention, when used as acceptors in organic electronic devices, particularly semi-transparent organic photovoltaic devices, exhibit excellent photoelectric properties. Attached Figure Description

[0023] Figure 1 Schematic diagram of a semi-transparent organic photovoltaic device.

[0024] Wherein: 101-substrate, 102-cathode, 103-cathode buffer layer, 104-photoactive layer, 105-anode buffer layer, 106-anode. Detailed Implementation

[0025] To make the objectives, technical solutions, and effects of this application clearer and more explicit, the following provides a further detailed description of this application. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the scope of this application. All other embodiments obtained by those skilled in the art based on the described embodiments of the present invention without inventive effort are within the scope of protection of this invention.

[0026] The terms "and / or," "or / and," and "and / or" as used herein include any one of two or more of the related listed items, as well as any and all combinations of the related listed items. These arbitrary and all combinations include any two related listed items, any more related listed items, or a combination of all related listed items. It should be noted that when at least three items are connected by at least two conjunctions selected from "and / or," "or / and," and "and / or," it should be understood that in this application, the technical solution undoubtedly includes technical solutions connected by "logical AND," and also undoubtedly includes technical solutions connected by "logical OR." For example, "A and / or B" includes three parallel solutions: A, B, and A+B. For example, the technical solution of "A, and / or, B, and / or, C, and / or, D" includes any one of A, B, C, and D (that is, a technical solution that is connected by "logical OR"), as well as any and all combinations of A, B, C, and D, that is, combinations of any two or three of A, B, C, and D, and also combinations of all four of A, B, C, and D (that is, a technical solution that is connected by "logical AND").

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

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

[0029] In this invention, when the same group contains multiple substituents with the same symbol, the substituents can be the same as or different from each other, for example... The six R's on the benzene ring can be the same or different from each other.

[0030] In this invention, "substitution" means that one or more hydrogen atoms in the substituent are replaced by the substituent.

[0031] In this invention, "ring atom number" refers to the number of atoms in the ring itself of a structural compound (e.g., monocyclic compound, fused-ring compound, cross-linked compound, carbocyclic compound, heterocyclic compound) obtained by atomic bonding to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The same applies to the "ring atom number" described below unless otherwise specified. In aromatic groups, the ring atom number is the same as the carbon atom number; in heteroaromatic groups, the ring atom number is the carbon atom number plus the heteroatom number; for example, the ring atom number of a benzene ring is 6, the ring atom number of a naphthalene ring is 10, the ring atom number of a quinoline ring is 10, the ring atom number of a thiophene group is 5, and the ring atom number of a thiophene is 8.

[0032] In this invention, "aromatic group" refers to any optional functional group or substituent derived from an aromatic carbon ring. The aromatic group can be a monocyclic aryl (e.g., phenyl) or a polycyclic aryl; in other words, the aromatic group can be a monocyclic aromatic group, a fused-ring aromatic group, two or more monocyclic aromatic groups conjugated by carbon-carbon bonds, a monocyclic aromatic group and a fused-ring aromatic group conjugated by carbon-carbon bonds, or two or more fused-ring aromatic groups conjugated by carbon-carbon bonds. That is, unless otherwise stated, two or more aromatic groups conjugated by carbon-carbon bonds can also be considered as the aromatic group of this application. Preferably, the aromatic group is selected from aromatic groups having 6-30 carbon atoms; further, it is selected from aromatic groups having 6-20 carbon atoms; further, it is selected from aromatic groups having 6-10 carbon atoms; the aromatic group includes, but is not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthraceneyl, phenanthrene, fluoranyl, triphenylene, pyrene, perylene, tetraphenyl, fluorenyl, dinaphthylphenyl, acenaphthyl, and their derivatives.

[0033] In this invention, a "heteroaromatic group" refers to a heteroaromatic ring or its derivative containing one, two, three, four, five, six or more heteroatoms, wherein the heteroatoms can be at least one of B, O, N, P, Si, Se and S. The heteroaromatic group can be a monocyclic heteroaryl or a polycyclic heteroaryl. The term "heteroaromatic group" as used herein also includes groups formed by the fusion of one or more heteroaromatic groups with one or more aromatic rings, aliphatic rings or heterocycles. Preferably, the heteroaromatic group is selected from those having 5-30 ring atoms; further, it is selected from those having 5-20 ring atoms; and further, it is selected from those having 5-10 ring atoms. Heteroaromatic groups include, but are not limited to: thiophene, furanyl, pyrrolyl, diazolyl, triazolyl, imidazolyl, pyridinyl, bipyridinyl, pyrimidinyl, triazinyl, acridineyl, pyridazinyl, quinolinyl, isoquinolinyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridinylpyrimidinyl, pyridinylpyrazinyl, benzothiophene, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrol, thienopyrrol, thienopyrrol, furanol, furanol, thienofuranyl, benzoisoxazolyl, benzoisothiazolyl, benzoimidazolyl, o-diazonyl, phenanthridine, primidyl, quinazolinone, dibenzothiophene, dibenzofuranyl, carbazole and their derivatives.

[0034] In this invention, the number of carbon atoms in a straight-chain alkyl group can be 1 to 30, 1 to 20, 1 to 16, 1 to 10, or 1 to 6. The number of carbon atoms in a branched-chain alkyl group can be 3 to 30, 3 to 20, 3 to 16, 3 to 10, or 3 to 6. Non-limiting examples of straight-chain alkyl groups include methyl (-CH3), ethyl (-C2H5), n-propyl (-C3H7), n-butyl (-C4H9), and n-pentyl (-C5H9). 11), n-hexyl (-C6H) 13 ), heptyl (-C7H) 15 ), n-octyl (-C8H) 17 ), non-nonyl (-C9H) 19 -C 10 H 21 -C 11 H 23 -C 12 H 25 -C 13 H 27 -C 14 H 29 -C 15 H 31 -C 16 H 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.

[0035] The term "alkoxy" refers to a group with the structure "-O-alkyl", that is, an alkyl group as defined above that is attached to other groups via an oxygen atom. The straight-chain alkoxy means that the alkyl group in "-O-alkyl" is selected from straight-chain alkyl groups, wherein the number of carbon atoms in the straight-chain alkyl group can be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the branched-chain alkoxy means that the alkyl group in "-O-alkyl" is selected from branched-chain alkyl groups, wherein the number of carbon atoms in the branched-chain alkyl group can be 3 to 20, 3 to 16, 3 to 10, or 3 to 6.

[0036] The term "alkoxythio" refers to a group with the structure "-S-alkyl", that is, an alkyl group as defined above that is attached to other groups via a sulfur atom. The straight-chain alkoxythio group indicates that the alkyl group in the "-S-alkyl" is selected from straight-chain alkyl groups, wherein the number of carbon atoms in the straight-chain alkyl group can be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the branched-chain alkoxythio group indicates that the alkyl group in the "-S-alkyl" is selected from branched-chain alkyl groups, wherein the number of carbon atoms in the branched-chain alkyl group can be 3 to 20, 3 to 16, 3 to 10, or 3 to 6.

[0037] In this invention, when no linking site is specified in the group, it means that any linkable site in the group is selected as the linking site.

[0038] In this invention, the phrase "independently selected" means that when one or more groups appear simultaneously and in multiple places in the compound, they are all independently selected and can be the same or different.

[0039] In this invention, the single bond connecting the substituents extends through the corresponding ring, indicating that the substituent can be connected to any position on the ring, for example... R is attached to any substituted site on the benzene ring.

[0040] In describing the structural elements of the present invention, the terms "comprising" or "including" or similar terms used in the present invention mean that the device or material preceding the word covers the device or material listed after the word and its equivalents, but does not exclude other devices or materials.

[0041] In the description of this invention, it should be understood that the terms "upper," "lower," "between layers," etc., indicate the orientation or positional relationship based on the orientation or positional relationship shown in the drawings, or the orientation or positional relationship commonly used when organic solar cell devices are in use, or the orientation or positional relationship commonly understood by those skilled in the art. They are only used to facilitate the description of this invention and to simplify the description, and are not intended to indicate or imply that the device or element referred to must have a specific orientation, or be constructed and operated in a specific orientation. Therefore, they should not be construed as limiting this invention.

[0042] The terms “combinations thereof,” “any combination thereof,” “any combination thereof,” and “combination” used in this invention include all suitable combinations of any two, any three, or any three or more groups listed.

[0043] In this invention, terms such as "further," "even more," and "particularly" are used for descriptive purposes and to indicate differences in content, but should not be construed as limiting the scope of protection of this invention.

[0044] In this invention, "optionally," "optionally," and "optional" mean that they are optional, that is, they are selected from either "with" or "without." If multiple "options" appear in a technical solution, unless otherwise specified and there are no contradictions or mutual constraints, each "option" is independent.

[0045] In this invention, the technical features described in an open-ended manner include both closed-ended technical solutions composed of the listed features and open-ended technical solutions that include the listed features.

[0046] The first aspect of this invention relates to an organic compound having a structure as shown in general formula (I):

[0047]

[0048] in:

[0049] Y is selected from O, S, or Se;

[0050] Z is selected from O, S, or Se;

[0051] W is selected from O, S, or Se;

[0052] Each time R1 appears, it is independently selected from a straight-chain alkyl group having 1-30 carbon atoms, or a branched alkyl group having 3-30 carbon atoms;

[0053] Each time R2 appears, it is independently selected from a straight-chain alkoxy group having 1-30 carbon atoms, or a branched-chain alkoxy group having 3-30 carbon atoms;

[0054] Each time R3 appears, it is independently selected from a straight-chain alkyl group having 1-30 carbon atoms, or a branched alkyl group having 3-30 carbon atoms;

[0055] Each occurrence of R4 is independently selected from -H, -D, -F, -Cl, -Br, -I, -CN, or -CF3;

[0056] Each time M appears, it is independently selected from O or C(CN)2;

[0057] Ar1 and Ar2 each time they appear, they are independently selected from substituted or unsubstituted heteroaromatic groups having 5-20 ring atoms, or substituted or unsubstituted aromatic groups having 6-20 carbon atoms.

[0058] The term "substituted or unsubstituted" means that the defined group is not substituted, or is substituted by one or more substituents R, wherein R is selected from -D, -F, -Cl, -Br, -I, -CF3, -CN, straight-chain alkyl having 1 to 10 carbon atoms, branched-chain alkyl having 3 to 10 carbon atoms, straight-chain alkoxy having 1 to 10 carbon atoms, or branched-chain alkoxy having 3 to 10 carbon atoms.

[0059] In one embodiment, each occurrence of R4 is independently selected from -H or -F.

[0060] In one embodiment, the Selected from

[0061] In one embodiment, the Selected from

[0062] Furthermore, the organic compound has a structure as shown in general formula (II-1) or (II-2):

[0063]

[0064] In one embodiment, Y is selected from S or Se.

[0065] In one embodiment, Z is selected from S or Se.

[0066] In one embodiment, W is selected from S or Se.

[0067] In a specific embodiment, Y, Z and W are all selected from S.

[0068] In one embodiment, each occurrence of R1 is independently selected from branched alkyl groups having 3-20 carbon atoms.

[0069] In one embodiment, each occurrence of R1 is independently selected from branched alkyl groups having 8-12 carbon atoms.

[0070] Furthermore, each occurrence of R1 is independently selected from...

[0071] In an alternative embodiment, each occurrence of R2 is independently selected from straight-chain alkoxy groups having 1-20 carbon atoms or branched-chain alkoxy groups having 3-20 carbon atoms.

[0072] Furthermore, each occurrence of R2 is independently selected from straight-chain alkoxy groups having 1-10 carbon atoms or branched-chain alkoxy groups having 3-10 carbon atoms.

[0073] In a preferred embodiment, the organic compound has a structure as shown in general formula (III):

[0074]

[0075] in:

[0076] Each time R4 appears, it is independently selected from straight-chain alkyl groups having 1-20 carbon atoms or branched alkyl groups having 3-20 carbon atoms.

[0077] Furthermore, each occurrence of R4 is independently selected from straight-chain alkyl groups having 1-10 carbon atoms or branched alkyl groups having 3-10 carbon atoms.

[0078] In one embodiment, each occurrence of R3 is independently selected from straight-chain alkyl groups having 1-10 carbon atoms or branched alkyl groups having 3-10 carbon atoms.

[0079] Preferably, each occurrence of R3 is independently selected from methyl, ethyl, and -C6H. 13 -C8H 17 -C4H9

[0080] In one embodiment, each occurrence of Ar1 and Ar2 is independently selected from substituted or unsubstituted heteroaromatic groups having 5-10 ring atoms, or substituted or unsubstituted aromatic groups having 6-10 carbon atoms.

[0081] Furthermore, each occurrence of Ar1 and Ar2 is independently selected from any of the following groups:

[0082]

[0083] in:

[0084] 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;

[0085] # indicates a fusion site, which is selected from carbon atoms.

[0086] In one embodiment, R is selected from -D, -F, -Cl, -Br, -I, -CF3, -CN, methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, or methoxy.

[0087] Furthermore, the aforementioned Independently selected from the following structures:

[0088]

[0089] In one specific embodiment, the organic compound according to the present invention is selected from, but is not limited to, the following structures:

[0090]

[0091]

[0092]

[0093] A second aspect of the present invention provides a mixture comprising the organic compound as described in the first aspect.

[0094] In an optional embodiment, the mixture further comprises another organic functional material selected from active layer donor materials.

[0095] Furthermore, the active layer donor material is selected from polymer donor materials. Specifically, the active layer donor material is selected from PM6, PM7, PBDB-T, D18, D18-Cl, PTQ10, PTQ11, PBQx-TCl, PBQx-TF, PCE10, etc., but is not limited to these.

[0096] A third aspect of the present invention provides a composition comprising an organic compound as described in the first aspect or a mixture as described in the second aspect, and at least one organic solvent.

[0097] The organic solvent is selected from, but not limited to: tetrahydronaphthalene, 1,5-dimethyltetrahydrofuran, methyltetrahydrofuran, decahydronaphthalene, chlorobenzene, o-dichlorobenzene, 1,2,4-trichlorobenzene, 1,4-dimethylnaphthalene, toluene, o-xylene, m-xylene, p-xylene, mesitylene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3,4-tetramethylbenzene, 1,2,3,5-tetramethylbenzene, 1,2,4,5-tetramethylbenzene, acetophenone, diphenyl ether, 2-methylthiophene, 3-methylthiophene, monochloromethane, dichloromethane, chloroform, dichloroethylene, trichloroethylene, 1,2-trichlorobenzene, etc. One or a mixture of two or more of the following: trichlorofluoroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2,2-tetrachloroethane, carbon tetrachloride, tetrahydrofuran, anisole, 2,4-dimethylanisole, 1-methylnaphthalene, morpholine, 1,4-dioxane, N-methylpyrrolidone, acetone, cyclopentanone, cyclohexanone, methyl ethyl ketone, ethyl acetate, n-butyl acetate, carbon disulfide, carbon tetrachloride, N,N-dimethylformamide, dimethylacetamide, dimethyl sulfoxide, indane, methyl benzoate, ethyl benzoate, acetonitrile, and hexamethylphosphoramide.

[0098] Preferably, the organic solvent is selected from, but not limited to, chlorobenzene, toluene, o-xylene, or chloroform.

[0099] In some alternative embodiments, the composition further includes additives for adjusting viscosity, adjusting film-forming properties, and improving adhesion.

[0100] In some alternative embodiments, the additive is selected from, but not limited to, 1,8-diiodooctane, diphenyl ether, anthracene, 1,4-diiodobenzene, 1,3-dibromo-5-chlorobenzene, 3,5-dichlorobromobenzene, 1-chloronaphthalene, and 1,3,5-tribromobenzene.

[0101] The fourth aspect of the present invention relates to an organic electronic device that protects a cathode, an anode, and a photoactive layer located between the cathode and the anode, the photoactive layer comprising an organic compound as described in the first aspect or a mixture as described in the second aspect, or prepared from a composition as described in the third aspect.

[0102] In one embodiment, the organic electronic device is selected from organic photovoltaic (OPV) devices or organic photodetectors (OPD).

[0103] In one specific embodiment, the organic electronic device is selected from organic photovoltaic devices.

[0104] In one embodiment, the photoactive layer material comprises an active layer donor material and an active layer acceptor material, wherein the active layer acceptor material is selected from organic compounds as described in the first aspect.

[0105] Furthermore, the active layer donor material is selected from, but not limited to, PM6, PM7, PBDB-T, D18, D18-Cl, PTQ10, PTQ11, PBQx-TCl, PBQx-TF, PCE10, etc.

[0106] The method for preparing the active layer material solution is as follows: the active layer donor material and acceptor material are dissolved in an organic solvent at a certain mass ratio, and the mixture is stirred until fully dissolved to obtain the photoactive layer solution. The meaning of the organic solvent is the same as described above.

[0107] The above solution is used to prepare the photoactive layer by printing or coating methods. These printing or coating methods can include, but are not limited to, inkjet printing, gravure printing, inkjet printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, torsional roller printing, offset printing, flexographic printing, rotary printing, spraying, brush coating, pad printing, and slot-loaded extrusion coating. Slot-loaded coating, spin coating, and inkjet printing are preferred.

[0108] The preferred mass ratio of the active layer donor material to the acceptor material in the organic solvent is 1:0.5 to 1:4; further, the preferred mass ratio of the photoactive layer donor material to the acceptor material in the organic solvent is 1:1 to 1:2.

[0109] The concentration of the photoactive layer donor material in the organic solvent is preferably 3 to 15 mg / mL; further, the concentration of the photoactive layer donor material in the organic solvent is preferably 4 to 10 mg / mL.

[0110] In one embodiment, the anode and cathode may be made of a transparent or translucent conductive material, but are not limited thereto. Conductive materials can be conductive metal oxides, such as indium oxide, zinc oxide, tin oxide, indium tin oxide (ITO), fluorine-doped tin oxide (FTO), gallium-doped zinc oxide (GZO), aluminum-doped zinc oxide (AZO), indium zinc oxide (IZO), and indium gallium zinc oxide (IGZO); conductive polymers, such as poly(3,4-ethylenedioxythiophene) / poly(4-styrene sulfonate) (PEDOT / PSS), polypyrrole, and polyaniline; conductive carbon materials, such as graphene and carbon nanotubes; nanoconductive materials, such as metal nanoparticles or nanowires; ultrathin metal layers that can maintain a certain degree of light transmittance and composite stacks containing them, such as metal layers formed of metals such as gold, platinum, silver, copper, cobalt, nickel, indium, or aluminum, or film stacks of alloys containing any of these metals; ultrathin metal layers that can maintain a certain degree of light transmittance and composite stacks with metal oxides, such as MoO3 and Ag composite stacks, MoO3 and Cu and Ag composite stacks, etc.

[0111] In one embodiment, the organic photovoltaic device comprises an anode, an anode buffer layer, a photoactive layer, a cathode buffer layer, and a cathode stacked sequentially, wherein the photoactive layer comprises an organic compound as described in the first aspect or a mixture as described in the second aspect, or is prepared from a composition as described in the third aspect.

[0112] Preferably, the cathode buffer layer material can be selected from low work function metal complexes, metal oxides, metal salts, etc., such as metal complexes of 8-hydroxyquinoline, complexes containing Alq3, metal complexes containing Liq, PEI-Zn, LiF, Ca, and titanium oxide (TiO2). x It can be zinc oxide (ZnO), cesium carbonate (Cs2CO3), etc.; it can also be polymer materials, such as PFN-Br or PFN or PDINN or PDINO or PNDIT-F3N-Br or PNDIT-F3N, etc., but is not limited to these.

[0113] The anode buffer layer material is selected from PEDOT:PSS and molybdenum oxide (MoO). x ), vanadium oxide (V₂O₅), nickel oxide (NiO), tungsten oxide (WO₂) x Preferably, x is selected from 2 or 3), small molecule self-assembled materials such as 2PACz, MeO-2PACz, etc., but not limited to these.

[0114] It should be noted that, in order to improve the performance of organic photovoltaic devices, the organic photovoltaic devices may further include other functional layers, including but not limited to charge blocking layers and charge transport layers.

[0115] Furthermore, the organic photovoltaic device also includes a substrate. In one embodiment, the substrate is disposed on one side of the anode and on a different side from the photoactive layer. In another embodiment, the substrate is disposed on one side of the cathode and on a different side from the photoactive layer.

[0116] In one embodiment, a substrate with excellent transparency, surface smoothness, ease of handling, and water resistance can be used as the substrate. Specifically, a glass substrate, a thin-film glass substrate, or a transparent plastic substrate can be used. The plastic substrate may include, but is not limited to, single-layer or multi-layer films such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK), polyimide (PI), parylene, etc., and substrates commonly used in organic solar cells may also be used.

[0117] In an optional embodiment, the organic photovoltaic device according to the present invention is a semi-transparent organic photovoltaic device.

[0118] In an alternative embodiment, the anode is selected from ITO, and the cathode is selected from ultrathin metal layers and composite stacks containing them, such as ultrathin silver layers or ultrathin gold and silver composite stacks.

[0119] In another alternative embodiment, the cathode is selected from ITO, and the anode is selected from ultrathin metal layers and composite stacks containing them, such as ultrathin silver layers or ultrathin gold and silver composite stacks.

[0120] The present invention also provides that the organic photovoltaic device is mainly used in outdoor photovoltaics, such as building photovoltaics, vehicle photovoltaics, agricultural photovoltaics and smart windows.

[0121] Synthesis Examples

[0122] The following embodiments are provided to facilitate a better understanding of the disclosure of this invention, but are not intended to limit it in any way. Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods, and the materials and reagents used are prior art and commercially available unless otherwise specified.

[0123] Synthesis Example 1: Synthesis of Compound (1)

[0124]

[0125] Synthesis of compound 1-a:

[0126] Accurately weigh 500 mg (1.3 mmol) of compound 4,7-dibromo-5,6-dinitrobenzo[c][1,2,5]thiadiazole and 1.4 g (2.99 mmol) of tributyl(4-(hexyloxy)thiophene-2-yl)stanane into 20 mL of toluene solution. After purging with nitrogen for 30 min, tetrakis(triphenylphosphine)palladium (15 mg, 0.013 mmol) was rapidly added. The mixture was heated to 100 °C and reacted for 3 hours. After the reactants had completely reacted, the mixture was cooled to room temperature, potassium fluoride solution was added, and stirring was continued for 20 min. The insoluble solids were filtered off, and the liquid phase was extracted with DCM. The organic phases were combined, dried over anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. The mixture was purified by column chromatography with PE:DCM = 3:1 (v / v). Approximately 635 mg of compound 1-a was obtained, yield: 82.7%. MS: 590.68.

[0127] Synthesis of compound 1-b:

[0128] Accurately weigh compound 1-a (600 mg, 1.02 mmol) and triphenylphosphine (1.3 g, 5.09 mmol) into a three-necked flask containing N-methylpyrrolidone (NMP, 8 mL). Stir the mixture overnight at 180 °C. After the reaction is complete, cool to room temperature, add potassium carbonate (703 mg, 5.09 mmol), potassium iodide (68 mg, 0.41 mmol), and 1-bromo-2-ethylhexane (2.0 g, 10.18 mmol), and heat to 85 °C, continuing the reaction for 8 h. After the starting material has completely reacted, quench with water and extract with DCM. Combine the organic phases and wash three times with water. Dry over anhydrous sodium sulfate, remove the solvent by vacuum distillation, and purify by column chromatography using PE:DCM = 4:1 (v / v) to give approximately 430 mg of compound 1-b, yield: 56.1%. MS: 751.13.

[0129] Synthesis of compound 1-c:

[0130] Under a nitrogen atmosphere, compound 1-b (420 mg, 0.56 mmol) and anhydrous THF (10 mL) were added to a 50 mL single-necked reaction flask. Butyllithium (0.5 mL, 2.5 mol / L) was added dropwise at -78 °C, and the mixture was stirred for 1 h. Then, trimethyltin chloride (250 mg, 1.23 mmol) was added, and the mixture was gradually brought to room temperature and stirred overnight. After the reactants had completely reacted, the mixture was quenched with water and extracted with EA. The combined organic phases were washed three times with water. After drying with anhydrous sodium sulfate, excess solvent was removed by vacuum distillation. The mixture was purified by column chromatography using PE:DCM = 6:1 (v / v) as the eluent, yielding approximately 522 mg of compound 1-c, yield: 86.6%. MS: 1076.24.

[0131] Synthesis of compound 1-d:

[0132] Under nitrogen protection, compound 1-c (150 mg, 0.14 mmol) and octyl-4-bromo-3-fluoro-6-carboxythiopheno[3,4-B]thiophene-2-carboxylate (147 mg, 0.35 mmol) were added to 15 mL of toluene and stirred. Nitrogen gas was bubbled through the mixture for 30 min, and then tetrakis(triphenylphosphine)palladium (1.6 mg, 0.0014 mmol) was rapidly added. The mixture was heated to 100 °C and reacted for 3 hours. After the reactants had completely reacted, the mixture was cooled to room temperature, and potassium fluoride solution was added. The mixture was stirred for another 20 min. The insoluble solids were filtered off, and the mixture was then extracted with DCM in the liquid phase. The organic phases were combined, dried over anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. The mixture was purified by column chromatography using PE:DCM at a volume ratio of 1:1. Approximately 143 mg of compound 1-d was obtained, with a yield of 71.3%. MALDI-TOF-MS: 1431.77.

[0133] Synthesis of compound (1):

[0134] Accurately weigh compound 1-d (115 mg, 0.08 mmol) and 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile (57 mg, 0.25 mmol) and dissolve them in 8 mL of toluene. Then add boron trifluoride diethyl ether (0.3 mL) and acetic anhydride (0.3 mL) and react at room temperature under a nitrogen atmosphere for 20 min. After the starting materials have completely reacted, pour the solution into methanol to precipitate the solid and filter. Purify by column chromatography with PE:DCM = 1:2 (volume ratio) as eluent to obtain approximately 103 mg of compound (1), yield: 69.4%. MALDI-TOF-MS: 1856.89.

[0135] Synthesis Example 2: Synthesis of Compound (3)

[0136]

[0137] Synthesis of compound 3-a:

[0138] Under a nitrogen atmosphere, 4,7-dibromo-5,6-dinitrobenzo[c][1,2,5]thiadiazole (500 mg, 1.3 mmol) and (4-butoxythiophene-2-yl)tributyltinane (1.3 g, 2.99 mmol) were added to 15 mL of anhydrous toluene and stirred. After purging with nitrogen for 30 min, tetrakis(triphenylphosphine)palladium (15 mg, 0.013 mmol) was rapidly added. The reaction was carried out at 100 °C for 3 h. After the starting materials had completely reacted, the mixture was cooled to room temperature, potassium fluoride solution was added, and stirring was continued for 20 min. The insoluble solids were filtered off, and the liquid phase was extracted with DCM. The organic phases were combined, dried over anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. The mixture was purified by column chromatography with PE:DCM = 4:1 (v / v) as the eluent, yielding approximately 558 mg of compound 3-a, yield: 80.3%. MS: 534.66.

[0139] Synthesis of compound 3-b:

[0140] Compound 3-a (540 mg, 1.01 mmol) and triphenylphosphine (1.3 g, 5.04 mmol) were accurately weighed into N-methylpyrrolidone (NMP, 8 mL), and stirred overnight at 180 °C. After the reaction was complete, the mixture was cooled to room temperature, and potassium carbonate (697 mg, 5.04 mmol), potassium iodide (66 mg, 0.40 mmol), and 1-bromo-2-ethylhexane (1.95 g, 10.08 mmol) were added. The temperature was raised to 85 °C, and the reaction was continued for 8 h. After the starting material had completely reacted, the mixture was quenched with water and extracted with DCM. The organic phases were combined, washed three times with water, dried over anhydrous sodium sulfate, and excess solvent was removed by vacuum distillation. The mixture was purified by column chromatography with PE:DCM = 5:1 (v / v) as the eluent, yielding approximately 359 mg of compound 3-b, yield: 51.1%. MS: 695.52.

[0141] Synthesis of compound 3-c:

[0142] Under a nitrogen atmosphere, compound 3-b (340 mg, 0.49 mmol) and anhydrous THF (10 mL) were added to a 50 mL single-necked flask. Butyllithium (0.4 mL, 2.5 mol / L) was added dropwise at -78 °C, and the mixture was stirred for 1 h. Then, trimethyltin chloride (210 mg, 1.07 mmol) was added, and the mixture was gradually brought to room temperature and stirred overnight. After the reactants had completely reacted, the mixture was quenched with water and extracted with EA. The combined organic phases were washed three times with water. After drying with anhydrous sodium sulfate, excess solvent was removed by vacuum distillation. The mixture was purified by column chromatography using PE:DCM = 8:1 (v / v) as the eluent, yielding approximately 415 mg of compound 3-c, in 83.0% yield. MS: 1020.48.

[0143] Synthesis of compound 3-d:

[0144] Under nitrogen protection, compound 3-c (153 mg, 0.15 mmol) and 2-ethylhexyl-4-bromo-3-fluoro-6-carboxythiopheno[3,4-b]thiophene-2-carboxylate (156 mg, 0.37 mmol) were added to 8 mL of toluene and stirred. After purging with nitrogen for 30 min, tetrakis(triphenylphosphine)palladium (1.7 mg, 0.0015 mmol) were rapidly added, and the mixture was heated to 100 °C and reacted for 3 hours. After the reactants had completely reacted, the mixture was cooled to room temperature, potassium fluoride solution was added, and stirring was continued for 20 min. The insoluble solids were filtered off, and the mixture was then extracted with DCM in the liquid phase. The organic phases were combined, dried over anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. The mixture was purified by column chromatography with PE:DCM = 2:1 (v / v) as the eluent, yielding approximately 152 mg of compound 3-d, with a yield of 73.7%. MALDI-TOF-MS: 1375.80.

[0145] Synthesis of compound (3):

[0146] Accurately weigh compound 3-d (138 mg, 0.10 mmol) and 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile (71 mg, 0.31 mmol) and dissolve them in 8 mL of toluene. Then add boron trifluoride diethyl ether (0.3 mL) and acetic anhydride (0.3 mL) and react at room temperature under a nitrogen atmosphere for 20 min. After the starting materials have completely reacted, pour the solution into methanol to precipitate the solid and filter. Purify by column chromatography with PE:DCM = 1:3 (volume ratio) as eluent to obtain approximately 102 mg of compound (3), yield: 56.7%. MALDI-TOF-MS: 1800.15.

[0147] Synthesis Example 3: Synthesis of Compound (4)

[0148]

[0149] Synthesis of compound 4-a:

[0150] Compound 1-c (300 mg, 0.28 mmol), 2-ethylhexyl-4-bromo-3-fluoro-6-carboxythiopheno[3,4-b]thiophene-2-carboxylate (295 mg, 0.70 mmol) was accurately weighed into 16 mL of anhydrous toluene. After purging with nitrogen for 30 min, tetrakis(triphenylphosphine) palladium (3.2 mg, 0.0028 mmol) was rapidly added. The mixture was heated to 100 °C and reacted for 3 hours. After the reactants had completely reacted, the mixture was cooled to room temperature, potassium fluoride solution was added, and the mixture was stirred for another 20 min. The insoluble solids were filtered off, and the liquid phase was extracted with DCM. The organic phases were combined, dried over anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. The mixture was purified by column chromatography with PE:DCM = 1:1 (v / v) as the eluent, yielding approximately 311 mg of compound 4-a, with a yield of 77.5%. MALDI-TOF-MS: 1432.26.

[0151] Synthesis of compound (4):

[0152] Accurately weigh compound 4-a (143 mg, 0.10 mmol) and 2-(5,6-dichloro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile (82 mg, 0.31 mmol) and dissolve them in 8 mL of toluene. Then add boron trifluoride diethyl ether (0.3 mL) and acetic anhydride (0.3 mL) and react at room temperature under a nitrogen atmosphere for 20 min. After the starting materials have completely reacted, pour the solution into methanol to precipitate the solid and filter. Purify by column chromatography with PE:DCM = 1:2 (volume ratio) as eluent to obtain approximately 140 mg of compound (4), yield: 72.8%. MALDI-TOF-MS: 1921.78.

[0153] Synthesis Example 4: Synthesis of Compound (5)

[0154]

[0155] Synthesis of compound 5-a:

[0156] Under a nitrogen atmosphere, 4,7-dibromo-5,6-dinitrobenzo[c][1,2,5]selenodiazole (500 mg, 1.16 mmol) and tributyl(4-(hexyloxy)thiophene-2-yl)stanane (1.4 g, 2.90 mmol) were added to 15 mL of anhydrous toluene. After stirring and purging with nitrogen for 30 min, tetrakis(triphenylphosphine)palladium (14 mg, 0.012 mmol) was rapidly added, and the reaction was carried out at 100 °C for 3 h. After the reactants had completely reacted, the mixture was cooled to room temperature, potassium fluoride solution was added, and stirring was continued for 20 min. The insoluble solids were removed by filtration, and the liquid phase was extracted with DCM. The organic phases were combined, dried over anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. The mixture was purified by column chromatography with PE:DCM = 4:1 (v / v) as the eluent, yielding approximately 543 mg of compound 5-a, yield: 73.4%. MS: 637.82.

[0157] Synthesis of compound 5-b:

[0158] Compound 5-a (523 mg, 0.82 mmol) and triphenylphosphine (1.1 g, 4.08 mmol) were accurately weighed into N-methylpyrrolidone (NMP, 8 mL), and stirred overnight at 180 °C. After the reaction was complete, the mixture was cooled to room temperature, and potassium carbonate (562 mg, 4.07 mmol), potassium iodide (55 mg, 0.33 mmol), and 1-bromo-2-ethylhexane (1.6 g, 8.16 mmol) were added. The mixture was heated to 85 °C and the reaction was continued for 8 h. After the starting material had completely reacted, the mixture was quenched with water and extracted with DCM. The organic phases were combined, washed three times with water, dried over anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. The mixture was purified by column chromatography with PE:DCM = 4:1 (v / v) as the eluent, yielding approximately 348 mg of compound 5-b, yield: 53.2%. MS: 798.29.

[0159] Synthesis of compound 5-c:

[0160] Under a nitrogen atmosphere, compound 5-b (327 mg, 0.41 mmol) and anhydrous THF (10 mL) were added to a 50 mL single-necked flask. Butyllithium (0.34 mL, 2.5 mol / L) was added dropwise at -78 °C, and the mixture was stirred for 1 h. Trimethyltin chloride (181 mg, 0.910 mmol) was then added, and the mixture was gradually brought to room temperature and stirred overnight. After the reactants had completely reacted, the mixture was quenched with water and extracted with EA. The organic phases were combined and washed three times with water. After drying with anhydrous sodium sulfate, excess solvent was removed by vacuum distillation. The mixture was purified by column chromatography using PE:DCM = 6:1 (v / v) as the eluent, yielding approximately 391 mg of compound 5-c, with a yield of 84.8%. MALDI-TOF-MS: 1124.06.

[0161] Synthesis of compound 5-d:

[0162] Compound 5-c (382 mg, 0.34 mmol) and 2-ethylhexyl-4-bromo-3-fluoro-6-carboxythiopheno[3,4-b]thiophene-2-carboxylate (329 mg, 0.78 mmol) were accurately weighed into 8 mL of anhydrous toluene. After purging with nitrogen for 30 min, tetrakis(triphenylphosphine)palladium (4 mg, 0.0034 mmol) was rapidly added. The mixture was heated to 100 °C and reacted for 3 hours. After the reactants had completely reacted, the mixture was cooled to room temperature, potassium fluoride solution was added, and the mixture was stirred for another 20 min. The insoluble solids were filtered off, and the liquid phase was extracted with DCM. The organic phases were combined, dried over anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. The mixture was purified by column chromatography using PE:DCM at a ratio of 1:1 (v / v). Approximately 316 mg of compound 5-d was obtained, yield: 62.9%. MALDI-TOF-MS: 1478.70.

[0163] Synthesis of compound (5):

[0164] Accurately weigh compound 5-d (207 mg, 0.14 mmol) and 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile (94 mg, 0.41 mmol) and dissolve them in 8 mL of toluene. Then add boron trifluoride diethyl ether (0.5 mL) and acetic anhydride (0.5 mL) and react at room temperature under a nitrogen atmosphere for 20 min. After the starting materials have completely reacted, pour the solution into methanol to precipitate the solid and filter. Purify by column chromatography with PE:DCM = 1:2 (volume ratio) as eluent to obtain approximately 148 mg of compound (5), yield: 55.5%. MALDI-TOF-MS: 1903.42.

[0165] Synthesis Example 5: Synthesis of Compound (8)

[0166]

[0167] Accurately weigh compound 4-a (143 mg, 0.10 mmol) and 2-(5-oxo-5,6-dihydro-7H-indeno[5,6-b]thiophene-7-ylidene)malonitrile (78 mg, 0.31 mmol) and dissolve them in 8 mL of toluene. Then add boron trifluoride diethyl ether (0.3 mL) and acetic anhydride (0.3 mL) and react at room temperature under a nitrogen atmosphere for 20 min. After the starting materials have completely reacted, pour the solution into methanol to precipitate the solid and filter. Purify by column chromatography with PE:DCM = 1:2 (volume ratio) as eluent to obtain approximately 127 mg of compound (8), yield: 67.0%. MALDI-TOF-MS: 1896.12.

[0168] Synthesis Example 6: Synthesis of Compound (9)

[0169]

[0170] Synthesis of compound 9-a:

[0171] Under a nitrogen atmosphere, 4,7-dibromo-5,6-dinitrobenzo[c][1,2,5]thiadiazole (500 mg, 1.3 mmol) and (4-butoxyseleno-2-yl)tributyltinane (1.5 g, 2.99 mmol) were added to 15 mL of anhydrous toluene and stirred. After purging with nitrogen for 30 min, tetrakis(triphenylphosphine) palladium (15 mg, 0.013 mmol) was rapidly added, and the reaction was carried out at 100 °C for 3 h. After the reactants had completely reacted, the mixture was cooled to room temperature, potassium fluoride solution was added, and stirring was continued for 20 min. The insoluble solids were removed by filtration, and the liquid phase was extracted with DCM. The organic phases were combined, dried over anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. The mixture was purified by column chromatography with PE:DCM = 4:1 (v / v). Approximately 704 mg of compound 9-a was obtained, yield: 86.1%. MS: 628.75.

[0172] Synthesis of compound 9-b:

[0173] Compound 9-a (700 mg, 1.11 mmol) and triphenylphosphine (1.5 g, 5.57 mmol) were accurately weighed into N-methylpyrrolidone (NMP, 8 mL), and stirred overnight at 180 °C. After the reaction was complete, the mixture was cooled to room temperature, and potassium carbonate (770 mg, 5.57 mmol), potassium iodide (73 mg, 0.44 mmol), and 1-bromo-2-ethylhexane (2.2 g, 11.14 mmol) were added. The temperature was raised to 85 °C and the reaction was continued for 8 h. After the starting material had completely reacted, the mixture was quenched with water and extracted with DCM. The organic phases were combined, washed three times with water, dried over anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. The mixture was purified by column chromatography with PE:DCM = 2:1 (v / v) as the eluent, yielding approximately 476 mg of compound 9-b, yield: 54.3%. MS: 789.30.

[0174] Synthesis of compound 9-c:

[0175] Under a nitrogen atmosphere, compound 9-b (450 mg, 0.57 mmol) and anhydrous THF (10 mL) were added to a 50 mL single-necked flask. Butyllithium (0.25 mL, 2.5 mol / L) was added dropwise at -78 °C for one hour. The mixture was stirred for 1 hour, and then trimethyltin chloride (136 mg, 0.68 mmol) was added, gradually reducing the temperature to room temperature. After the reactants had completely reacted, the mixture was quenched with water and extracted with EA. The organic phases were combined and washed three times with water. After drying with anhydrous sodium sulfate, excess solvent was removed by vacuum distillation. The mixture was purified by column chromatography using PE:DCM = 3:1 (v / v) as the eluent, yielding approximately 532 mg of compound 9-c, in 83.7% yield. MS: 1114.62.

[0176] Synthesis of compound 9-d:

[0177] Accurately weigh compound 9-c (500 mg, 0.45 mmol) and octyl-4-bromo-3-fluoro-6-carboxythiopheno[3,4-B]thiophene-2-carboxylate (472 mg, 1.12 mmol) into 8 mL of anhydrous toluene. After purging with nitrogen for 30 min, tetrakis(triphenylphosphine)palladium (5 mg, 0.0045 mmol) was rapidly added, and the mixture was heated to 100 °C and reacted for 3 hours. After the reactants had completely reacted, the mixture was cooled to room temperature, potassium fluoride solution was added, and stirring was continued for 20 min. The insoluble solids were filtered off, and the liquid phase was extracted with DCM. The organic phases were combined, dried over anhydrous sodium sulfate, and the excess solvent was removed by vacuum distillation. The mixture was purified by column chromatography using PE:DCM at a ratio of 1:1 (v / v). Approximately 452 mg of compound 9-d was obtained, yield: 68.4%. MALDI-TOF-MS: 1469.71.

[0178] Synthesis of compound (9):

[0179] Accurately weigh compound 9-d (206 mg, 0.14 mmol) and 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile (94 mg, 0.41 mmol) and dissolve them in 8 mL of toluene. Then add boron trifluoride diethyl ether (0.3 mL) and acetic anhydride (0.3 mL) and react at room temperature under a nitrogen atmosphere for 20 min. After the starting materials have completely reacted, pour the solution into methanol to precipitate the solid and filter. Purify by column chromatography with PE:DCM = 1:2 (volume ratio) as eluent to obtain approximately 178 mg of compound (9), yield: 67.2%. MALDI-TOF-MS: 1894.45.

[0180] Synthesis Example 7: Synthesis of Compound (15)

[0181]

[0182] Synthesis of compound 15-b:

[0183] Accurately weigh compound 1-c (150 mg, 0.14 mmol) and compound 15-a (141 mg, 0.35 mmol) into 8 mL of anhydrous toluene. After purging with nitrogen for 30 min, tetrakis(triphenylphosphine) palladium (1.6 mg, 0.0014 mmol) was rapidly added. The mixture was heated to 100 °C and reacted for 3 hours. After the reactants had completely reacted, the mixture was cooled to room temperature, potassium fluoride solution was added, and stirring was continued for 20 min. The insoluble solids were filtered off, and the liquid phase was extracted with DCM. The organic phases were combined, dried over anhydrous sodium sulfate, and excess solvent was removed by vacuum distillation. The mixture was purified by column chromatography using PE:DCM at a volume ratio of 2:1. Approximately 148 mg of compound 15-b was obtained, yield: 75.7%. MALDI-TOF-MS: 1395.99.

[0184] Synthesis of compound (15):

[0185] Accurately weigh compound 15-b (140 mg, 0.10 mmol) and 2-(5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-yl)malononitrile (71 mg, 0.31 mmol) and dissolve them in 8 mL of toluene. Then add boron trifluoride diethyl ether (0.3 mL) and acetic anhydride (0.3 mL) and react at room temperature under a nitrogen atmosphere for 20 min. After the starting materials have completely reacted, pour the solution into methanol to precipitate the solid and filter. Purify by column chromatography with PE:DCM = 1:1 (volume ratio) as eluent to obtain approximately 151 mg of compound (15), yield: 82.9%. MALDI-TOF-MS: 1820.43.

[0186] Synthesis Example 8: Synthesis of Compound (20)

[0187]

[0188] Synthesis of compound 20-a:

[0189] Compound 3-a (438 mg, 0.82 mmol) and triphenylphosphine (1.1 g, 4.08 mmol) were accurately weighed into N-methylpyrrolidone (NMP, 8 mL), and stirred overnight at 180 °C. After the reaction was complete, the mixture was cooled to room temperature, and potassium carbonate (562 mg, 4.07 mmol), potassium iodide (55 mg, 0.33 mmol), and 2-butyl-1-bromooctane (2.0 g, 8.16 mmol) were added. The mixture was heated to 85 °C and the reaction was continued for 8 h. After the starting material had completely reacted, the mixture was quenched with water and extracted with DCM. The organic phases were combined, washed three times with water, dried over anhydrous sodium sulfate, and excess solvent was removed by vacuum distillation. The mixture was purified by column chromatography with PE:DCM = 4:1 (v / v) as the eluent, yielding approximately 374 mg of compound 20-a, yield: 56.5%. MS: 807.16.

[0190] Synthesis of compound 20-b:

[0191] Under a nitrogen atmosphere, compound 20-a (330 mg, 0.41 mmol) and anhydrous THF (10 mL) were added to a 50 mL single-necked flask. Butyllithium (0.34 mL, 2.5 mol / L) was added dropwise at -78 °C, and the mixture was stirred for 1 h. Trimethyltin chloride (181 mg, 0.910 mmol) was then added, and the mixture was gradually brought to room temperature and stirred overnight. After the reactants had completely reacted, the mixture was quenched with water and extracted with EA. The organic phases were combined and washed three times with water. After drying with anhydrous sodium sulfate, excess solvent was removed by vacuum distillation. The mixture was purified by column chromatography using PE:DCM = 6:1 (v / v) as the eluent, yielding approximately 361 mg of compound 20-b, with a yield of 77.7%. MALDI-TOF-MS: 1132.75.

[0192] Synthesis of compound 20-d:

[0193] Compound 20-b (170 mg, 0.15 mmol) and compound 20-c (149 mg, 0.37 mmol) were accurately weighed into 8 mL of anhydrous toluene. After purging with nitrogen for 30 min, tetrakis(triphenylphosphine)palladium (1.7 mg, 0.0015 mmol) was rapidly added, and the mixture was heated to 100 °C and reacted for 3 hours. After the reactants had completely reacted, the mixture was cooled to room temperature, and potassium fluoride solution was added. The mixture was stirred for another 20 min, filtered to remove insoluble solids, and extracted with DCM in the liquid phase. The organic phases were combined, dried over anhydrous sodium sulfate, and then distilled under reduced pressure to remove excess solvent. The mixture was purified by column chromatography using PE:DCM at a volume ratio of 1:1. Approximately 147 mg of compound 20-d was obtained, with a yield of 67.5%. MALDI-TOF-MS: 1452.33.

[0194] Synthesis of compound (20):

[0195] Accurately weigh compound 20-d (130 mg, 0.09 mmol) and 2-(6,7-difluoro-3-oxo-2,3-dihydro-1H-cyclopenta[b]naphthyl-1-ylidene)malonitrile (73 mg, 0.26 mmol), dissolve in 8 mL of toluene, then add boron trifluoride diethyl ether (0.3 mL) and acetic anhydride (0.3 mL), and react at room temperature under a nitrogen atmosphere for 20 min. After the starting materials have completely reacted, pour into methanol to precipitate the solid and filter. Purify by column chromatography with PE:DCM = 1:2 (volume ratio) as eluent to obtain approximately 98 mg of compound (20), yield: 55.1%. MALDI-TOF-MS: 1976.46.

[0196] Organic photovoltaic device examples

[0197] The following detailed description of the fabrication process and characterization of organic photovoltaic devices comprising the above-mentioned organic compounds is provided through specific device embodiments.

[0198] refer to Figure 1 The semi-transparent organic photovoltaic device includes a substrate 101, a cathode 102, a cathode buffer layer 103, a photoactive layer 104, an anode buffer layer 105, and an anode 106 stacked sequentially. The materials of the cathode, cathode buffer layer, photoactive layer, anode buffer layer, and anode are, in turn: indium tin oxide (ITO) / ZnO / photoactive layer material / MoO3 / ultra-thin metal layer Ag.

[0199] The fabrication steps of device example 1 are as follows:

[0200] 1) ITO substrate cleaning:

[0201] Clean the ITO conductive glass with detergent, rinse it thoroughly, and then ultrasonically clean it for 15 minutes with deionized water, acetone, and isopropanol. After that, dry it with nitrogen and treat it in a plasma cleaner for 5 minutes to further clean the surface and improve wettability.

[0202] 2) Preparation of cathode buffer layer

[0203] A ZnO solution was uniformly spin-coated onto an ITO layer in air at a speed of 4000 rpm for 30 s, followed by annealing at 200 °C for 30 min to obtain a cathode buffer layer with a thickness of approximately 30 nm.

[0204] 3) Preparation of photoactive layer

[0205] In a glove box (inert gas atmosphere), the photoactive layer material solution is uniformly spin-coated onto the cathode buffer layer at a rotation speed of 1800-4000 rpm to obtain an active material layer with a total thickness of about 100 nm; wherein the donor material in the photoactive layer material solution is selected from polymer PCE10 and the acceptor material is selected from compound (1); PCE10:compound (1) is added to chloroform solution at a mass ratio of 1:2, and the total concentration is 17 mg / mL.

[0206] 4) Preparation of the anode buffer layer

[0207] In high vacuum (1×10) -6 In millibars, MoO3 is vapor-deposited on the photoactive layer to form an anode buffer layer with a thickness of about 10 nm.

[0208] 5) Anode layer preparation

[0209] In high vacuum (1×10) -6 In millibars, metallic Ag is vapor-deposited onto the anode buffer layer to form an anode layer with a thickness of approximately 15 nm.

[0210] 6) Packaging

[0211] The device is encapsulated in a nitrogen glove box using UV-cured resin.

[0212] Device Examples 2-8

[0213] The preparation methods of device examples 2-8 are the same as those of device example 1. The difference lies in the selection of the acceptor material in the photoactive layer. Specifically, the acceptor material compound (1) is replaced with compound (3), compound (4), compound (5), compound (8), compound (9), compound (15), and compound (20), respectively. See Table 1 for details.

[0214] Device Comparison Example 1

[0215] The preparation method of the device in Comparative Example 1 is the same as that in Device Example 1, except that the selection of the acceptor material in the photoactive layer is different. Specifically, the acceptor material compound (1) is replaced with compound (Ref-1).

[0216]

[0217] The prepared organic photovoltaic cells were subjected to performance testing. Under the illumination of the AM1.5 standard light simulator, the test device data are shown in Table 1.

[0218] Table 1

[0219] Device Examples Photoactive layer for acceptor material Photoelectric conversion efficiency (%) Device Example 1 PCE10: Compound (1) 10.85 Device Example 2 PCE10: Compound (3) 11.16 Device Example 3 PCE10: Compound (4) 11.08 Device Example 4 PCE10: Compound (5) 10.72 Device Example 5 PCE10: Compound (8) 9.94 Device Example 6 PCE10: Compound (9) 10.25 Device Example 7 PCE10: Compound (15) 9.88 Device Example 8 PCE10: Compound (20) 9.57 Device Comparison Example 1 PCE10: Compound (Ref-1) 8.78

[0220] As shown in Table 1, the compound described in this invention, when used as an acceptor material in a semi-transparent organic photovoltaic device, exhibits a higher photoelectric conversion efficiency compared to the device in Comparative Example 1. This may be because the compound described in this invention has a Y-shaped molecular configuration, which is beneficial for molecular stacking and charge transport.

[0221] Furthermore, the compound described in this invention is easier to synthesize and has a lower synthesis cost than compound (Ref-1), making it more suitable for industrial production.

[0222] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. An organic compound characterized in that: having the structure of Formula (I): wherein: Y is selected from O, S or Se; Z is selected from O, S or Se; W is selected from O, S or Se; R1is, at each occurrence, independently selected from a linear alkyl group having 1-30 carbon atoms, or a branched alkyl group having 3-30 carbon atoms; R2is, at each occurrence, independently selected from a linear alkoxy group having 1-30 carbon atoms, or a branched alkoxy group having 3-30 carbon atoms; R3is, at each occurrence, independently selected from a linear alkyl group having 1-30 carbon atoms, or a branched alkyl group having 3-30 carbon atoms; R4is, at each occurrence, independently selected from -H, -D, -F, -Cl, -Br, -I, -CN or -CF3; M is, at each occurrence, independently selected from O or C(CN)2; Ar1, Ar2is, at each occurrence, independently selected from a substituted or unsubstituted heteroaromatic group having 5-20 ring atoms, or a substituted or unsubstituted aromatic group having 6-20 carbon atoms; "substituted or unsubstituted" means that the defined group is either not substituted, or substituted with one or more substituents R selected from -D, -F, -Cl, -Br, -I, -CF3, -CN, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, a linear alkoxy group having 1 to 10 carbon atoms, or a branched alkoxy group having 3 to 10 carbon atoms.

2. The organic compound according to claim 1, characterized by: said organic compound having the structure of Formula (II-1) or (II-2):

3. The organic compound according to claim 2, characterized by: said R2is, at each occurrence, independently selected from a linear alkoxy group having 1-10 carbon atoms, or a branched alkoxy group having 3-10 carbon atoms.

4. The organic compound according to claim 2, characterized by: said R3is, at each occurrence, independently selected from a linear alkyl group having 1-10 carbon atoms, or a branched alkyl group having 3-10 carbon atoms.

5. The organic compound according to claim 2, characterized by: said Ar1, Ar2is, at each occurrence, independently selected from any one of the following groups: wherein: m1is selected from 0, 1, 2, 3 or 4; m2is selected from 0, 1, 2, 3, 4, 5 or 6; m2is selected from 0, 1 or 2; # denotes a site of fusion selected from a carbon atom.

6. The organic compound according to claim 5, characterized by: R is selected from -D, -F, -Cl, -Br, -I, -CF3, -CN, methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, or methoxy.

7. The organic compound according to claim 1, characterized by: said organic compound is selected from any one of the following structures:

8. A mixture characterized in that: said mixture comprises the organic compound of any one of claims 1-7.

9. An organic electronic device protecting a cathode, an anode, and a photoactive layer located between the cathode and the anode, said photoactive layer comprising the organic compound of any one of claims 1-7 or the mixture of claim 8.

10. Organic electronic device according to claim 9, characterized in that: said organic electronic device is selected from an organic photovoltaic device or an organic photodetector.

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