Heterocyclic organic compound and application thereof

Abstract

The invention relates to a heterocyclic organic compound which can be applied to an organic electronic device as a hole transport material, and the heterocyclic organic compound has good hole extraction performance, so that effective transfer and extraction of holes are ensured, and a solar cell shows excellent device performance. The heterocyclic organic compound has universality as a hole transport material, and is suitable for various solar cell devices.

Description

Technical Field

[0001] The invention relates to the technical field of organic photoelectric materials, in particular to a heterocyclic organic compound and application thereof. Background Art

[0002] As a green and sustainable clean energy, solar energy has attracted widespread attention due to its advantages such as cleanliness, pollution-free and abundant reserves. As an efficient device that converts solar energy into electrical energy, solar cells are one of the important ways to achieve effective utilization of solar energy and achieve "carbon peak and carbon neutrality".

[0003] The solar cells that are developing rapidly at present mainly include organic solar cells (OPV), perovskite solar cells (PSC), silicon solar cells, fuel sensitized solar cells, etc. Among them, organic solar cells and perovskite solar cells have outstanding advantages such as low cost, high efficiency and flexibility, and are the key development direction of future industrialization.

[0004] Organic solar cell / perovskite solar cell devices are usually sandwich structures, generally composed of five parts: transparent conductive electrode, electron transport layer, photoactive layer, hole transport layer, and metal electrode. The working principle of organic solar cells is: when sunlight shines on the semiconductor photoactive layer, it will excite the formation of hole-electron pairs (excitons). Under the action of the extreme energy difference at the donor-acceptor interface, the excitons are first separated into electrons and holes, and transported to the anode and cathode respectively through the interpenetrating network of the donor and the acceptor. Among them, the existence of electron and hole transport layers can prevent electrons and holes from running to the same side and recombining, thereby improving the charge extraction ability of the device. The active layer of perovskite solar cells is different from that of organic solar cells. Due to the relatively low exciton binding energy of perovskite materials, it is generally believed that free electrons and holes can be directly generated at room temperature, and move to the cathode and anode under the action of the built-in power plant. However, the functions of the hole and electron transport layers of organic and perovskite solar cells are very similar, and the same type of materials are often used. Therefore, for solar cell devices, the selection of charge transport layer materials is crucial.

[0005] At present, hole transport materials are generally selected from three categories, namely: inorganic (V2O5, MoO3, WO3, NiO, etc.), organic polymer (PTAA, PEDOT:PSS, etc.) and organic small molecules (Spiro-OMeTAD, MeO-2PACz, etc.). Among them, inorganic hole transport materials usually require high vacuum process or high temperature annealing treatment during their preparation, which is not conducive to large-scale industrialization. Organic polymer hole transport materials have problems such as high price, need to add dopants to improve the hole mobility of the material, and the material itself is corrosive and hygroscopic, which will destroy the perovskite layer and affect the stability of the battery, and large-scale application is limited. Small molecule hole transport materials have the characteristics of simple synthesis, low cost, and high material utilization, but the current organic small molecule hole transport materials are mostly selected from carbazole phosphonic acid derivatives. Due to the influence of the π structure, the hole transport performance of carbazole phosphonic acid derivatives is low and the thermal stability is poor.

[0006] Therefore, in order to further improve the performance of solar cell devices, it is necessary to develop new small molecule hole transport materials. Summary of the invention

[0007] The purpose of the present invention is to provide a novel heterocyclic organic compound, which can be used as a hole transport material in an organic solar cell or a perovskite solar cell device to improve its photoelectric conversion efficiency. According to the heterocyclic organic compound of the present invention, the synthesis steps are simple, the overall preparation cost is low, and industrial application can be realized.

[0008] To achieve the purpose of the present invention, the technical solution is as follows:

[0009] A heterocyclic organic compound, wherein the heterocyclic organic compound has a structure as shown in general formula (I) or general formula (II):

[0010]

[0011] in:

[0012] x is selected from 0 or 1;

[0013] Each occurrence of R1, R2, and R3 is independently selected from -D (deuterium), -F, -Cl, -Br, -I, cyano, hydroxyl, nitro, amine, straight-chain alkyl having 1-20 C atoms, straight-chain alkoxy having 1-20 C atoms, straight-chain alkylthio having 1-20 C atoms, branched or cyclic alkyl having 3-20 C atoms, branched or cyclic alkoxy having 3-20 C atoms, branched or cyclic alkylthio having 3-20 C atoms, substituted or unsubstituted aromatic group having 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic group having 5-20 ring atoms, or a group formed by a combination of the above groups;

[0014] L is selected from a linear alkyl group having 1 to 20 C atoms, a branched alkyl group having 3 to 20 C atoms, a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms;

[0015] n, at each occurrence, is independently selected from 0, 1, 2, 3, 4, 5 or 6;

[0016] m is independently selected from 0, 1, 2, 3 or 4;

[0017] v is independently selected from 0, 1, 2 or 3;

[0018] The “substituted or unsubstituted” means that the defined group is not substituted or is substituted by one or more substituents R, wherein each occurrence of R is independently selected from -D (deuterium), -F, -Cl, -Br, -I, cyano, hydroxyl, nitro, amine, straight-chain alkyl having 1-20 C atoms, straight-chain alkoxy having 1-20 C atoms, straight-chain alkylthio having 1-20 C atoms, branched or cyclic alkyl having 3-20 C atoms, branched or cyclic alkoxy having 3-20 C atoms, branched or cyclic alkylthio having 3-20 C atoms, aromatic groups having 6-20 carbon atoms, or heteroaromatic groups having 5-20 ring atoms, or groups formed by combinations of the above groups.

[0019] A composition comprises at least one heterocyclic organic compound as described above and at least one organic solvent.

[0020] A hole transport material, wherein the hole transport material is selected from the heterocyclic organic compounds mentioned above.

[0021] An organic electronic device comprises at least one functional layer, wherein the material of the functional layer comprises the heterocyclic organic compound as described above.

[0022] Compared with the prior art, the present invention has the following significant advantages: the heterocyclic organic compound provided by the present invention is used as a hole transport material in both organic solar cells and perovskite cells, and exhibits excellent device performance. The heterocyclic organic compound is universal as a hole transport material and is suitable for multiple types of solar cell devices. The heterocyclic organic compound provided by the present invention has good hole extraction performance, thereby ensuring the effective transfer and extraction of holes, so that when it is used as a hole transport material in an organic solar cell device, the photoelectric conversion efficiency can be close to 18%; when it is used as a hole transport material in a perovskite solar cell device, the photoelectric conversion efficiency exceeds 24%. BRIEF DESCRIPTION OF THE DRAWINGS

[0023] Figure 1Schematic diagram of the structure of an organic solar cell in an embodiment of the device of the present invention.

[0024] Figure 2 Schematic diagram of the structure of a perovskite solar cell in a device embodiment of the present invention.

[0025] Figure 3 This is the NMR spectrum of the compound (1) of the present invention.

[0026] Figure 4 This is the NMR spectrum of the compound (25) of the present invention. DETAILED DESCRIPTION

[0027] In order to make the purpose, technical solution and effect of the present invention clearer and more specific, the present application is further described in detail below. It should be understood that the specific embodiments described herein are only used to explain the present application and are not used to limit the present application.

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

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

[0030] In the present invention, perovskite photovoltaic device, perovskite solar cell, and PSC have the same meaning and can be interchangeable.

[0031] In the present invention, aromatic group, aromatic series, aromatic ring system and aryl have the same meaning and can be interchanged.

[0032] In the present invention, heteroaromatic group, heteroaromatic series, heteroaromatic ring system and heteroaryl have the same meaning and can be interchanged.

[0033] In the present invention, the “heteroatom” is a non-carbon atom and may be at least one of B, O, N, P, Si, Se and S.

[0034] In the present invention, "substituted" means that one or more hydrogen atoms in a substituted group are replaced by a substituent.

[0035] In the present invention, when the same substituent appears multiple times, it can be independently selected from different groups. If the general formula contains multiple R, each occurrence of R can be selected from the same or different groups.

[0036] In the present invention, the "number of ring atoms" refers to the number of atoms constituting the ring itself of a structural compound (e.g., a monocyclic compound, a condensed ring compound, a cross-linked compound, a carbocyclic compound, a heterocyclic compound) in which atoms are bonded to form a ring. When the ring is substituted by a substituent, the atoms contained in the substituent are not included in the ring atoms. The "number of ring atoms" described below is the same unless otherwise specified. 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 thienyl group is 5, and the number of ring atoms of a benzothiadiazole group is 9.

[0037] 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 (such as phenyl) or a polycyclic aromatic group. In other words, the aromatic group can be a monocyclic aromatic group, a condensed aromatic group, two or more monocyclic aromatic groups conjugated by carbon-carbon bonds, monocyclic aromatic groups and condensed aromatic groups conjugated by carbon-carbon bonds, and two or more condensed aromatic groups conjugated by carbon-carbon bonds. That is, unless otherwise specified, two or more aromatic groups conjugated by carbon-carbon bonds can also be regarded as aromatic groups of the present application. Preferably, the aromatic group is selected from aromatic groups with 6-30 C atoms; further, selected from aromatic groups with 6-20 C atoms; further, selected from aromatic groups with 6-10 C atoms; specifically, the aromatic group includes but is not limited to: phenyl, biphenyl, terphenyl, naphthyl, anthracenyl, phenanthrenyl, fluoranthenyl, triphenylene, pyrenyl, perylene, naphthyl, fluorenyl, perylene, acenaphthene and its derivatives.

[0038] In the present invention, "heteroaromatic group" refers to a monovalent aromatic ring or a derivative thereof containing 1, 2, 3, 4, 5, 6 or more heteroatoms in the ring, and the heteroatom may be at least one of B, O, N, P, Si, Se and S. The heteroaromatic group may be a monocyclic heteroaromatic group or a polycyclic heteroaromatic group. In other words, the heteroaromatic group may be a single heteroaromatic ring system or a plurality of heteroaromatic ring systems conjugated by carbon-carbon bonds, and any heteroaromatic ring system is a heteroaromatic monocyclic ring or a heteroaromatic condensed ring. Preferably, the heteroaromatic group is selected from heteroaromatic groups having 6-30 ring atoms; further, selected from heteroaromatic groups having 6-20 ring atoms; further, selected from heteroaromatic groups having 6-10 ring atoms. Specifically, heteroaromatic groups include, but are not limited to, thienyl, furanyl, pyrrolyl, oxadiazolyl, triazolyl, imidazolyl, pyridyl, bipyridyl, pyrimidyl, triazine, acridinyl, pyridazinyl, pyrazinyl, quinolyl, isoquinolyl, quinazolinyl, quinoxalinyl, phthalazinyl, pyridopyrimidinyl, pyridopyrazinyl, benzothienyl, benzofuranyl, indolyl, pyrroloimidazolyl, pyrrolopyrrolyl, thienopyrrolyl, thienothiphenyl, furopyrrolyl, furanofuranyl, thienofuranyl, benzisoxazolyl, benzisothiazolyl, benzimidazolyl, o-naphthyl, phenanthridinyl, primary pyridyl, quinazolinone, dibenzothienyl, dibenzofuranyl, carbazolyl and derivatives thereof.

[0039] In the present invention, "alkyl" may mean a linear, branched or cyclic alkyl group. The carbon number of the linear alkyl group may be 1 to 20, 1 to 16, 1 to 10 or 1 to 6; the carbon number of the branched alkyl group may be 3 to 20, 3 to 16, 3 to 10 or 3 to 6; the carbon number of the cyclic alkyl group may be 3 to 20, 3 to 16, 3 to 10 or 3 to 6. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl , 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2,2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, 3,7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, etc.

[0040] The term "alkoxy" refers to a group with the structure "-O-alkyl", i.e., an alkyl group as defined above is connected to other groups via an oxygen atom. The straight-chain alkoxy group means that the alkyl group in "-O-alkyl" is selected from a straight-chain alkyl group, wherein the carbon atoms of the straight-chain alkyl group may be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the branched-chain alkoxy group means that the alkyl group in "-O-alkyl" is selected from a branched-chain alkyl group, wherein the carbon number of the branched-chain alkyl group may be 3 to 20, 3 to 16, 3 to 10, or 3 to 6; the cyclic alkoxy group means that the alkyl group in "-O-alkyl" is selected from a cyclic alkyl group, wherein the carbon number of the cyclic alkyl group may be 3 to 20, 3 to 16, 3 to 10, or 3 to 6. Suitable examples of phrases containing this term include, but are not limited to, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, pentoxy, 2-pentoxy, isopentoxy, neopentoxy, hexoxy, 2-hexoxy, 3-hexoxy, 3-methylpentoxy.

[0041] The term "alkylthio" refers to a group having the structure "-S-alkyl", i.e., an alkyl group as defined above connected to another group via a sulfur atom. The straight-chain alkylthio group means that the alkyl group in the "-S-alkyl" is selected from a straight-chain alkyl group, wherein the carbon atoms of the straight-chain alkyl group may be 1 to 20, 1 to 16, 1 to 10, or 1 to 6; the branched-chain alkylthio group means that the alkyl group in the "-S-alkyl" is selected from a branched-chain alkyl group, wherein the carbon number of the branched-chain alkyl group may be 3 to 20, 3 to 16, 3 to 10, or 3 to 6; the cyclic alkylthio group means that the alkyl group in the "-S-alkyl" is selected from a cyclic alkyl group, wherein the carbon number of the branched-chain alkyl group may be 3 to 20, 3 to 16, 3 to 10, or 3 to 6. Suitable examples of phrases containing this term include, but are not limited to, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio, pentylthio, 2-pentylthio, isopentylthio, neopentylthio, hexylthio, 2-hexylthio, 3-hexylthio, 3-methylpentylthio.

[0042] In the present invention, "*" connected to a single bond indicates a connection site.

[0043] 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.

[0044] 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. The six Rs on the benzene ring may be the same as or different from each other.

[0045] In the present invention, one or more groups “independently selected from” means that when one or more groups appear simultaneously and in multiple places in a compound, they are all independently selected and may be the same or different.

[0046] In the present invention, the single bond to which the substituent is connected 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.

[0047] The "combinations thereof", "any combinations thereof", "any combinations thereof", "combinations" and the like used in the present invention include all suitable combinations of any two, three or four or more of the listed groups.

[0048] In the present invention, “further”, “furthermore”, “particularly”, etc. are used for descriptive purposes to indicate differences in content, but should not be construed as limiting the scope of protection of the present invention.

[0049] In the present invention, "optionally", "optional", and "optional" mean optional, that is, any one of the two parallel solutions of "yes" or "no". If multiple "options" appear in a technical solution, unless otherwise specified and there is no contradiction or mutual restriction, each "optional" is independent.

[0050] In the present invention, the technical features described in an open manner include closed technical solutions composed of the listed features, and also include open technical solutions composed of the listed features.

[0051] A heterocyclic organic compound having a structure as shown in general formula (I) or general formula (II):

[0052]

[0053] in:

[0054] x is selected from 0 or 1;

[0055] Each occurrence of R1, R2, and R3 is independently selected from -D (deuterium), -F, -Cl, -Br, -I, cyano, hydroxyl, nitro, amine, straight-chain alkyl having 1-20 C atoms, straight-chain alkoxy having 1-20 C atoms, straight-chain alkylthio having 1-20 C atoms, branched or cyclic alkyl having 3-20 C atoms, branched or cyclic alkoxy having 3-20 C atoms, branched or cyclic alkylthio having 3-20 C atoms, substituted or unsubstituted aromatic group having 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic group having 5-20 ring atoms, or a group formed by a combination of the above groups;

[0056] L is selected from a linear alkyl group having 1 to 20 C atoms, a branched alkyl group having 3 to 20 C atoms, a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms;

[0057] n, at each occurrence, is independently selected from 0, 1, 2, 3, 4, 5 or 6;

[0058] m is independently selected from 0, 1, 2, 3 or 4;

[0059] v is independently selected from 0, 1, 2 or 3.

[0060] The “substituted or unsubstituted” means that the defined group is not substituted or is substituted by one or more substituents R, wherein each occurrence of R is independently selected from -D (deuterium), -F, -Cl, -Br, -I, cyano, hydroxyl, nitro, amine, straight-chain alkyl having 1-20 C atoms, straight-chain alkoxy having 1-20 C atoms, straight-chain alkylthio having 1-20 C atoms, branched or cyclic alkyl having 3-20 C atoms, branched or cyclic alkoxy having 3-20 C atoms, branched or cyclic alkylthio having 3-20 C atoms, aromatic groups having 6-20 carbon atoms, or heteroaromatic groups having 5-20 ring atoms, or groups formed by combinations of the above groups.

[0061] Further, the "substituted or unsubstituted" means that the defined group is not substituted or is substituted by one or more substituents R, wherein each occurrence of R is independently selected from -D (deuterium), -F, -Cl, -Br, -I, cyano, hydroxyl, nitro, amine, straight-chain alkyl having 1-10 C atoms, straight-chain alkoxy having 1-10 C atoms, straight-chain alkylthio having 1-10 C atoms, branched or cyclic alkyl having 3-10 C atoms, branched or cyclic alkoxy having 3-10 C atoms, branched or cyclic alkylthio having 3-10 C atoms, aromatic groups having 6-10 carbon atoms, or heteroaromatic groups having 5-10 ring atoms, or groups formed by combinations of the above groups.

[0062] Further, the "substituted or unsubstituted" means that the defined group is not substituted or is substituted by one or more substituents R, wherein each occurrence of R is independently selected from -D (deuterium), -F, -Cl, -Br, -I, cyano, hydroxyl, nitro, amine, straight-chain alkyl having 1-6 C atoms, straight-chain alkoxy having 1-6 C atoms, straight-chain alkylthio having 1-6 C atoms, branched or cyclic alkyl having 3-6 C atoms, branched or cyclic alkoxy having 3-6 C atoms, branched or cyclic alkylthio having 3-6 C atoms, aromatic group having 6-10 carbon atoms, or heteroaromatic group having 5-6 ring atoms, or a group formed by a combination of the above groups.

[0063] In one embodiment, x is selected from 0, and the heterocyclic organic compound is selected from the structure represented by the general formula (III-1) or the general formula (III-2):

[0064]

[0065] In another embodiment, x is selected from 1, and the heterocyclic organic compound is selected from the structure represented by the general formula (III-3) or the general formula (III-4):

[0066]

[0067] In one embodiment, L is independently selected from a linear alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms.

[0068] In one embodiment, L in Formula (III-1) or (III-2) is independently selected from a straight-chain alkyl group having 1 to 10 C atoms, a branched alkyl group having 3 to 10 C atoms, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms.

[0069] The meaning of "substituted or unsubstituted" is as described above.

[0070] In a preferred embodiment, L in the general formula (III-1) or (III-2) is selected from -(CH2)-, -(CH2)-(CH2)-, -(CH2)-(CH2)-(CH2)-, -(CH2)-(CH2)-(CH2)-(CH2)-, -(CH2)-(CH2)-(CH2)-(CH2)-, -(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-, -(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-, phenyl, pyridyl, pyrimidinyl, triazine, thienyl, furanyl, benzothiadiazolyl, biphenyl, thiophenebiphenyl, and thiophenebithienyl; the above groups are unsubstituted or further substituted by R, and R has the same meaning as above.

[0071] In a more preferred embodiment, L in the general formula (III-1) is selected from -(CH2)-, -(CH2)-(CH2)-, -(CH2)-(CH2)-(CH2)-(CH2)-, -(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-, phenyl, pyridyl, thienyl, benzothiadiazolyl or biphenyl.

[0072] In a more preferred embodiment, L in the general formula (III-2) is selected from -(CH2)-, -(CH2)-(CH2)-, -(CH2)-(CH2)-(CH2)-(CH2)-, -(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-, phenyl, pyridyl, thienyl, benzothiadiazolyl or biphenyl.

[0073] In one embodiment, L in Formula (III-3) or (III-4) is independently selected from a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms.

[0074] The meaning of "substituted or unsubstituted" is as described above.

[0075] In a preferred embodiment, L in the general formula (III-3) or (III-4) is selected from phenyl, pyridyl, pyrimidinyl, triazine, thienyl, furanyl, benzothiadiazolyl, biphenyl, thiophenebiphenyl, thiophenebithiophene; the above groups are unsubstituted or further substituted by R, and R has the same meaning as described above.

[0076] In a more preferred embodiment, L in the general formula (III-3) is selected from phenyl, pyridyl, thienyl, benzothiadiazolyl or biphenyl.

[0077] In a more preferred embodiment, L in the general formula (III-4) is selected from phenyl, pyridyl, thienyl, benzothiadiazolyl or biphenyl.

[0078] In one embodiment, each occurrence of R1, R2, and R3 is independently selected from -D (deuterium), -F, -Cl, -Br, -I, cyano, hydroxyl, nitro, amine, a straight-chain alkyl group having 1-10 C atoms, a straight-chain alkoxy group having 1-10 C atoms, a straight-chain alkylthio group having 1-10 C atoms, a branched or cyclic alkyl group having 3-10 C atoms, a branched or cyclic alkoxy group having 3-10 C atoms, a branched or cyclic alkylthio group having 3-10 C atoms, 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.

[0079] In one embodiment, each occurrence of R1, R2, and R3 is independently selected from -D (deuterium), -F, -Cl, -Br, -I, cyano, hydroxyl, nitro, amine, a straight-chain alkyl group having 1-6 C atoms, a straight-chain alkoxy group having 1-6 C atoms, a straight-chain alkylthio group having 1-6 C atoms, a branched or cyclic alkyl group having 3-6 C atoms, a branched or cyclic alkoxy group having 3-6 C atoms, a branched or cyclic alkylthio group having 3-6 C atoms, 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.

[0080] In one embodiment, each occurrence of R1, R2, and R3 is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2-hexyl, 3-hexyl, 3-methylpentyl, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio, hydroxyl, cyano, nitro, -Cl, -Br, -F, -I, -CF3, phenyl, pyridyl, pyrimidinyl, triazine, thienyl, furanyl, or a group formed by a combination of the above groups.

[0081] In a specific embodiment, the heterocyclic organic compound represented by the general formula (III-1) or the general formula (III-2) is further selected from the structure represented by any one of the general formulas (IV-1) to (IV-4):

[0082]

[0083] In a specific embodiment, the heterocyclic organic compound represented by the general formula (III-3) and the general formula (III-4) is further selected from the structure represented by any one of the general formulas (IV-5) to (IV-8):

[0084]

[0085] In one embodiment, each occurrence of R1 and R2 in the general formula (IV-3), general formula (IV-4), general formula (IV-7), and general formula (IV-8) is independently selected from -D, -F, -Cl, -Br, -I, cyano, hydroxyl, nitro, amine, a straight-chain alkyl group having 1-6 C atoms, a straight-chain alkoxy group having 1-6 C atoms, a straight-chain alkylthio group having 1-6 C atoms, a branched or cyclic alkyl group having 3-6 C atoms, a branched or cyclic alkoxy group having 3-6 C atoms, a branched or cyclic alkylthio group having 3-6 C atoms, a phenyl group, a pyridyl group, a thienyl group, a furanyl group, or a group formed by a combination of the above groups.

[0086] In a specific embodiment, in the general formula (IV-3), general formula (IV-4), general formula (IV-7), and general formula (IV-8), each occurrence of R1 and R2 is independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2-hexyl, 3-hexyl, 3-methylpentyl, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, methylthio, ethylthio, propylthio, isopropylthio, n-butylthio, sec-butylthio, tert-butylthio, hydroxyl, cyano, nitro, -Cl, -Br, -F, -I, -CF3, phenyl, pyridyl, pyrimidinyl, triazine, thienyl, furanyl, or a group formed by a combination of the above groups.

[0087] In a more specific embodiment, in general formula (IV-3), general formula (IV-4), general formula (IV-7), and general formula (IV-8), each occurrence of R1 and R2 is independently selected from methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, methoxy, -Cl, -Br, -F, -I, -CF3, phenyl, or phenyl substituted with methoxy.

[0088] In one embodiment, the heterocyclic organic compound is selected from any of the following structures, but is not limited thereto:

[0089]

[0090]

[0091]

[0092] The present invention further relates to a hole transport material, wherein the hole transport material is selected from the heterocyclic organic compounds as described above.

[0093] The present invention further relates to a composition comprising at least one of the heterocyclic organic compounds described above and at least one organic solvent. In one embodiment, the organic solvent is selected from alcohols; preferably, the organic solvent is selected from at least one of methanol, ethanol, isopropanol, ethylene glycol, etc.; more preferably, the organic solvent is selected from methanol, ethanol or isopropanol.

[0094] Furthermore, the concentration of the heterocyclic organic compound in the composition in the organic solvent is selected from 0.1 to 5 mg / ml; further, the concentration of the heterocyclic organic compound in the composition in the organic solvent is selected from 0.5 to 1 mg / ml; in a specific embodiment, the organic solvent is selected from methanol.

[0095] The present invention also relates to an organic electronic device, comprising at least one functional layer, wherein the material of the functional layer comprises the heterocyclic organic compound as described above.

[0096] Furthermore, the organic electronic device includes an anode, a cathode, a photoactive layer located between the cathode and the anode, an electron transport layer located between the cathode and the photoactive layer, and a hole transport layer located between the anode and the photoactive layer, wherein the hole transport layer contains the heterocyclic organic compound as described above or is prepared from the above-mentioned composition.

[0097] It should be noted that, in order to improve the performance of organic / perovskite solar cell devices, the functional layer may further include other functional layers, including but not limited to a charge injection layer and / or a charge blocking layer. The charges include holes and electrons.

[0098] Preferably, the organic electronic device is selected from organic solar cells (OPV), perovskite solar cells (PSC), organic light emitting diodes (OLED), organic photodetectors (OPD), etc., but is not limited thereto.

[0099] In one embodiment, the organic electronic device is selected from perovskite solar cells.

[0100] Furthermore, the present invention relates to a perovskite solar cell, wherein an anode layer, a hole transport layer, a photoactive layer, an electron transport layer, a hole blocking layer, and a cathode layer are stacked in sequence from bottom to top.

[0101] Preferably, the anode layer of the perovskite solar cell is preferably selected from metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO), etc.

[0102] Furthermore, the hole transport layer of the perovskite solar cell is selected from the heterocyclic organic compounds described above.

[0103] Furthermore, the photoactive layer of the perovskite solar cell is preferably selected from polycrystalline or single crystalline organic-inorganic hybrid ABX3 structure perovskite materials, wherein A is a cation and is MA + , FA + , Cs + One or more of alkylamine, alkylamidine and alkali metal elements, B is a cation such as Pb 2+ Sn 2+ ,Ge 2+ , Sb 2+ 、Bi 3+ One or more of the fourth, fifth and sixth main group elements or Ag + , Cu 2+ One or more of the first subgroup elements are equally distributed, X is an anion of Cl - Br - ,I -One or more of the halogen elements; in a specific embodiment, the photoactive layer material is selected from FAPbI3.

[0104] Further, the electron transport layer material of the perovskite solar cell is selected from: one or more of tin oxide (SnO2), titanium dioxide (TiO2), metal phthalocyanine molecular materials, zinc oxide (ZnO), zinc tin oxide, fullerene (such as C60), fullerene derivatives (such as PCBM), BCP, graphene and other compounds and their derivatives, but not limited thereto. In a specific embodiment, the electron transport layer material is selected from PC61BM, PC71BM or C60.

[0105] Furthermore, the hole blocking layer material of the perovskite solar cell is selected from BCP.

[0106] Furthermore, the cathode layer material of the perovskite solar cell is 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; the cathode layer can be a single-layer or multi-layer structure. When it is a multi-layer structure, it can be selected from LiF / Al, LiO2 / Al, LiF / Fe, MoO3 / Al, Al:Li, Al:BaF2 and Al:BaF2:Ba, etc., but is not limited to this.

[0107] In another embodiment, the organic electronic device is selected from organic solar cells.

[0108] Preferably, the anode layer of the organic solar cell is selected from metal oxides, such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO) and the like.

[0109] Further, the hole transport layer of the organic solar cell is selected from the heterocyclic organic compounds as described above. Further, the photoactive layer material of the organic solar cell comprises a photoactive layer donor material and a photoactive layer acceptor material; preferably, the photoactive layer acceptor material can be selected from a condensed ring type non-fullerene small molecule acceptor based on a Y6 skeleton, such as: Y6, BTP-4Cl-8, L8-BO, BO-4Cl, N3, BTP-eC9 and its derivatives; or a non-condensed ring small molecule acceptor material, or a dimer, trimer or polymer based on a Y6 skeleton, but not limited thereto. The photoactive layer donor material is selected from: one or more of PBDB-T, PM6, PM7, D18, D18-Cl, PTO2, PB2, PB2F, PTQ10, PTQ11, or a small molecule donor material, but not limited thereto.

[0110] Furthermore, the electron transport layer material of the organic solar cell can be a metal complex, metal oxide, metal salt, etc. with a low work function, such as a metal complex containing 8-hydroxyquinoline, a complex containing Alq3, a metal complex containing Liq, LiF, Ca, titanium oxide (TiOx), zinc oxide (ZnO), cesium carbonate (Cs2CO3), etc.; it can also be a polymer material, such as PFN-Br or PFN or PDINO or PDINN or PNDIT-F3N-Br or PNDIT-F3N, etc., but is not limited to this.

[0111] The cathode material of the organic solar cell can be selected from metals, such as vanadium (V), chromium (Cr), zinc (Zn), silver (Ag), aluminum (Al), platinum (Pt), tungsten (W), copper (Cu), molybdenum (Mo), gold (Au), nickel (Ni), palladium (Pd), or alloys of the above metals; conductive nanomaterials, such as metal nanowires, nanoparticle slurries, graphene, carbon nanotubes, etc.; combinations of metals and oxides, such as ZnO:Al or SnO2:Sb, etc.; and conductive polymers, such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole and polyaniline, etc.; or materials with a multilayer structure, such as LiF / Al, LiO2 / Al, LiF / Fe, MoO3 / Al, Al:Li, Al:BaF2 and Al:BaF2:Ba, etc., but are not limited thereto.

[0112] Further, the organic electronic device (organic solar cell and perovskite solar cell) of the present invention further comprises a substrate, and the substrate uses a substrate with excellent transparency, surface smoothness, ease of operation and waterproofness. Specifically, a glass substrate, a thin film glass substrate or a transparent plastic substrate can be used. The plastic substrate may include a film in a single or multilayer form, such as polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyetheretherketone (PEEK) and polyimide (PI), but is not limited thereto.

[0113] The present invention also relates to the application of the organic electronic device according to the present invention in various devices, including, but not limited to, automobiles and building integrated photovoltaics (BIPV), electronic price tags, indoor photovoltaics, the Internet of Things, smart agriculture, etc.

[0114] In the description of the present invention, it is to be understood that the terms "upper", "lower", "between layers", etc. indicate orientations or positional relationships that are conventionally placed when organic electronic devices are used, or are orientations or positional relationships conventionally understood by those skilled in the art. These are merely 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 operated in a specific orientation, and therefore should not be understood as a limitation on the present invention.

[0115] The present invention will be described below in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the attached claims summarize the scope of the present invention. Under the guidance of the concept of the present invention, those skilled in the art should be aware that certain changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention.

[0116] Here, the heterocyclic organic compound and the organic electronic device described in the present invention are exemplified, but the present invention is not limited to the following embodiments.

[0117] Preparation of heterocyclic organic compounds:

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

[0119]

[0120] Synthesis of compound 1-2:

[0121] Accurately weigh compound 1-1 (13.4 g, 50 mmol) and 1,4-dibromobutane (16.2 g, 75 mmol) and add them to a 500 mL three-necked flask in sequence, add about 100 mL of NaOH aqueous solution (50%), 100 mL of dioxane, and tetrabutylammonium bromide (1.6 g, 5 mmol), replace nitrogen three times, heat to 70 ° C and react for 4 hours, cool to room temperature after the raw materials are completely reacted, add water to quench, and extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent, mix with silica gel column chromatography, and eluent is PE:EA=5:1 (volume ratio) to obtain about 12.6 g of compound 1-2, yield: 62.6%. MS: 402.51

[0122] Synthesis of compound 1-3:

[0123] Accurately weigh compound 1-2 (4 g, 10 mmol) and add it to a 100 mL three-necked flask, add about 60 mL of triethyl phosphite, replace nitrogen three times and heat to 160 ° C for 1 hour. After the raw materials are completely reacted, remove the excess solvent by vacuum distillation, and silica gel column chromatography with eluent PE: EA = 1: 1 (volume ratio) to obtain about 4.4 g of compound 1-3, yield: 95.8%. MS: 460.33 Synthesis of compound (1):

[0124] Accurately weigh compound 1-3 (4.4 g, 9.6 mmol) in a 100 mL three-necked flask, add about 50 mL of anhydrous dioxane, replace nitrogen three times, slowly drop about 5 mL of trimethylsilyl bromide into the reaction system, then heat to 70 ° C and react for 2 hours. After the raw materials are completely reacted, remove the excess solvent by vacuum distillation, add methanol and water to precipitate solids, filter, and slurry the filter cake with ethyl acetate to obtain about 2.6 g of compound (1), yield: 67.1%. MADLI-TOF-MS: 403.55, such as Figure 3 Shown is the NMR spectrum of compound (1).

[0125] Example 2: Synthesis of Compound (6)

[0126]

[0127] Synthesis of compound 6-3:

[0128] Accurately weigh compound 1-1 (13.4 g, 50 mmol), compound 6-2 (9.3 g, 50 mmol), Pd(dba)2 (0.3 g 0.5 mmol), sodium tert-butoxide (9.6 g, 100 mmol) and add them into a 500 mL three-necked flask in turn, add about 300 mL of xylene, replace nitrogen three times and add 0.4 mL of tri-tert-butylphosphine (10% by volume), then heat to 160 ° C and react for 4 hours. After the raw materials are completely reacted, cool to room temperature, add water to quench and extract with ethyl acetate, combine the organic phases, dry over anhydrous sodium sulfate and distill under reduced pressure to remove excess solvent, mix with silica gel column chromatography, eluent is PE: EA = 5: 1 (volume ratio) to obtain about 13.4 g of compound 6-3, yield: 75.4%.

[0129] MS:371.68

[0130] Synthesis of compound 6-5:

[0131] Accurately weigh compound 6-3 (3.7 g, 10 mmol) and about 3.2 mL of compound 6-4, add them into a 100 mL three-necked flask, add 40 mL of DMF, replace nitrogen three times, add 2 mL of pyridine, and then heat to 160 ° C for 2 hours. After the raw materials are completely reacted, dilute with water and extract with ethyl acetate. Combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Mix the sample with silica gel column chromatography, eluent EA to obtain about 4.6 g of compound 6-5, yield: 86.7%. MS: 530.88 Synthesis of compound (6):

[0132] Accurately weigh compound 6-5 (4.6 g, 8.7 mmol) in a 100 mL three-necked flask, add about 50 mL of anhydrous dioxane, replace nitrogen three times, slowly drop about 5 mL of trimethylsilyl bromide into the reaction system, then heat to 70 ° C and react for 2 hours. After the raw materials are completely reacted, remove the excess solvent by vacuum distillation, add methanol and water to precipitate solids, filter, and slurry the filter cake with ethyl acetate to obtain about 2.5 g of compound (6), yield: 60.6%. MADLI-TOF-MS: 474.60

[0133] Example 3: Synthesis of Compound (12)

[0134]

[0135] Synthesis of compound 12-2:

[0136] Accurately weigh compound 12-1 (21.3 g, 50 mmol) and 1,4-dibromobutane (16.2 g, 75 mmol) and add them to a 500 mL three-necked flask in sequence, add about 100 mL of NaOH aqueous solution (50%), 200 mL of dioxane, and tetrabutylammonium bromide (1.6 g, 5 mmol), replace nitrogen three times, and heat to 70 ° C for 4 hours. After the raw materials react completely, cool to room temperature, add water to quench, and extract with ethyl acetate. Combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent. Silica gel mixed sample column chromatography, eluent PE: EA = 5: 1 (volume ratio) to obtain about 21.6 g of compound 12-2, yield: 77.1%. MS: 560.88

[0137] Synthesis of compound 12-3:

[0138] Accurately weigh compound 12-2 (5.6 g, 10 mmol) and add it to a 100 mL three-necked flask, add about 60 mL of triethyl phosphite, replace nitrogen three times, and then heat to 160 ° C for 1 hour. After the raw materials are completely reacted, remove the excess solvent by vacuum distillation, and silica gel column chromatography, eluent PE: EA = 1: 1 (volume ratio) to obtain about 5.7 g of compound 12-3, yield: 92.3%.

[0139] MS:617.56

[0140] Synthesis of compound (12):

[0141] Accurately weigh compound 12-3 (5.7 g, 9.2 mmol) in a 100 mL three-necked flask, add about 60 mL of anhydrous dioxane, replace nitrogen three times, slowly add about 5 mL of trimethylsilyl bromide to the reaction system, then heat to 70 ° C and react for 2 hours. After the raw materials are completely reacted, remove the excess solvent by vacuum distillation, add methanol and water to precipitate solids, filter, and slurry the filter cake with ethyl acetate to obtain about 3.6 g of compound (12), with a yield of 64.2%. MADLI-TOF-MS: 561.54

[0142] Example 4: Synthesis of Compound (21)

[0143]

[0144] Synthesis of compound 21-1:

[0145] Accurately weigh compound 12-1 (21.3 g, 50 mmol), cuprous iodide (1 g, 5 mmol), sodium methoxide (2.2 g, 200 mmol) and add them to a 500 mL three-necked flask in sequence, add about 220 mL of anhydrous DMF, replace nitrogen three times and heat to 100 ° C for 4 hours, cool to room temperature after the raw materials are completely reacted, dilute with water and extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate and remove excess solvent by vacuum distillation, mix with silica gel column chromatography, eluent is PE: EA = 5: 1 (volume ratio) to obtain about 8.6 g of compound 21-1, yield: 52.5%. MS: 327.56

[0146] Synthesis of compound 21-2:

[0147] Accurately weigh compound 21-1 (6.5g, 20mmol), compound 6-2 (4.1g, 22mmol,) Pd(dba)2 (0.3g0.5mmol), X-phos (0.5g, 1mmol), sodium tert-butoxide (3.8g, 40mmol) and add them to a 250mL three-necked flask in sequence, add about 100mL of xylene, replace nitrogen three times and heat to 160℃ for 4 hours, cool to room temperature after the raw materials are completely reacted, add water to quench and extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate and remove excess solvent by vacuum distillation, mix with silica gel column chromatography, eluent is PE:EA=5:1 (volume ratio) to obtain about 6.6g of compound 21-2, yield: 76.5%. MS: 431.68 Synthesis of compound 21-3:

[0148] Accurately weigh compound 21-2 (4.3 g, 10 mmol) and about 3.2 mL of compound 6-4, add them into a 100 mL three-necked flask, add 40 mL of DMF, replace nitrogen three times, add 2 mL of pyridine, and then heat to 160 ° C for 2 hours. After the raw materials are completely reacted, dilute with water and extract with ethyl acetate. Combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Mix the sample with silica gel column chromatography, eluent EA to obtain about 4.8 g of compound 21-3, yield: 81.3%. MS: 590.88 Synthesis of compound (21):

[0149] Accurately weigh compound 21-3 (4.8 g, 8.1 mmol) in a 100 mL three-necked flask, add about 50 mL of anhydrous dioxane, replace nitrogen three times, slowly add about 5 mL of trimethylsilyl bromide to the reaction system, then heat to 70 ° C and react for 2 hours. After the raw materials are completely reacted, remove the excess solvent by vacuum distillation, add methanol and water to precipitate solids, filter, and slurry the filter cake with ethyl acetate to obtain about 2.5 g of compound (21), yield: 57.8%. MADLI-TOF-MS: 534.64

[0150] Example 5: Synthesis of Compound (25)

[0151]

[0152] Synthesis of compound 25-2:

[0153] Accurately weigh compound 25-1 (14.6 g, 50 mmol) and 1,4-dibromobutane (16.2 g, 75 mmol) and add them to a 500 mL three-necked flask in sequence, add about 100 mL of NaOH aqueous solution (50%), 200 mL of dioxane, and tetrabutylammonium bromide (1.6 g, 5 mmol), replace nitrogen three times, heat to 70 ° C and react for 4 hours, cool to room temperature after the raw materials react completely, add water to quench, and extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and distill under reduced pressure to remove excess solvent, mix with silica gel column chromatography, eluent is PE:EA=5:1 (volume ratio) to obtain about 15.6 g of compound 25-2, yield: 73.2%. MS: 426.56

[0154] Synthesis of compound 25-3:

[0155] Accurately weigh compound 25-2 (4.3 g, 10 mmol) and add it to a 100 mL three-necked flask, add about 60 mL of triethyl phosphite, replace nitrogen three times, and then heat to 160 ° C for 1 hour. After the raw materials are completely reacted, remove the excess solvent by vacuum distillation, and silica gel column chromatography, eluent PE: EA = 1: 1 (volume ratio) to obtain about 4.6 g of compound 25-3, yield: 95.1%.

[0156] MS:483.68

[0157] Synthesis of compound (25):

[0158] Accurately weigh compound 25-3 (4.6 g, 9.5 mmol) in a 100 mL three-necked flask, add about 50 mL of anhydrous dioxane, replace nitrogen three times, slowly add about 5 mL of trimethylsilyl bromide to the reaction system, then heat to 70 ° C and react for 2 hours. After the raw materials are completely reacted, remove the excess solvent by vacuum distillation, add methanol and water to precipitate the solid, filter, and slurry the filter cake with ethyl acetate to obtain about 2.6 g of compound (25), yield: 65.1%. MADLI-TOF-MS: 427.66. Figure 4 Shown is the NMR spectrum of compound (25).

[0159] Example 6: Synthesis of Compound (30)

[0160]

[0161] Synthesis of compound 30-1:

[0162] Accurately weigh compound 25-1 (14.6 g, 50 mmol), 6-2 (9.3 g, 50 mmol), Pd(dba)2 (0.3 g 0.5 mmol), sodium tert-butoxide (9.6 g, 100 mmol) and add them into a 500 mL three-necked flask in turn, add about 300 mL of xylene, replace nitrogen three times and add 0.4 mL of tri-tert-butylphosphine (10% by volume), then heat to 160 ° C and react for 4 hours. After the raw materials are completely reacted, cool to room temperature, add water to quench and extract with ethyl acetate, combine the organic phases, dry over anhydrous sodium sulfate and distill under reduced pressure to remove excess solvent, mix with silica gel column chromatography, eluent is PE: EA = 5: 1 (volume ratio) to obtain about 13.9 g of compound 30-1, yield: 70.3%.

[0163] MS:395.68

[0164] Synthesis of compound 30-2:

[0165] Accurately weigh compound 30-1 (4 g, 10 mmol) and about 3.2 mL of compound 6-4, add them into a 100 mL three-necked flask, add 40 mL of DMF, replace nitrogen three times, add 2 mL of pyridine, and then heat to 160 ° C for 2 hours. After the raw materials are completely reacted, dilute with water and extract with ethyl acetate. Combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Mix the sample with silica gel column chromatography, eluent EA to obtain about 4.6 g of compound 30-2, yield: 82.9%. MS: 554.69 Synthesis of compound (30):

[0166] Accurately weigh compound 30-2 (4.6 g, 8.3 mmol) in a 100 mL three-necked flask, add about 50 mL of anhydrous dioxane, replace nitrogen three times, slowly add about 5 mL of trimethylsilyl bromide to the reaction system, then heat to 70 ° C and react for 2 hours. After the raw materials are completely reacted, remove the excess solvent by vacuum distillation, add methanol and water to precipitate solids, filter, and slurry the filter cake with ethyl acetate to obtain about 2.3 g of compound (30), yield: 55.7%. MADLI-TOF-MS: 498.55

[0167] Example 7: Synthesis of Compound (33)

[0168]

[0169] Synthesis of compound 33-2:

[0170] Accurately weigh compound 25-1 (14.6 g, 50 mmol), 33-1 (12.2 g, 50 mmol), Pd(dba)2 (0.3 g 0.5 mmol), sodium tert-butoxide (9.6 g, 100 mmol) and add them into a 500 mL three-necked flask in turn, add about 300 mL of xylene, replace nitrogen three times and add 0.4 mL of tri-tert-butylphosphine (10% by volume), then heat to 160 ° C and react for 4 hours. After the raw materials are completely reacted, cool to room temperature, add water to quench and extract with ethyl acetate, combine the organic phases, dry over anhydrous sodium sulfate and distill under reduced pressure to remove excess solvent, mix with silica gel column chromatography, eluent is PE: EA = 5: 1 (volume ratio) to obtain about 16.9 g of compound 33-2, yield: 74.5%.

[0171] MS:453.68

[0172] Synthesis of compound 33-3:

[0173] Accurately weigh compound 33-2 (4.5 g, 10 mmol) and about 3.2 mL of compound 6-4, add them into a 100 mL three-necked flask, add 40 mL of DMF, replace nitrogen three times, add 2 mL of pyridine, and then heat to 160 ° C for 2 hours. After the raw materials are completely reacted, dilute with water and extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Silica gel mixed sample column chromatography, eluent EA to obtain about 5.1 g of compound 33-3, yield: 83.2%. MS: 612.66 Synthesis of compound (33):

[0174] Accurately weigh compound 33-3 (5.1 g, 8.3 mmol) in a 100 mL three-necked flask, add about 50 mL of anhydrous dioxane, replace nitrogen three times, slowly add about 5 mL of trimethylsilyl bromide to the reaction system, then heat to 70 ° C and react for 2 hours. After the raw materials are completely reacted, remove the excess solvent by vacuum distillation, add methanol and water to precipitate solids, filter, and slurry the filter cake with ethyl acetate to obtain about 2.8 g of compound (33), yield: 60.6%. MADLI-TOF-MS: 556.62

[0175] Example 8: Synthesis of Compound (38)

[0176]

[0177] Synthesis of compound 38-2:

[0178] Accurately weigh compound 38-1 (44.9 g, 100 mmol) and Ni(dppp)Cl2 (2.7 g 5 mmol) in a 1000 mL three-necked flask, add about 400 mL of anhydrous THF, replace nitrogen three times and cool to -30°C, then slowly drop methylmagnesium bromide (3M 74 mL) into the reaction system, naturally warm to room temperature and react for 6 hours, add water to quench after the raw material is completely reacted, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation, mix with silica gel column chromatography, eluent is PE:EA=8:1 (volume ratio) to obtain about 14.2 g of compound 38-2, yield: 44.5%. MS: 319.54

[0179] Synthesis of compound 38-4:

[0180] Accurately weigh compound 38-2 (3.2 g, 10 mmol), add it to a 100 mL three-necked flask, add 30 mL of anhydrous DMSO, slowly add sodium hydride (60% 0.48 g) to the reaction system under nitrogen protection, react at 0°C for 1 hour, add compound 38-3 (3 ml) and palladium acetate (0.1 g) to the reaction system, replace nitrogen three times, and then heat to 120°C to react for 2 hours. After the raw material is completely reacted, dilute it with water and extract it with ethyl acetate. Combine the organic phases, dry it with anhydrous sodium sulfate, and distill it under reduced pressure to remove excess solvent. Silica gel mixed sample column chromatography, eluent EA to obtain about 2.6 g of compound 38-4, yield: 53.8%. MS: 483.61

[0181] Synthesis of compound (38):

[0182] Accurately weigh compound 38-4 (2.6 g, 5.4 mmol) in a 100 mL three-necked flask, add about 50 mL of anhydrous dioxane, replace nitrogen three times, slowly add about 3 mL of trimethylsilyl bromide to the reaction system, then heat to 70 ° C and react for 2 hours. After the raw materials are completely reacted, remove the excess solvent by vacuum distillation, add methanol and water to precipitate solids, filter, and slurry the filter cake with ethyl acetate to obtain about 1.4 g of compound (38), yield: 60.8%. MADLI-TOF-MS: 427.54

[0183] Example 9: Synthesis of Compound (43)

[0184]

[0185] Synthesis of compound 43-1:

[0186] Accurately weigh compound 25-1 (14.6 g, 50 mmol), 4-bromoiodobenzene (21.2 g 75 mmol), cuprous iodide (1 g 5 mmol), cesium carbonate (32.6 g 100 mmol) and add them to a 500 mL three-necked flask in sequence, add about 300 mL of anhydrous DMF, replace nitrogen three times and heat to 140 ° C for 6 hours, after the raw materials react completely, add water to quench and extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate and remove excess solvent by vacuum distillation, mix with silica gel column chromatography, eluent is PE: EA = 20: 1 (volume ratio) to obtain about 18.8 g of compound 43-1, yield: 84.2%. MS: 446.57

[0187] Synthesis of compound 43-2:

[0188] Accurately weigh compound 43-1 (4.5 g, 10 mmol), add it to a 100 mL three-necked flask, add 30 mL of anhydrous dioxane (about 50 mL), then add palladium acetate (0.03 g), dppf (0.03 g), triethyl phosphite (3.5 mL), replace nitrogen three times and heat to 100 ° C for 12 hours, after the raw material is completely reacted, dilute with water and extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate and remove excess solvent by vacuum distillation, mix with silica gel column chromatography, eluent is EA to obtain about 4.5 g of compound 43-2, yield: 89.6%. MS: 503.66

[0189] Synthesis of compound (43):

[0190] Accurately weigh compound 43-2 (4.5 g, 9 mmol) in a 100 mL three-necked flask, add about 50 mL of anhydrous dioxane, replace nitrogen three times, slowly drop about 5 mL of trimethylsilyl bromide into the reaction system, then heat to 70 ° C and react for 2 hours. After the raw materials are completely reacted, remove the excess solvent by vacuum distillation, add methanol and water to precipitate solids, filter, and slurry the filter cake with ethyl acetate to obtain about 2.1 g of compound (43), yield: 52.1%. MADLI-TOF-MS: 447.52

[0191] Device preparation and characterization

[0192] 1. Preparation and characterization of OPV devices

[0193] The preparation of OPV device embodiment 1 includes the following steps:

[0194] Cleaning of ITO substrate containing anode: Clean the ITO conductive glass anode layer, then ultrasonically clean the ITO substrate with deionized water, acetone, and isopropyl alcohol for 15 minutes, and then treat it in a plasma cleaner for 5 minutes to further clean the surface and improve surface wettability.

[0195] Preparation of hole transport layer: Compound (1) was dissolved in methanol to prepare a hole transport layer solution (0.5 mg / mL), and the solution was spin-coated on a clean ITO surface in air at a speed of 3000 rpm for 30 seconds, followed by annealing at 100°C for 15 minutes. The annealed and cooled substrate was dynamically cleaned twice with methanol to remove compound (1) not anchored on ITO.

[0196] Preparation of the photoactive layer: The prepared device containing the hole transport layer is placed in a glove box, and the photoactive layer material is evenly spin-coated on the anode buffer layer at a rotation speed of 1800-4000 rpm to obtain an active material layer with a thickness of 100 nm; wherein the donor material in the photoactive layer material is selected from PM6, and the acceptor material is selected from L8-BO, wherein: PM6:L8-BO are dissolved in chloroform at a mass ratio of 1:1.2, with a concentration of 16.5 mg / mL, and 0.25% by volume of 1,8-diiodooctane (DIO) is added as an additive.

[0197] Preparation of electron transport layer: After thermal annealing on a hot plate at 100° C. for 10 min, the electron transport layer material PDINN (PDINN was dissolved in methanol with a concentration of 1.0 mg / mL) was evenly spin-coated on the photoactive layer with a thickness of 10 nm.

[0198] Cathode layer preparation: In high vacuum (1×10 -6 Ag was evaporated onto the electron transport layer at 400 mbar to form a cathode layer with a thickness of 100 nm.

[0199] Device Encapsulation: The devices were encapsulated with UV-curable resin in a nitrogen glove box.

[0200] OPV device examples 2-9:

[0201] OPV device embodiments 2-9 use compound (6), compound (12), compound (21), compound (25), compound (30), compound (33), compound (38), and compound (43) as hole transport materials to prepare OPV devices; the rest of the preparation methods of OPV device embodiments 2-9 are the same as those of OPV device embodiment 1, the only difference being that different hole transport layer materials are used. The selection of hole transport materials for specific OPV device embodiments is detailed in Table 1.

[0202] The prepared OPV device was tested for performance. Under the irradiation of AM1.5G standard light of a solar simulator (SS-F5-3A), the battery current-voltage curve was tested and the photoelectric conversion efficiency was calculated as shown in Table 1:

[0203] Table 1

[0204] Hole transport layer materials Photoelectric conversion efficiency (%) OPV device example 1 Compound (1) 17.42 OPV device example 2 Compound (6) 16.86 OPV device example 3 Compound (12) 17.94 OPV device example 4 Compound (21) 16.58 OPV device example 5 Compound (25) 17.23 OPV Device Example 6 Compound (30) 17.04 OPV device example 7 Compound (33) 16.47 OPV device example 8 Compound (38) 16.95 OPV device example 9 Compound (43) 16.04

[0205] 2. Preparation and Characterization of PSC Devices

[0206] Preparation of PSC Device Example 1:

[0207] Cleaning of ITO substrate containing anode: Clean the ITO conductive glass anode layer, then ultrasonically clean the ITO substrate with deionized water, acetone, and isopropyl alcohol for 15 minutes, and then treat it in a plasma cleaner for 5 minutes to further clean the surface and improve surface wettability.

[0208] Preparation of hole transport layer: Compound (1) was dissolved in methanol to prepare a hole transport layer solution (0.5 mg / mL), and the solution was spin-coated on a clean ITO surface in air at a speed of 3000 rpm for 30 seconds, followed by annealing at 100°C for 15 minutes. The annealed and cooled substrate was dynamically cleaned twice with methanol to remove compound (1) not anchored on ITO.

[0209] Preparation of the photoactive layer: In a glove box (inert gas atmosphere), the perovskite active layer solution is evenly spin-coated on the hole transport layer to obtain a photoactive material layer; wherein the perovskite active layer solution is prepared by dissolving FAI, PbI2, and MACl in a mixed solution of DMF:DMSO = 9:1 (volume ratio) (concentration is 1M) to form a precursor solution FAPbI3. After stirring at room temperature for more than 8 hours, the perovskite film is prepared by spin coating.

[0210] The preparation method of the perovskite active layer solution is as follows: 240.8 mg FAI, 677.7 mg PbI2, and 28.4 mg MACl are dissolved in 1 ml DMF:DMSO = 9:1 (volume ratio) mixed solution to form a precursor solution FAPbI3. After stirring evenly, the perovskite film is prepared by spin coating: the perovskite is prepared by a two-step process of spin coating at 1000 rpm for 10s and 5000 rpm for 30s, and the acceleration is the same as the rotation speed. 10s after the start of the second step of spin coating, 1000 μl of anti-solvent ether solution is dropped on the perovskite surface, and annealed at 150 ° C for 15 minutes at 30% humidity in the air. Then, 2-thiopheneethylammonium chloride TEACl (concentration 1 mg / ml) dissolved in IPA is spin coated at a speed of 3000 rpm for 30s, and annealed at a temperature of 110 ° C for 3 minutes to form a surface passivation layer on the perovskite surface.

[0211] Preparation of electron transport layer and hole blocking layer: PCBM was dissolved in chlorobenzene at a concentration of 20 mg / ml to prepare a PCBM solution, and the PCBM solution was evenly spin-coated on the photoactive layer at a spin-coating speed of 1500-2500 rpm. After annealing at 60°C, an electron transport layer with a thickness of 30 nm was obtained. A saturated solution of BCP (solvent is isopropanol) was filtered and spin-coated on the electron transport layer to form a hole blocking layer, wherein the spin-coating condition was spin-coating at a speed of 2000 rpm for 30 seconds.

[0212] Cathode layer preparation: In high vacuum (1×10 -6 Under the condition of 100 mbar, a silver electrode with a thickness of 100 nm was evaporated on the surface of the hole blocking layer.

[0213] Packaging: The device was packaged with ultraviolet curing resin in a nitrogen glove box to obtain a perovskite solar cell device.

[0214] Preparation of PSC Device Examples 2-4:

[0215] PSC device examples 2-4 use compounds (12), (25), and (30) as hole transport materials in sequence to prepare PSC devices. The preparation methods of PSC device examples 2-4 are the same as those of PSC device example 1, except that different hole transport layer materials are used. See Table 2 for details.

[0216] The prepared PSC device was tested for performance. Under the irradiation of AM1.5G standard light from a solar simulator (SS-F5-3A), the battery current-voltage curve was tested and the photoelectric conversion efficiency was calculated as shown in Table 2:

[0217] Table 2

[0218] Hole transport layer materials Photoelectric conversion efficiency (%) PSC Device Example 1 Compound (1) 23.67 PSC device embodiment 2 Compound (12) 24.19 PSC device embodiment 3 Compound (25) 24.02 PSC Device Example 4 Compound (30) 23.14

[0219] It can be seen from the device test data in Table 1 and Table 2 that the heterocyclic organic compounds described in the present invention as hole transport materials show excellent devices both in organic solar cells and perovskite cells. Therefore, the heterocyclic organic compounds described in the present invention are universal as hole transport materials and are suitable for many types of solar cell devices.

[0220] The heterocyclic organic compound described in the present invention has excellent hole extraction performance, thereby ensuring the effective transfer and extraction of holes. When it is used as a hole transport material in an organic solar cell device, the photoelectric conversion efficiency can be close to 18%; when it is used as a hole transport material in a perovskite solar cell device, the photoelectric conversion efficiency exceeds 24%.

[0221] The preferred specific embodiments of the present invention are described in detail above. It should be understood that a person skilled in the art can make many modifications and changes based on the concept of the present invention without creative work. Therefore, any technical solution that can be obtained by a person skilled in the art through logical analysis, reasoning or limited experiments based on the concept of the present invention on the basis of the prior art should be within the scope of protection determined by the claims.

Claims

1. A heterocyclic organic compound, characterized in that: the heterocyclic organic compound is selected from the structure shown in the general formula (I) or the general formula (II): in: x is selected from 0 or 1; Each occurrence of R1, R2, and R3 is independently selected from -D, -F, -Cl, -Br, -I, cyano, hydroxyl, nitro, amine, straight-chain alkyl having 1-20 C atoms, straight-chain alkoxy having 1-20 C atoms, straight-chain alkylthio having 1-20 C atoms, branched or cyclic alkyl having 3-20 C atoms, branched or cyclic alkoxy having 3-20 C atoms, branched or cyclic alkylthio having 3-20 C atoms, substituted or unsubstituted aromatic group having 6-20 carbon atoms, or substituted or unsubstituted heteroaromatic group having 5-20 ring atoms, or a group formed by a combination of the above groups; L is independently selected from a straight chain alkyl group having 1 to 20 C atoms, a branched chain alkyl group having 3 to 20 C atoms, a substituted or unsubstituted aromatic group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 20 ring atoms; n, at each occurrence, is independently selected from 0, 1, 2, 3, 4, 5 or 6; m is independently selected from 0, 1, 2, 3 or 4; v is independently selected from 0, 1, 2 or 3; The "substituted or unsubstituted" means that the defined group is not substituted or is substituted by one or more substituents R, wherein each occurrence of R is independently selected from -D, -F, -Cl, -Br, -I, cyano, hydroxyl, nitro, amine, straight-chain alkyl having 1-20 C atoms, straight-chain alkoxy having 1-20 C atoms, straight-chain alkylthio having 1-20 C atoms, branched or cyclic alkyl having 3-20 C atoms, branched or cyclic alkoxy having 3-20 C atoms, branched or cyclic alkylthio having 3-20 C atoms, aromatic groups having 6-20 carbon atoms, or heteroaromatic groups having 5-20 ring atoms, or groups formed by combinations of the above groups.

2. The heterocyclic organic compound according to claim 1, characterized in that: The heterocyclic organic compound is selected from the structure shown in any one of the general formulas (III-1) to (III-4): Wherein: in the general formula (III-1) or the general formula (III-2), L is independently selected from a straight-chain alkyl group having 1 to 10 C atoms, a branched-chain alkyl group having 3 to 10 C atoms, a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms; In the general formula (III-3) or (III-4), L is independently selected from a substituted or unsubstituted aromatic group having 6 to 10 carbon atoms, or a substituted or unsubstituted heteroaromatic group having 5 to 10 ring atoms.

3. A heterocyclic organic compound according to claim 2, characterized in that: In the general formula (III-1) or the general formula (III-2), L is selected from -(CH2)-, -(CH2)-(CH2)-, -(CH2)-(CH2)-(CH2)-(CH2)-, -(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-(CH2)-, phenyl, pyridyl, thienyl, benzothiadiazolyl or biphenyl; In the general formula (III-3) or (III-4), L is selected from phenyl, pyridyl, thienyl, benzothiadiazolyl or biphenyl.

4. The heterocyclic organic compound according to any one of claims 1 to 3, characterized in that: The heterocyclic organic compound is selected from any one of the structures shown in general formula (IV-1) to (IV-8):

5. The heterocyclic organic compound according to claim 4, characterized in that: Each occurrence of R1 and R2 is independently selected from -D, -F, -Cl, -Br, -I, cyano, hydroxyl, nitro, amine, straight-chain alkyl having 1-6 C atoms, straight-chain alkoxy having 1-6 C atoms, straight-chain alkylthio having 1-6 C atoms, branched or cyclic alkyl having 3-6 C atoms, branched or cyclic alkoxy having 3-6 C atoms, branched or cyclic alkylthio having 3-6 C atoms, phenyl, pyridyl, thienyl, furanyl, or a group formed by a combination of the above groups.

6. The heterocyclic organic compound according to claim 1, characterized in that: The heterocyclic organic compound is selected from any of the following structures:

7. A composition, characterized in that: The composition comprises at least one heterocyclic organic compound as claimed in any one of claims 1 to 6, and at least one organic solvent.

8. A hole transport material, characterized in that: The hole transport material is selected from the heterocyclic organic compound according to any one of claims 1 to 6.

9. An organic electronic device comprising at least one functional layer, characterized in that: The functional layer material comprises the heterocyclic organic compound as claimed in any one of claims 1 to 6.

10. An organic electronic device, characterized in that: The organic electronic device comprises an anode, a cathode, a photoactive layer between the cathode and the anode, an electron transport layer between the cathode and the photoactive layer, and a hole transport layer between the anode and the photoactive layer; the hole transport layer comprises a heterocyclic organic compound as described in any one of claims 1 to 6 or the hole transport layer is prepared from a composition as described in claim 7.

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