An organic compound containing an anchoring group and its use

Abstract

The present application relates to an organic compound containing an anchoring group and its application, and belongs to the field of organic materials. The organic compound according to the present application can be applied to an organic electronic device as an anode buffer layer material to improve the photoelectric conversion performance of the organic electronic device.

Description

Technical Field

[0001] This invention relates to organic optoelectronic materials, and in particular to an organic compound containing an anchoring group and its applications. Background Technology

[0002] Solar energy, as the world's largest renewable and clean energy source, is environmentally friendly and its utilization can help alleviate human energy needs. Two important branches of solar cells—perovskite solar cells and organic solar cells—have attracted widespread attention as next-generation photovoltaic technologies due to their excellent photovoltaic efficiency, simple fabrication methods, and low production costs.

[0003] Anode buffer layer materials are functional modification materials used at the anode / organic layer interface of solar cells. They can suppress the quenching of photogenerated excitons at the anode / organic layer interface and improve the transport of photogenerated holes from the highest occupied molecular orbital (HOMO) level of the donor to the anode conduction band. Therefore, selecting a suitable anode buffer layer material plays a crucial role in optimizing the power conversion efficiency and device performance of solar cells. Currently, commonly used anode buffer layer materials in perovskite solar cells include poly(3,4-ethylenedioxythiophene)-polystyrene sulfonic acid (PEDOT:PSS), poly[bis(4-phenyl)(2,4,6-trimethylphenyl)amine] (PTAA), Spiro-OMeTAD, nickel oxide (NiOX), copper oxide (CuOX), cuprous thiocyanate (CuSCN), and poly[bis(4-phenyl)(4-butylphenyl)amine] (poly-TPD), etc.; the commonly used anode buffer layer material in organic solar cells is PEDOT:PSS. However, the high price of existing anode buffer layer materials makes them difficult to mass-produce, which affects the improvement of the photoelectric conversion efficiency and stability of the devices, thus limiting the further development of photovoltaic technology.

[0004] In recent years, anode buffer layer materials containing anchoring groups have begun to attract widespread attention. These are molecularly modified layers that utilize anchoring groups in the molecule to react with electrode layers or oxide layers such as ITO, forming a self-assembly property. These molecules mainly consist of an anchoring group at the head, a linking group in the middle, and a functional group at the tail. They possess advantages such as simple structure, ease of synthesis, high transmittance, and adjustable work function.

[0005] However, the selection of existing organic small molecule anode buffer layer materials containing anchoring groups is currently limited, and they cannot fully match different types of active layer materials. Furthermore, the stability of devices after application still needs improvement. Therefore, the design and development of novel organic small molecule materials containing anchoring groups is of great significance for realizing a new generation of efficient and stable solar cell devices. Summary of the Invention

[0006] The purpose of this invention is to provide a novel small organic molecule compound containing an anchoring group, which can be applied to the anode buffer layer of organic electronic devices to improve the stability and photoelectric conversion performance of the devices.

[0007] To achieve the above objectives, the present invention adopts the following technical solution:

[0008] An organic compound containing an anchoring group has a structure as shown in general formula (I):

[0009]

[0010] in,

[0011] L is selected from substituted or unsubstituted aromatic groups having 6 to 10 carbon atoms, or from substituted or unsubstituted heteroaromatic groups having 5 to 10 cyclic atoms.

[0012] X is selected from single bonds, O, S, or CR4R5;

[0013] Z is selected from single bonds, O, S, or CR6R7;

[0014] R1, R2, and R3, each time appearing independently, are selected from -D, straight-chain alkyl groups having 1 to 20 carbon atoms, straight-chain alkoxy groups having 1 to 20 carbon atoms, straight-chain alkylthio groups having 1 to 20 carbon atoms, branched or cyclic alkyl groups having 3 to 20 carbon atoms, branched or cyclic alkoxy groups having 3 to 20 carbon atoms, branched or cyclic alkylthio groups having 3 to 20 carbon atoms, cyano, hydroxy, nitro, -Cl, -Br, -F, -I, substituted or unsubstituted aromatic groups having 6 to 10 ring atoms, substituted or unsubstituted heteroaromatic groups having 5 to 10 ring atoms, or groups formed by combinations of the above groups;

[0015] m is selected from 0, 1, 2, 3, or 4; n is selected from 0, 1, 2, 3, or 4; r is selected from 0, 1, 2, 3, or 4;

[0016] R4, R5, R6, and R7 are independently selected from straight-chain alkyl groups having 1 to 10 carbon atoms, or branched or cyclic alkyl groups having 3 to 10 carbon atoms.

[0017] The term "substituted or unsubstituted" means that the defined group is not substituted, or is substituted by one or more R groups. * Replace; where R *Each occurrence is independently selected from -D, cyano, hydroxy, nitro, -Cl, -Br, -F, -I, straight-chain alkyl with 1 to 10 carbon atoms, branched or cyclic alkyl with 3 to 10 carbon atoms, straight-chain alkoxy with 1 to 10 carbon atoms, branched or cyclic alkoxy with 3 to 10 carbon atoms, straight-chain alkylthio with 1 to 10 carbon atoms, branched or cyclic alkylthio with 3 to 10 carbon atoms, aromatic groups with 6 to 10 carbon atoms, or heteroaromatic groups with 5 to 10 cyclic atoms, or groups formed by combinations of the above groups. In this invention, "one or more" means one, two, three, four, or more than four.

[0018] When m is chosen as 2, 3, or 4, the choices of each R1 group can be the same or different; when n is chosen as 2, 3, or 4, the choices of each R2 group can be the same or different; when r is chosen as 2, 3, or 4, the choices of each R3 group can be the same or different. Furthermore, the choices of R1, R2, and R3 groups can be the same or different.

[0019] When multiple R * When replacing, R * The selected functional groups may be the same or different.

[0020] In this invention, in the general formula (I) Selected from the following structure:

[0021]

[0022] In this context, * indicates a connection site.

[0023] In this invention, when the position of the substituent on the ring is not fixed, it means that it can be connected to any of the corresponding optional sites on the ring; for example, in one embodiment: When r = 1, it can be represented as When r = 2, it can be represented as When r = 3, it can be represented as When r = 4, it can be represented as * indicates a connection site with X, and # indicates a connection site with N.

[0024] Similarly, When n=1, it can be represented as When n=2, it can be represented as When n = 3, it can be represented as When n=4, it can be represented as * indicates a connection site with Z; # indicates a connection site with N.

[0025] Similarly, When m = 1, it can represent When m = 2, it can be represented as When m = 3, it can be represented as When m = 4, it can be represented as * indicates a connection site with Z; # indicates a connection site with N.

[0026] In one embodiment, R4, R5, R6, and R7 are independently selected from straight-chain alkyl groups having 1 to 6 carbon atoms, or branched or cyclic alkyl groups having 3 to 6 carbon atoms.

[0027] In one embodiment, R4, R5, R6, and R7 are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, and 2-ethylbutyl.

[0028] Preferably, R4, R5, R6, and R7 are all selected from methyl groups.

[0029] In one embodiment, X and Z are selected from the same group.

[0030] Furthermore, the organic compound containing the anchoring group provided according to the present invention has a structure as described in any one of general formulas (II-1)-(II-4):

[0031]

[0032]

[0033] In one embodiment, L is selected from R. * Substituted or unsubstituted phenyl, R * Substituted or unsubstituted biphenyl, R * Substituted or unsubstituted thiophene group, R * Substituted or unsubstituted bithienyl group, R * Substituted or unsubstituted furanyl groups, by R * Substituted or unsubstituted bifuranyl, R * Substituted or unsubstituted benzothiadiazole group, R * Substituted or unsubstituted phenylbibenzothiadiazole group. R * The meaning is the same as described above.

[0034] Furthermore, L is selected from the following structure:

[0035]

[0036] Where: * indicates a connection site.

[0037] In one specific embodiment, L is selected from

[0038] In one embodiment, R1, R2, and R3 each time they appear, are independently selected from -D, a straight-chain alkyl group having 1 to 6 carbon atoms, a straight-chain alkoxy group having 1 to 6 carbon atoms, a straight-chain alkylthio group having 1 to 6 carbon atoms, a branched or cyclic alkyl group having 3 to 6 carbon atoms, a branched or cyclic alkoxy group having 3 to 6 carbon atoms, a branched or cyclic alkylthio group having 3 to 6 carbon atoms, a cyano group, a hydroxyl group, a nitro group, -Cl, -Br, -F, -I, an aromatic group having 6 to 10 ring atoms, a heteroaromatic group having 5 to 10 ring atoms, or a group formed by a combination of the above groups.

[0039] In one embodiment, R1 and R2, each time they appear, are selected from the same or different groups: -D, a straight-chain alkyl group having 1 to 4 carbon atoms, a branched alkyl group having 3 to 4 carbon atoms, a straight-chain alkoxy group having 1 to 4 carbon atoms, a straight-chain alkylthio group having 1 to 4 carbon atoms, a cyano group, a hydroxyl group, a nitro group, -Cl, -Br, -F, -I, or a phenyl group, or a group formed by a combination of the above groups.

[0040] In one embodiment, each occurrence of R3 is independently selected from -D, a straight-chain alkyl group having 1 to 6 carbon atoms, a straight-chain alkoxy group having 1 to 6 carbon atoms, a straight-chain alkylthio group having 1 to 6 carbon atoms, a branched or cyclic alkyl group having 3 to 6 carbon atoms, a branched or cyclic alkoxy group having 3 to 6 carbon atoms, a branched or cyclic alkylthio group having 3 to 6 carbon atoms, a cyano group, a hydroxyl group, a nitro group, -Cl, -Br, -F, -I, a phenyl group, a pyridyl group, a pyrimidinyl group, a triazine group, or a group formed by a combination of the above groups.

[0041] In one specific embodiment, each occurrence of R3 is independently selected from phenyl, cyano, -Cl, -Br, -F, -I, methoxy, methylthio, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, and one or more methoxy-substituted phenyl groups.

[0042] In one embodiment, R3 is selected from phenyl groups substituted with one or more straight-chain alkoxy groups having 1 to 6 carbon atoms; further, each occurrence of R3 is independently selected from phenyl groups substituted with one or more methoxy groups. When R3 is selected from phenyl groups substituted with one or more methoxy groups, the performance of organic electronic devices can be improved because: the introduction of phenyl groups can enhance the conjugation system of the tail functional groups, which is beneficial for charge transport and increases the thermal stability of the material; the addition of alkoxy groups can prevent direct contact between the substrate and the active layer; it is beneficial for increasing the adsorption density of organic compounds containing anchoring groups; the increased adsorption density of organic compounds containing anchoring groups can improve the interface passivation capability, thereby improving the performance of organic electronic devices.

[0043] In a preferred embodiment, r is selected from 0 or 1. Further, when r is selected from 1, preferably, the organic compound containing the anchoring group has a structure as described in any of general formulas (III-1)-(III-4):

[0044]

[0045] In a preferred embodiment, R3 in general formulas (III-1)-(III-4) is independently selected from phenyl, cyano, -Cl, -Br, -F, -I, methoxy, methylthio, methyl, ethyl, propyl, isopropyl, butyl, tert-butyl, and one or more methoxy-substituted phenyl groups.

[0046] In this invention, "alkyl" can refer to a straight-chain, branched, and / or cyclic alkyl group. The number of carbon atoms in a straight-chain alkyl group can be 1 to 20, preferably 1 to 10, more preferably 1 to 6. The number of carbon atoms in a branched alkyl group can be 3 to 20, preferably 3 to 10, more preferably 3 to 6. Examples of alkyl groups include, but are not limited to: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2-hexyl, 3-hexyl, and 3-methylpentyl.

[0047] In this invention, "alkoxy" refers to -O-(alkyl), wherein the definition of alkyl is as described herein, and non-limiting examples of alkoxy include: methoxy (-O-CH3 or -OMe), ethoxy (-O-CH2CH3 or -OEt), propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy (-OC(CH3)3 or -OtBu), pentooxy, 2-pentoxy, isopentoxy, neopentoxy, hexoxy, 2-hexoxy, 3-hexoxy, and 3-methylpentoxy.

[0048] In this invention, "alkathioyl" refers to -S-(alkyl), wherein the definition of alkyl is as described herein, and non-limiting examples of alkathioyl include: methylthioyl (-S-CH3 or -SMe), ethylthioyl (-S-CH2CH3 or -SEt), propylthioyl, isopropylthioyl, n-butylthioyl, sec-butylthioyl, tert-butylthioyl (-SC(CH3)3 or -StBu), pentylthioyl, 2-pentylthioyl, isopentylthioyl, neopentylthioyl, hexylthioyl, 2-hexylthioyl, 3-hexylthioyl, and 3-methylpentylthioyl.

[0049] In this invention, the "aromatic group having 6 to 10 carbon atoms" is preferably phenyl or naphthyl; the "heteroaromatic group having 5 to 10 ring atoms" is preferably thiophene, furanyl, pyridyl, pyrimidinyl, triazine, benzothiophene, benzofuranyl, benzothiadiazolyl, quinolinyl, isoquinolinyl, but is not limited thereto.

[0050] In one specific embodiment, an organic compound containing an anchoring group according to the present invention may be selected from, but is not limited to, the following structures:

[0051]

[0052]

[0053]

[0054] The above lists some specific chemical structures of organic compounds containing anchoring groups as shown in general formula (I) according to the present invention. However, the present invention is not limited to these listed chemical structures. Any structure based on general formula (I) with substituents as defined above should be included.

[0055] The present invention further relates to an anode buffer layer material, said anode buffer layer material being selected from at least one organic compound containing an anchoring group as described above.

[0056] The present invention further relates to a composition comprising at least one of the aforementioned organic compounds containing anchoring groups, and at least one organic solvent. In one embodiment, the organic solvent is selected from alcohols; in another embodiment, the alcohol is selected from at least one of methanol, ethanol, isopropanol, ethylene glycol, etc. In a preferred embodiment, the organic solvent is selected from ethanol.

[0057] The present invention further relates to an organic electronic device comprising at least one functional layer, wherein the functional layer material comprises at least one organic compound containing an anchoring group as described above.

[0058] Preferably, the organic electronic device comprises at least a cathode, an anode, a photoactive layer located between the cathode and the anode, and an anode buffer layer located between the anode and the photoactive layer, wherein the anode buffer layer material comprises at least one organic compound containing an anchoring group as described above.

[0059] Preferably, the organic electronic device further includes a cathode buffer layer located between the cathode and the photoactive layer.

[0060] Preferably, the anode buffer layer includes a first anode buffer layer and / or a second anode buffer layer, wherein the first anode buffer layer is located between the anode and the photoactive layer, and the second anode buffer layer is located between the first anode buffer layer and the photoactive layer.

[0061] Preferably, the cathode buffer layer includes a first cathode buffer layer and / or a second cathode buffer layer, wherein the first cathode buffer layer is located between the cathode and the photoactive layer, and the second cathode buffer layer is located between the first cathode buffer layer and the photoactive layer.

[0062] Preferably, the organic electronic device is selected from, but not limited to, organic solar cells (OPV), perovskite solar cells (PSC), organic light-emitting diodes (OLED), organic photodetectors (OPD), etc. Further, the organic electronic device is selected from organic solar cells (OPV) or perovskite solar cells (PSC).

[0063] 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 besides the cathode buffer layer and the anode buffer layer, such as a charge injection layer and / or a charge blocking layer.

[0064] This invention does not impose any particular limitation on the materials of the thin films in the organic electronic devices, and substances known in the art can be used.

[0065] The organic electronic devices provided by this invention can be used in various devices, such as automotive and building-integrated photovoltaics (BIPV), electronic shelf labels, indoor photovoltaics, the Internet of Things, smart agriculture, etc., but are not limited thereto.

[0066] Compared with the prior art, the present invention has at least one of the following significant advantages:

[0067] ① The tail functional groups of the organic compounds protected by this invention contain two This group has good hole transport capability and a large rigid planar structure. At the same time, the tail functional group of the compound protected by this invention has a large π-conjugated system, which can effectively adjust the molecular packing. Therefore, the organic compound containing the anchoring group of this invention has excellent hole transport performance and good film-forming properties, thereby improving the photoelectric conversion performance of the device.

[0068] ② This invention uses a cyanocarboxylic acid group as an anchoring group. The carboxylic acid group has strong binding strength, which is beneficial for improving the assembly rate, density, and compactness of self-assembled monolayers, thereby enhancing charge collection and suppressing interfacial recombination. The introduction of the strongly electron-withdrawing cyano group increases the deprotonation ability of the carboxylic acid and the hydrophilicity of the anchoring group, giving this small molecule material unique amphiphilic characteristics and making it readily soluble in solvents of various polarities. This ultra-wide solvent window provides the material with flexible processing methods and a wide range of applications.

[0069] ③ The organic compound protected by this invention has an asymmetric structure, which exhibits a better dipole moment, thereby producing an ideal energy arrangement and improving the extraction and migration ability of holes;

[0070] ④ This invention utilizes a simple synthesis method to prepare the organic small molecule self-assembled material shown in formula (I). This type of self-assembled material has the advantages of good stability, easy processing, no dopants, and low cost. At the same time, its excellent charge selectivity enables the acquisition of efficient and stable organic electronic devices. Attached Figure Description

[0071] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0072] Figure 1 This is a schematic diagram of the structure of an organic solar energy device provided in an embodiment of this application.

[0073] In the diagram, 101 is the substrate, 102 is the anode, 103 is the anode buffer layer, 104 is the active layer, 105 is the cathode buffer layer, and 106 is the cathode. Detailed Implementation

[0074] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative and not intended to limit the invention.

[0075] In this invention, organic photovoltaic devices, organic solar cells, and OPV have the same meaning and can be used interchangeably.

[0076] In this invention, perovskite photovoltaic devices, perovskite solar cells, and PSCs have the same meaning and can be used interchangeably.

[0077] In this invention, when the same substituent appears multiple times, it can be independently selected from the same or different groups. If the general formula contains multiple R, then R can be independently selected from the same or different groups.

[0078] 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. For example, the benzene ring has 6 ring atoms, the naphthalene ring has 10 ring atoms, and the thiophene group has 5 ring atoms.

[0079] In this invention, the phrases "independently selected" and "selected from the same or different groups" indicate 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.

[0080] 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 items of the listed groups.

[0081] 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.

[0082] 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.

[0083] 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.

[0084] The present invention provides a method for synthesizing an organic compound containing an anchoring group, the specific steps of which are as follows:

[0085]

[0086] The main steps of the method are:

[0087] Step 1: Accurately weigh certain amounts of compounds A-1 and A-2, and sequentially add appropriate amounts of sodium tert-butoxide, bis(dibenzylacetone)palladium, and 4,5-bisdiphenylphosphine-9,9-dimethyloxanthracene to a reaction flask. Add an appropriate amount of toluene, purge with nitrogen three times, and then heat to 100℃ and react for 12 h. Cool to room temperature, extract with water and ethyl acetate, and remove excess solvent from the organic phase by vacuum distillation. Purify the crude product by column chromatography to obtain compound A-3.

[0088] Step 2: Accurately weigh a certain amount of compounds A-3 and A-4, add an appropriate amount of toluene, add piperidine to the reaction flask, purge with nitrogen three times, and then heat to 110℃ and react for 12 h. After cooling to room temperature, remove the organic solvent by rotary evaporation. Dissolve the remaining product in dichloromethane, wash with water, collect the organic phase, and dry it with anhydrous sodium sulfate. Remove excess solvent by vacuum distillation. The crude product is purified by column chromatography to obtain compound A.

[0089] The present invention will now be described in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the appended claims summarize the scope of the present invention. Under the guidance of the inventive concept, those skilled in the art should realize that any 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.

[0090] Compound preparation:

[0091] Example 1: Synthesis of compound (1)

[0092]

[0093] Synthesis of compounds 1-3:

[0094] Accurately weigh compound 1-1 (16.6 g, 50 mmol), compound 1-2 (9.3 g, 50 mmol), sodium tert-butoxide (9.6 g, 100 mmol), bis(benzylacetone)palladium (0.28 g, 0.5 mmol), and 4,5-bisdiphenylphosphine-9,9-dimethyloxanthracene (0.58 g, 1 mmol) into a 500 mL three-necked flask. Add 150 mL of toluene, purge with nitrogen three times, and then heat to 100 °C and react for 12 h. Cool to room temperature, extract with water and ethyl acetate, and remove excess solvent from the organic phase by vacuum distillation. Purify the crude product by column chromatography (PE:DCM = 10:1, v / v) to give approximately 18.6 g of compound 1-3, yield: 85.6%. MS: 436.78.

[0095] Synthesis of compound (1):

[0096] Accurately weigh compounds 1-3 (10.9 g, 25 mmol) and compounds 1-4 (4.3 g, 50 mmol) into 150 mL toluene and 30 mL piperidine in a 250 mL three-necked flask. After purging with nitrogen three times, the mixture was heated to 110 °C and reacted for 12 h. After cooling to room temperature, the organic solvent was removed by rotary evaporation. The remaining product was dissolved in dichloromethane, washed with water, and the organic phase was collected and dried over anhydrous sodium sulfate. Excess solvent was removed by vacuum distillation. The crude product was subjected to column chromatography with EA (1% acetic acid added, v / v) to give approximately 5.4 g of compound (1), yield: 42.8%. MALDI-TOF MS: 504.25.

[0097] Example 2: Synthesis of compound (4)

[0098]

[0099] Synthesis of compound 4-2:

[0100] Accurately weigh 30.8 g (75 mmol) of compound 4-1, 1.5 g (7.5 mmol) of cuprous iodide, and 4.5 g (82.5 mmol) of sodium methoxide into a 500 mL three-necked flask. Add approximately 300 mL of N,N-dimethylformamide, purge with nitrogen three times, and heat to reflux. React for 16 h. After the starting material has completely reacted, wash with water, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Analyze the crude product by column chromatography (PE:DCM = 25:1, v / v) to give approximately 22.3 g of compound 4-2. Yield: 82.5%. MS: 363.11.

[0101] Synthesis of compound 4-3:

[0102] Compound 4-2 (18.1 g, 50 mmol), compound 1-2 (9.3 g, 50 mmol), sodium tert-butoxide (9.6 g, 100 mmol), bis(benzylacetone)palladium (0.28 g, 0.5 mmol), and 4,5-bisdiphenylphosphine-9,9-dimethyloxanthracene (0.58 g, 1 mmol) were accurately weighed and added sequentially to a 500 mL three-necked flask. The crude product was prepared according to the synthetic method for compound 1-3. Purification was achieved by column chromatography with PE:DCM = 15:1 (v / v), yielding approximately 17 g of compound 4-3, yield: 72.9%. MS: 466.85.

[0103] Synthesis of compound (4):

[0104] Accurately weigh 11.7 g (25 mmol) of compound 4-3 and 4.3 g (50 mmol) of compound 1-4 into 150 mL of toluene and 30 mL of piperidine in a 250 mL three-necked flask. Prepare the crude product according to the synthesis method of compound (1). Analyze the crude product by column chromatography with EA (1% acetic acid added by volume) to obtain approximately 5.3 g of compound (4), yield: 39.5%. MALDI-TOF MS: 533.84.

[0105] Example 3: Synthesis of compound (8)

[0106]

[0107] Synthesis of compound 8-2:

[0108] Accurately weigh compound 4-1 (30.8 g, 75 mmol), compound 8-1 (11.3 g, 75 mmol), Pd(PPh3)4 (1.7 g, 1.5 mmol), and potassium carbonate (20.7 g, 150 mmol) and add them sequentially to a 1000 mL three-necked flask, followed by 400 mL of toluene and 100 mL of water. After purging with nitrogen three times, the entire reaction system was heated to reflux and reacted for 20 h. After cooling the reaction solution, the product was poured into water and extracted with EA, then dried over anhydrous magnesium sulfate. The solvent was removed by rotary evaporation of the organic phase, and the product was separated by silica gel column chromatography using PE:EA = 15:1 (v / v) as eluent to obtain approximately 27.6 g of compound 8-2, with a yield of 83.8%. MS: 438.67.

[0109] Synthesis of compound 8-3:

[0110] Compound 8-2 (21.9 g, 50 mmol), compound 1-2 (9.3 g, 50 mmol), sodium tert-butoxide (9.6 g, 100 mmol), bis(benzylacetone)palladium (0.28 g, 0.5 mmol), and 4,5-bisdiphenylphosphine-9,9-dimethyloxanthracene (0.58 g, 1 mmol) were accurately weighed and added sequentially to a 500 mL three-necked flask. The crude product was prepared according to the synthetic method for compound 1-3. The crude product was purified by column chromatography (PE:DCM = 10:1, v / v) to give approximately 22.1 g of compound 8-3, yield: 81.7%. MS: 542.46.

[0111] Synthesis of compound (8):

[0112] Accurately weigh 13.6 g (25 mmol) of compound 8-3 and 4.3 g (50 mmol) of compound 1-4 into 150 mL of toluene and 30 mL of piperidine in a 250 mL three-necked flask. Prepare the crude product according to the synthesis method of compound (1). The crude product was subjected to column chromatography with EA (1% acetic acid added by volume) to obtain approximately 5.9 g of compound (8), yield: 38.9%. MALDI-TOF MS: 609.67.

[0113] Example 4: Synthesis of compound (24)

[0114]

[0115] Synthesis of compound 24-3:

[0116] Accurately weigh compound 24-1 (34.1 g, 100 mmol), compound 24-2 (18.3 g, 100 mmol), sodium tert-butoxide (19.2 g, 200 mmol), palladium acetate (0.91 g, 4 mmol), and 1,1'-bis(diphenylphosphine)ferrocene (4.4 g, 8 mmol) and add them sequentially to a 1000 mL three-necked flask. Add 500 mL of toluene, purge with nitrogen three times, and then heat to 100 °C and react for 12 h. Cool to room temperature, wash with water, and extract with ethyl acetate. Remove excess solvent from the organic phase by vacuum distillation. Purify the crude product by column chromatography (PE:DCM = 10:1, v / v) to give approximately 26.8 g of compound 24-3, yield: 62%. MS: 433.53

[0117] Synthesis of compound 24-5:

[0118] Compound 24-3 (22.2 g, 50 mmol), compound 24-4 (9.1 g, 50 mmol), Pd(PPh3)4 (1.7 g, 1.5 mmol), and potassium carbonate (13.8 g, 100 mmol) were accurately weighed and added sequentially to a 1000 mL three-necked flask. The product was prepared according to the synthetic method of compound 8-2. The organic phase of the obtained product was removed by rotary evaporation to remove the solvent. Using PE:EA = 10:1 (v / v) as the eluent, the product was separated by silica gel column chromatography to obtain approximately 21.2 g of compound 24-5, with a yield of 84.6%. MS: 50 1.12.

[0119] Synthesis of compound 24-6:

[0120] Compound 24-5 (20 g, 40 mmol), compound 1-2 (7.4 g, 40 mmol), sodium tert-butoxide (9.6 g, 100 mmol), bis(benzylacetone)palladium (0.28 g, 0.5 mmol), and 4,5-bisdiphenylphosphine-9,9-dimethyloxanthracene (0.58 g, 1 mmol) were accurately weighed and added sequentially to a 500 mL three-necked flask. The crude product was prepared according to the synthetic method for compound 1-3. The crude product was purified by column chromatography (PE:DCM = 5:1, v / v) to give approximately 18.7 g of compound 24-6, yield: 77.5%. MS: 605.43.

[0121] Synthesis of compound (24):

[0122] Accurately weigh 15.1 g (25 mmol) of compound 24-6 and 4.3 g (50 mmol) of compound 1-4 into 150 mL of toluene and 30 mL of piperidine in a 250 mL three-necked flask, and prepare the crude product according to the synthesis method of compound (1). The crude product was subjected to column chromatography with EA (1% acetic acid added by volume) to obtain approximately 7.2 g of compound (24), yield: 43.2%. MALDI-TOF MS: 672.07.

[0123] Example 5: Synthesis of compound (34)

[0124]

[0125] Synthesis of compound 34-1:

[0126] Accurately weigh compound 34-0 (48 g, 100 mmol), 2-amino-5-methylthiophenol (13.9 g, 100 mmol), sodium tert-butoxide (19.2 g, 200 mmol), and bis(dibenzylacetone)palladium (1.2 g, 2 mmol) into a 1000 mL three-necked flask. Add approximately 500 mL of anhydrous toluene, purge the mixture three times with nitrogen, and then slowly add a toluene solution of tri-tert-butylphosphine (10% bulk ratio, 11.5 mL). Heat to 100 °C and react overnight. After the reactants have completely reacted, cool to room temperature, dilute with water, and extract with ethyl acetate. Combine the organic phases, dry to anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:EA = 8:1 (v / v) as eluent to obtain approximately 31.3 g of compound 34-1, yield: 63.7%. MS: 491.74

[0127] Synthesis of compound 34-2:

[0128] Accurately weigh compound 34-1 (29.5 g, 60 mmol), potassium carbonate (16.6 g, 120 mmol), and palladium acetate (0.15 g, 0.6 mmol) into a 500 mL three-necked flask. Add approximately 300 mL of DMF, purge with nitrogen three times, and then heat to 140 °C and react overnight. After the reactants have completely reacted, cool to room temperature, wash with water, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Perform silica gel column chromatography with PE:EA = 8:1 (v / v) as the eluent to obtain approximately 19.6 g of compound 34-2, yield: 79.6%. MS: 410.85.

[0129] Synthesis of compound 34-3:

[0130] Compound 34-2 (16.4 g, 40 mmol), compound 1-2 (9.3 g, 50 mmol), sodium tert-butoxide (9.6 g, 100 mmol), bis(benzylacetone)palladium (0.28 g, 0.5 mmol), and 4,5-bisdiphenylphosphine-9,9-dimethyloxanthracene (0.58 g, 1 mmol) were accurately weighed and added sequentially to a 500 mL three-necked flask. The crude product was prepared according to the synthetic method for compound 1-3. The crude product was purified by column chromatography (PE:DCM = 15:1, v / v) to give approximately 15.6 g of compound 34-3, yield: 75.8%. MS: 514.89.

[0131] Synthesis of compound (34):

[0132] Accurately weigh 12.9 g (25 mmol) of compound 34-3 and 4.3 g (50 mmol) of compound 1-4 into 150 mL of toluene and 30 mL of piperidine in a 250 mL three-necked flask, and prepare the crude product according to the synthesis method of compound (1). The crude product was subjected to column chromatography with EA (1% acetic acid added by volume) to obtain approximately 5.4 g of compound (34), yield: 36.9%. MALDI-TOF MS: 581.97.

[0133] Example 6: Synthesis of compound (39)

[0134]

[0135] Synthesis of compound 39-3:

[0136] Accurately weigh compound 39-1 (35.7 g, 100 mmol), compound 39-2 (19.9 g, 100 mmol), sodium tert-butoxide (19.2 g, 200 mmol), palladium acetate (0.91 g, 4 mmol), and 1,1'-bis(diphenylphosphine)ferrocene (4.4 g, 8 mmol) into a 1000 mL three-necked flask. Add 500 mL of toluene, purge with nitrogen three times, and then heat to 100 °C and react for 12 h. Cool to room temperature, wash with water, and extract with ethyl acetate. Remove excess solvent from the organic phase by vacuum distillation. Purify the crude product by column chromatography (PE:DCM = 10:1, v / v) to give approximately 28 g of compound 39-3, yield: 59%. MS: 476.19

[0137] Synthesis of compound 39-4:

[0138] Accurately weigh 23.7 g (50 mmol) of compound 39-3, 1 g (5 mmol) of cuprous iodide, and 4.5 g (82.5 mmol) of sodium methoxide into a 500 mL three-necked flask. Add approximately 300 mL of N,N-dimethylformamide, purge with nitrogen three times, and heat to reflux. React for 16 h. After the starting material has completely reacted, wash with water, extract with ethyl acetate, combine the organic phases, dry with anhydrous sodium sulfate, and remove excess solvent by vacuum distillation. Column chromatography (PE:DCM = 30:1, v / v) yields approximately 17.3 g of compound 39-4. Yield: 81.2%. MS: 426.87

[0139] Synthesis of compound 39-6:

[0140] Compound 39-4 (17.1 g, 40 mmol), compound 39-5 (10.4 g, 40 mmol), sodium tert-butoxide (9.6 g, 100 mmol), bis(benzylacetone)palladium (0.28 g, 0.5 mmol), and 4,5-bisdiphenylphosphine-9,9-dimethyloxanthracene (0.58 g, 1 mmol) were accurately weighed and added sequentially to a 500 mL three-necked flask. The crude product was prepared according to the synthetic method for compounds 1-3. The crude product was purified by column chromatography (PE:DCM = 20:1, v / v) to give approximately 21 g of compound 39-6, yield: 86.4%. MS: 606.67

[0141] Synthesis of compound (39):

[0142] Accurately weigh 15.2 g (25 mmol) of compound 39-6 and 4.3 g (50 mmol) of compound 1-4 into 150 mL of toluene and 30 mL of piperidine in a 250 mL three-necked flask, and prepare the crude product according to the synthetic method of compound (1). The crude product was subjected to column chromatography with EA (1% acetic acid added, v / v) to obtain approximately 7.1 g of compound 39, yield: 41.9%. MALDI-TOF MS: 673.98

[0143] Example 7: Synthesis of compound (42)

[0144]

[0145] Synthesis of compound 42-2:

[0146] Compound 42-1 (20.8 g, 50 mmol), compound 1-2 (9.3 g, 50 mmol), sodium tert-butoxide (9.6 g, 100 mmol), bis(benzylacetone)palladium (0.28 g, 0.5 mmol), and 4,5-bisdiphenylphosphine-9,9-dimethyloxanthracene (0.58 g, 1 mmol) were accurately weighed and added sequentially to a 500 mL three-necked flask. The crude product was prepared according to the synthetic method for compound 1-3. The crude product was purified by column chromatography (PE:DCM = 25:1, v / v) to give approximately 22.1 g of compound 42-2, yield: 85.2%. MS: 520.86

[0147] Synthesis of compound (42):

[0148] Compound 42-2 (13 g, 25 mmol) and compounds 1-4 (4.3 g, 50 mmol) were accurately weighed and added to 150 mL of toluene and 30 mL of piperidine in a 250 mL three-necked flask. The crude product was prepared according to the synthetic method of compound (1). The crude product was subjected to column chromatography with EA (1% acetic acid added, v / v) to obtain approximately 6.4 g of compound (42), yield: 43.8%. MALDI-TOF MS: 588.08

[0149] Example 8: Synthesis of compound (54)

[0150]

[0151] Synthesis of compound 54-3:

[0152] Accurately weigh compound 54-1 (36.7 g, 100 mmol), compound 54-2 (20.9 g, 100 mmol), sodium tert-butoxide (19.2 g, 200 mmol), palladium acetate (0.91 g, 4 mmol), and 1,1'-bis(diphenylphosphine)ferrocene (4.4 g, 8 mmol) into a 1000 mL three-necked flask. Add 300 mL of toluene, purge with nitrogen three times, and then heat to 100 °C and react for 12 h. Cool to room temperature, wash with water, and extract with ethyl acetate. Remove excess solvent from the organic phase by vacuum distillation. Purify the crude product by column chromatography (PE:DCM = 10:1) to give approximately 26.7 g of compound 54-3, yield: 53.9%. MS: 495.64

[0153] Synthesis of compound 54-5:

[0154] Accurately weigh compound 54-3 (24.8 g, 50 mmol), compound 54-4 (7.6 g, 50 mmol), Pd(PPh3)4 (1.7 g, 1.5 mmol), and potassium carbonate (13.8 g, 100 mmol) and add them sequentially to a 1000 mL three-necked flask. Add 400 mL of toluene and 100 mL of water. After purging with nitrogen three times, heat the entire reaction system to reflux and react for 20 h. After cooling, the reaction solution is poured into water and extracted with EA, then dried over anhydrous magnesium sulfate. Remove the solvent by rotary evaporation of the organic phase. Using PE:EA = 15:1 (v / v) as eluent, separate by silica gel column chromatography to obtain approximately 33.6 g of compound 54-5, with a yield of 85.9%. Ms: 522.96

[0155] Synthesis of compound 54-7:

[0156] Compound 54-5 (20.9 g, 40 mmol), compound 54-6 (9.7 g, 40 mmol), sodium tert-butoxide (9.6 g, 100 mmol), bis(benzylacetone)palladium (0.28 g, 0.5 mmol), and 4,5-bisdiphenylphosphine-9,9-dimethyloxanthracene (0.58 g, 1 mmol) were accurately weighed and added sequentially to a 500 mL three-necked flask. The crude product was prepared according to the synthetic method for compounds 1-3. The crude product was purified by column chromatography (PE:DCM = 10:1, v / v) to give approximately 27.9 g of compound 54-7, yield: 81.6%. Ms: 684.68

[0157] Synthesis of compound (54):

[0158] Accurately weigh 17.1 g (25 mmol) of compound 54-7 and 4.3 g (50 mmol) of compound 1-4 into 150 mL of toluene and 30 mL of piperidine in a 250 mL three-necked flask, and prepare the crude product according to the synthesis method of compound (1). The crude product was subjected to column chromatography with EA (1% acetic acid added by volume) to obtain approximately 8.0 g of compound (54), yield: 42.4%. MALDI-TOF MS: 751.89.

[0159] Fabrication and characterization of OPV devices

[0160] The following specific examples illustrate in detail the process of preparing OPV devices using the above-mentioned organic compounds containing anchoring groups and the device characterization.

[0161] Fabrication of Device Example 1:

[0162] Cleaning of ITO substrates with anodes: Clean the ITO conductive glass anode layer, then ultrasonically clean it with deionized water, acetone, and isopropanol for 15 minutes, and then treat it in a plasma cleaner for 5 minutes to further clean the surface and improve surface wettability, etc.

[0163] Preparation of the anodic buffer layer: The compound (1) was dissolved in anhydrous ethanol to prepare an anodic buffer layer solution (1 mmol / L). The solution was spin-coated onto a clean ITO surface in air at a spin speed of 4000 rpm for 30 s. After spin-coating, the substrate was annealed at 100 °C for 10 min. The annealed and cooled substrate was dynamically washed twice with anhydrous ethanol to remove unanchored organic compounds containing anchored groups.

[0164] Preparation of the photoactive layer: The prepared device containing the anode buffer layer is placed in a glove box, and the photoactive layer material is uniformly spin-coated onto the anode buffer layer at a 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 D18, and the acceptor material is selected from L8-BO, wherein PM6:D18:L8-BO is dissolved in chloroform at a mass ratio of 0.8:0.2:1.2.

[0165] Preparation of the cathode buffer layer: After hot annealing on a hot stage at 100℃ for 10 min, the cathode buffer layer material PFN-Br was uniformly spin-coated onto the photoactive layer at a spin speed of 1800-4000 rpm to obtain a cathode buffer layer with a thickness of 5 nm.

[0166] Cathode layer fabrication: under high vacuum (1×10⁻⁶) -6 Ag is deposited onto the cathode buffer layer in millibars to form a cathode layer with a thickness of 100 nm.

[0167] Device packaging: The device is encapsulated in a nitrogen glove box using UV-cured resin.

[0168] Device structure diagram as shown Figure 1 As shown.

[0169] Fabrication of devices in Examples 2-8:

[0170] The preparation method is the same as that in Device Example 1, except that the anode buffer layer is prepared by replacing anode buffer layer compound 1 with the anode buffer layer material shown in Table 1.

[0171] The performance of the fabricated organic solar cell device was tested. Under AM1.5G standard light irradiation using a solar simulator (SS-F5-3A), the cell current-voltage curve was measured, and the photoelectric conversion efficiency was calculated. (Table 1 is shown.)

[0172] Table 1

[0173] Device Example 1 Compound (1) 16.09 Device Example 2 Compound (4) 16.24 Device Example 3 Compound (8) 17.19 Device Example 4 Compound (24) 17.38 Device Example 5 Compound (34) 16.11 Device Example 6 Compound (39) 16.73 Device Example 7 Compound (42) 15.66 Device Example 8 Compound (54) 16.52

[0174] As shown in Table 1, when the organic compound containing anchoring groups described in this invention is used as an anode buffer layer in organic photovoltaic devices, the photoelectric conversion efficiency exceeds 15%.

[0175] As shown in Table 1, the photoelectric conversion efficiency of Device Example 2 is better than that of Device Example 1 because: the addition of alkoxy groups can prevent direct contact between the substrate and the active layer; it is beneficial to increase the adsorption density of organic matter containing anchoring groups; the increase in the adsorption density of organic matter containing anchoring groups can improve the interface passivation ability, thereby improving the performance of organic electronic devices.

[0176] The principle that the photoelectric conversion efficiency of Device Example 3 is better than that of Device Example 2 is that the introduction of phenyl can improve the conjugation degree of the tail functional groups, thereby improving the thermal stability of the material; at the same time, the introduction of phenyl improves the spatial structure of the compound, which is more conducive to charge transport.

[0177] The above embodiments further illustrate the content of this application, but should not be construed as limiting this application. Modifications and substitutions made to the methods, steps, or conditions of this application without departing from the spirit and substance of this application are all within the scope of this application. Unless otherwise specified, the technical means used in the embodiments are conventional means well known to those skilled in the art.

Claims

1. An anode buffer layer material, wherein the anode buffer layer material is selected from organic compounds containing anchoring groups, characterized in that: The organic compound containing the anchoring group has a structure as shown in general formula (I): （I）； in, L is selected from the following structure: ； * indicates a connection point; X is selected from single bonds, O, S, or CR4R5; Z is selected from single bonds, O, S, or CR6R7; X and Z are selected from the same group; Each time R1 and R2 appear, they are independently selected from -D, straight-chain alkyl with 1 to 4 carbon atoms, branched alkyl with 3 to 4 carbon atoms, straight-chain alkoxy with 1 to 4 carbon atoms, straight-chain alkylthio with 1 to 4 carbon atoms, cyano, hydroxy, nitro, -Cl, -Br, -F, -I, or a group formed by a combination of the above groups. Each time R3 appears, it is independently selected from phenyl groups substituted with one or more straight-chain alkoxy groups having 1 to 6 C atoms; m is selected from 0; n is selected from 0; r is selected from 1; R4, R5, R6, and R7 are independently selected from straight-chain alkyl groups having 1 to 10 carbon atoms, or branched or cyclic alkyl groups having 3 to 10 carbon atoms.

2. The anode buffer layer material according to claim 1, characterized in that: R4, R5, R6, and R7 are independently selected from straight-chain alkyl groups having 1 to 6 carbon atoms, or branched or cyclic alkyl groups having 3 to 6 carbon atoms.

3. The anode buffer layer material according to claim 1, characterized in that: The organic compound containing the anchoring group has any structure of general formula (II-1)-(II-4): 。 4. The anode buffer layer material according to any one of claims 1-3, characterized in that: R3 is selected from phenyl groups substituted with one or more methoxy groups.

5. The anode buffer layer material according to claim 1, characterized in that: The organic compounds containing anchoring groups include the following structural formulas: 。 6. A composition, characterized in that: The composition comprises at least one of the anode buffer layer materials as described in any one of claims 1-5, and at least one organic solvent.

7. An organic electronic device, characterized in that: The organic electronic device includes at least a cathode, an anode, a photoactive layer located between the cathode and the anode, and an anode buffer layer located between the anode and the photoactive layer, wherein the anode buffer layer material comprises at least one anode buffer layer material as described in any one of claims 1-5.

8. An organic electronic device according to claim 7, characterized in that: The organic electronic device is selected from organic solar cells, perovskite solar cells, organic light-emitting diodes, or organic photodetectors.

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