Aromatic imide compounds or salts, processes for their preparation and use

Abstract

The present disclosure provides a compound having a structure of general formula (I) or a salt thereof as an n-type semiconductor material, a method of preparing the compound or the salt thereof, and an optoelectronic device comprising the compound or the salt thereof. In general formula (I), Ar is an optionally substituted C10-C30 aromatic fused ring; A1 and A2 are each independently selected from hydrogen, a carboxylic acid group, a sulfonic acid group, a sulfinic acid group, a phosphoric acid group, a sulfuric acid group, a nitric acid group, and a boric acid group, and A1 and A2 are not hydrogen at the same time; n is a natural number of 0 to 12; and [N] represents a tertiary amine group, wherein the carboxylic acid group, the sulfonic acid group, the sulfinic acid group, the phosphoric acid group, the sulfuric acid group, the nitric acid group, and the boric acid group optionally form a salt with an alkali metal, and / or the tertiary amine group optionally forms an ammonium salt with a halogen. Such a compound is simple in synthesis steps, easy to purify, accurate in structure, and easy to characterize.

Description

Technical Field

[0001] This disclosure generally relates to the field of semiconductor materials. More specifically, this disclosure relates to a compound or a salt thereof used as an n-type semiconductor material, a method for preparing said compound or a salt thereof, and an optoelectronic device comprising said compound or a salt thereof. Background Technology

[0002] Organic solar cells (OSCs) have demonstrated enormous potential in photoelectric conversion and exhibit remarkable application value due to their significant advantages such as lightweight, transparency, and flexibility. It is well known that there are two common device structures for OSCs: forward and reverse. Numerous studies have shown that devices with reverse structures generally offer better stability and are more compatible with roll-to-roll printing, both crucial factors for the commercialization of OSCs. However, to date, the vast majority of high-performance devices employ a forward structure: indium tin oxide (ITO) / hole transport layer (HTL) / active layer (AL) / electron transport layer (ETL) / metal electrode, with PEDOT:PSS being the most commonly used hole transport layer. However, PEDOT:PSS has shortcomings in stability, which may explain the overall lower stability and shorter lifetime of PEDOT:PSS-based forward devices. Although some reports have attempted to address this issue, the stability of devices using forward structures has not been very successful so far.

[0003] Conversely, reverse-polarity devices employing an ITO / ETL / AL / HTL / metal electrode structure generally exhibit considerable stability. However, the reported power conversion efficiency (PCE) of this system to date is low, failing to meet commercialization requirements. Meanwhile, ZnO is the most popular and commonly used ETL material in reverse-polarity OSC devices, benefiting from its good transmittance in the visible light region, high electron mobility, high tolerance to thick films, and stable chemical structure. However, one of the most challenging issues with this material is its catalytic decomposition of the active layer components under UV light, which can lead to a decrease in OSC stability. Therefore, the key to fabricating efficient and stable OSCs currently lies in fabricating ZnO-based reverse-polarity devices and addressing the catalytic decomposition of the active layer components. Summary of the Invention

[0004] This disclosure is intended to address one or more problems existing in the aforementioned organic solar cells, particularly stability-related problems in forward and reverse device structures.

[0005] Therefore, in a first aspect, this disclosure provides compounds having the structure of the following general formula (I):

[0006]

[0007] in,

[0008] Ar is an optionally substituted C10-C30 aromatic fused ring;

[0009] A1 and A2 are each independently selected from hydrogen, carboxylic acid group, sulfonic acid group, sulfinic acid group, phosphate group, sulfate group, nitrate group and boric acid group, and A1 and A2 are not both hydrogen;

[0010] n is a natural number from 0 to 12; and

[0011] [N] represents a tertiary amine group.

[0012] The carboxylic acid group, sulfonic acid group, sulfinic acid group, phosphate group, sulfate group, nitrate group and borate group optionally form salts with alkali metals, and / or the tertiary amine group optionally forms ammonium salts with halogens.

[0013] In one embodiment, Ar is an aromatic fused ring selected from the following:

[0014]

[0015] The aromatic fused ring may optionally be substituted with deuterium, halogen, or C1-C12 alkyl groups.

[0016] In one implementation, A1 and A2 are each independently selected from:

[0017]

[0018] In this embodiment, A1 and A2 optionally form salts with alkali metals, such as lithium, sodium, potassium, rubidium, cesium, especially sodium and potassium.

[0019] In one implementation, n is a natural number from 0 to 8 or from 0 to 6, preferably a natural number from 1 to 4, such as 1, 2, 3 and 4.

[0020] In one implementation, [N] is selected from:

[0021]

[0022] R1, R2 and R3 are each independently selected from C1-C12 alkyl, C1-C12 alkoxy and C1-C12 etheroxy, preferably selected from C1-C8 alkyl, C1-C8 alkoxy and C1-C8 etheroxy, more preferably selected from C1-C4 alkyl, C1-C4 alkoxy and C1-C4 etheroxy;

[0023] Hal represents fluorine, chlorine, bromine, or iodine.

[0024] In this embodiment, R1, R2 and R3 can be methyl, ethyl, propyl, butyl, etc.

[0025] In one implementation, general formula (I) is any one selected from formulas (1) to (16):

[0026]

[0027] In formulas (1), (3), (5), (7), (9), (11), (13) to (15), R1 and R2 are methyl groups and n is 0, 1, 2 or 3.

[0028] In formulas (2), (4), (6), (8), (10), (12), (14) to (16), R1, R2 and R3 are methyl groups and n is 0, 1, 2 or 3.

[0029] In formulas (2), (4), (6), (8), (10), (12), (14) to (16), R1 and R2 are methyl, R3 is ethyl, and n is 0, 1, 2 or 3.

[0030] Salts are formed by replacing the hydrogen atoms of one or both carboxylic acid groups in formulas (1), (2), (9) and (10) with potassium or sodium.

[0031] The hydrogen atoms of the carboxylic acid groups in formulas (3), (4), (11), and (12) are replaced by potassium or sodium to form salts.

[0032] Salts are formed by replacing one or two hydrogen atoms of one or two phosphate groups in formulas (5), (6), (13) and (14) with potassium or sodium.

[0033] One or both hydrogen atoms in the phosphate groups of formulas (7), (8), (15) and (16) are replaced by potassium or sodium to form salts.

[0034] In specific implementation schemes, the compounds mentioned above or their salts are selected from:

[0035]

[0036] In a second aspect, this disclosure provides a method for preparing the above-mentioned compound or a salt thereof, the method comprising:

[0037] (a) Hydrolyzing a compound having the structure of general formula (II) under alkaline conditions to obtain the hydrolysis product;

[0038] (b) The hydrolysis product is subjected to a condensation reaction with a compound having the structure of general formula (III) under weakly acidic conditions; and

[0039] (c) Optionally react the condensation product with a haloalkyl group R3-Hal;

[0040]

[0041] The definition of Ar in general formula (II) is the same as that in general formula (I);

[0042] In general formula (Ⅲ), R1, R2, and n are defined in the same way as in general formula (I); and

[0043] In the haloalkyl R3-Hal, the definitions of R3 and Hal are the same as in general formula (I).

[0044] Preferably, the molar ratio of the compound of formula (II) to the compound of formula (III) is 1:1 to 1:10, more preferably about 1:1.

[0045] In one embodiment, the condensation reaction is carried out under reflux. In another embodiment, the reaction time of the condensation reaction can be about 1 to 72 hours, for example 8 to 60 hours or 12 to 50 hours, or even 24 to 48 hours.

[0046] In one embodiment, the alkaline condition can be achieved by adding an alkali metal hydroxide such as potassium hydroxide or sodium hydroxide. In another embodiment, the weakly acidic condition can be achieved by adding an acid such as phosphoric acid, acetic acid, or sulfuric acid.

[0047] In a third aspect, this disclosure provides an optoelectronic device comprising a compound of the disclosed material as an electron transport layer. In one embodiment, the electron transport layer is a composite layer comprising a compound of the disclosed material and a metal oxide. In one embodiment, the metal oxide is selected from zinc oxide, tin dioxide, or combinations thereof. In another embodiment, the optoelectronic device can be an organic solar cell, a field-effect transistor, or an organic light-emitting diode. Additionally, the optoelectronic device can be a flexible device.

[0048] In a fourth aspect, this disclosure also provides the use of the compounds of this disclosure as electron transport materials in optoelectronic devices. In one embodiment, the electron transport layer of the optoelectronic device is a composite layer comprising the compounds of this disclosure and a metal oxide. In one embodiment, the optoelectronic device can be an organic solar cell, a field-effect transistor, or an organic light-emitting diode. Additionally, the optoelectronic device can be a flexible device.

[0049] Compounds or salts thereof having the structure of general formula (I) according to this disclosure can serve as n-type organic small molecule semiconductor materials, especially when combined with metal oxides such as zinc oxide and tin dioxide to form composite electron transport layers (also known as hybrid electron transport layers), effectively and synergistically improving the efficiency and stability of optoelectronic devices based on different active layers. Compounds or salts thereof having the structure of general formula (I) according to this disclosure also provide a general improvement in the efficiency and stability of organic solar cells with reverse structures based on different active layers.

[0050] Furthermore, the preparation method of this type of compound obtained by hydrolysis and reamidation according to this disclosure has outstanding advantages such as simplicity, high efficiency, low environmental pollution, large-scale preparation capability, and low cost, which is of great significance for the application and promotion of this type of interface modification layer material. Attached Figure Description

[0051] Figure 1 The absorption spectra of the n-type semiconductor thin film, zinc oxide thin film, and the hybrid electron transport layer formed by the two prepared in Example 2 are shown.

[0052] Figure 2 The photoelectron spectroscopy curves are shown for the n-type semiconductor thin film, zinc oxide thin film, and the hybrid electron transport layer formed by the two prepared in Example 2.

[0053] Figure 3 The image shows the hydrogen NMR spectrum of the n-type semiconductor prepared in Example 1.

[0054] Figure 4 The image shows the carbon NMR spectrum of the n-type semiconductor prepared in Example 1.

[0055] Figure 5 This is a high-resolution mass spectrometer of the n-type semiconductor prepared in Example 1.

[0056] Figure 6 The current density-voltage curves of the solar cells in Example 3, which use ZnO and ZnO / NMA as electron transport layers and D18:N3 as active layers, are shown.

[0057] Figure 7 The external quantum efficiency response spectra of the solar cells in Example 3, which use ZnO and ZnO / NMA as electron transport layers and D18:N3 as active layers, respectively.

[0058] Figure 8 The photosynthetic stability curves of the solar cells in Example 3, which use ZnO and ZnO / NMA as electron transport layers and D18:N3 as active layers, are shown.

[0059] Figure 9In Example 4, ZnO and ZnO / NMA were used as electron transport layers, respectively, and PM6:Y6:PC was used. 71 The current density-voltage curve of a solar cell with BM as the active layer.

[0060] Figure 10 In Example 4, ZnO and ZnO / NMA were used as electron transport layers, respectively, and PM6:Y6:PC was used. 71 External quantum efficiency response spectrum of a solar cell with BM as the active layer.

[0061] Figure 11 In Example 4, ZnO and ZnO / NMA were used as electron transport layers, respectively, and PM6:Y6:PC was used. 71 BM represents the photostability curve of the active layer of the solar cell.

[0062] Figure 12 The current density-voltage curves of the solar cells in Example 5, which use ZnO and ZnO / NMA as electron transport layers and PM6:L8-BO as active layers, are shown.

[0063] Figure 13 The external quantum efficiency response spectra of the solar cells in Example 5, which use ZnO and ZnO / NMA as electron transport layers and PM6:L8-BO as active layers, respectively.

[0064] Figure 14 The photostability curves of the solar cells in Example 5, which use ZnO and ZnO / NMA as electron transport layers and PM6:L8-BO as active layers, are shown.

[0065] Figure 15 The current density-voltage curves of the solar cells in Example 6, which use ZnO and ZnO / NMA as electron transport layers and PM6:F-2Cl as active layers, are shown.

[0066] Figure 16 The external quantum efficiency response spectra of the solar cells in Example 6, which use ZnO and ZnO / NMA as electron transport layers and PM6:F-2Cl as active layers, respectively.

[0067] Figure 17 The photostability curves of the solar cells in Example 6, which used ZnO and ZnO / NMA as electron transport layers and PM6:F-2Cl as active layers, are shown.

[0068] Figure 18 The current density-voltage curves of the solar cells in Example 7, which use ZnO and ZnO / NMA as electron transport layers and PCE10:PC71BM as active layers, are shown.

[0069] Figure 19The external quantum efficiency response spectra of the solar cells in Example 7, which use ZnO and ZnO / NMA as electron transport layers and PCE10:PC71BM as active layers, are shown.

[0070] Figure 20 The photostability curves of the solar cells in Example 7, which use ZnO and ZnO / NMA as electron transport layers and PCE10:PC71BM as active layers, are shown.

[0071] Figure 21 The current density-voltage curves of the solar cells in Example 8, which use SnO2 and SnO2 / NMA as electron transport layers and PM6:Y6 as active layers, are shown.

[0072] Figure 22 The photostability curves of the solar cells in Example 8, which used SnO2 and SnO2 / NMA as electron transport layers and PM6:Y6 as active layers, are shown.

[0073] Figure 23 The current density-voltage curves of PM6:Y6 solar cells with ZnO and ZnO / PMA as electron transport layers in Example 11 are shown.

[0074] Figure 24 The external quantum efficiency response spectra of PM6:Y6 solar cells with ZnO and ZnO / PMA as electron transport layers in Example 11 are shown.

[0075] Figure 25 The current density-voltage curves of PM6:L8-BO solar cells with SnO2 and SnO2 / PMA as electron transport layers in Example 13 are shown.

[0076] Figure 26 The external quantum efficiency response spectra of PM6:L8-BO solar cells with SnO2 and SnO2 / PMA as electron transport layers in Example 13 are shown. Detailed Implementation

[0077] The present disclosure is described in detail below through specific embodiments, but this does not imply any adverse limitation thereof. The present disclosure has been described in detail herein through specific embodiments, and various changes to the specific embodiments of the present disclosure will be apparent to those skilled in the art without departing from the spirit and scope thereof. All reagents used in this disclosure are commercially available and can be used without further purification.

[0078] In this disclosure, unless otherwise stated, % refers to wt%.

[0079] In this disclosure, the term "fused aromatic ring" refers to a fused-ring aromatic hydrocarbon, that is, a hydrocarbon composed of two or more benzene rings fused together by sharing two adjacent carbon atoms. In this disclosure, C10-C30 fused aromatic rings can include any aromatic fused ring within this range, such as C14-C28 fused aromatic rings, C18-C24 fused aromatic rings, etc. For example, fused aromatic rings can include, but are not limited to, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, etc.

[0080] In this disclosure, the term "alkyl" refers to a group formed by the loss of a hydrogen atom from a saturated alkane. In this disclosure, C1-C12 alkyl can include any alkyl group within its range, such as C1-C10 alkyl, C1-C8 alkyl, and C1-C6 alkyl. For example, alkyl can include, but is not limited to, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, and their homologues. The term "alkylene" is a divalent group corresponding to "alkyl," such as methylene, ethylene, propylene, butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, and their homologues.

[0081] In this disclosure, the term "acid group" includes both organic acid groups and inorganic acid groups. Organic acid groups include, for example, carboxylic acid groups, sulfonic acid groups, sulfinic acid groups, etc. Inorganic acid groups include, for example, sulfate groups, phosphate groups, boric acid groups, nitrate groups, etc.

[0082] In this disclosure, the term "halogen element" generally refers to fluorine, chlorine, bromine, and iodine.

[0083] In this disclosure, the term "alkoxy" refers to RO-, where R is an alkyl group as defined above.

[0084] In this disclosure, the term "etheroxy" refers to -ROR, where R is an alkyl group as defined above.

[0085] In this disclosure, Ca represents the number of carbon atoms in the modified group as a. Ca-Cb represents the number of carbon atoms in the modified group as a to b.

[0086] In this disclosure, "substituted or unsubstituted" means that the modified group is unsubstituted or substituted by one or more substituents selected from deuterium, halogen, cyano, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 etheroxy and C6-C20 aryl.

[0087] In this disclosure, the general formula in Indicates the connection position with adjacent groups, unless otherwise defined.

[0088] In this disclosure, the terms "hybrid electron transport layer" and "composite electron transport layer" can be used interchangeably.

[0089] This disclosure provides compounds having the structure of general formula (I) or salts thereof:

[0090]

[0091] Ar can be an optionally substituted C10-C30 aromatic fused ring, for example, it can be an aromatic fused ring selected from naphthalene ring, perylene ring or its derivatives;

[0092] A1 and A2 can each be independently selected from hydrogen (H), an acid group or a salt formed therefrom, and A1 and A2 are not both hydrogen, wherein the acid group is as defined above, and the salt can be a salt formed by the acid group and an alkali metal;

[0093] n can be a natural number from 0 to 12;

[0094] [N] represents a tertiary amine group or an ammonium salt formed therefrom, wherein the ammonium salt may be an ammonium salt formed by a tertiary amine group and a halogen.

[0095] The compound of general formula (I) is an aromatic imide derivative containing an acidic functional group. The inventors discovered that this compound can be used as an n-type organic small molecule semiconductor material.

[0096] In a preferred embodiment, Ar in general formula (I) is selected from the following aromatic fused rings or derivatives thereof:

[0097]

[0098] In this document, aromatic imides of general formula (I), or aromatic fused rings represented by Ar, may be substituted at appropriate positions. Derivatives of aromatic fused rings represented by Ar include, but are not limited to, aromatic fused rings with appropriate substitutions on the benzene ring, such as aromatic fused rings substituted on the benzene ring by substituents selected from alkyl groups (such as C1-C12 alkyl groups, especially C1-C6 alkyl groups) and halogen groups (e.g., fluorine, chlorine, bromine, or iodine).

[0099] In this disclosure, the acid group may include organic acid groups and inorganic acid groups. Preferably, the acid group may be selected from carboxylic acid groups, phosphate groups, and sulfate groups. Therefore, in a preferred embodiment, A1 and A2 in general formula I may each be independently selected from hydrogen (H), carboxylic acid groups, phosphate groups, sulfate groups, or salts formed therefrom, but A1 and A2 are not both hydrogen. In a further preferred embodiment, the acid group may be selected from carboxylic acid groups and phosphate groups as follows:

[0100]

[0101] In some embodiments, the salt formed by the acid group can be a salt formed by an organic acid group or an inorganic acid group and an alkali metal. Alkali metals include, for example, lithium, sodium, potassium, rubidium, and cesium, particularly sodium and potassium. Particularly preferred are sodium carboxylate groups, potassium carboxylate groups, potassium hydrogen phosphate groups, sodium hydrogen phosphate groups, potassium phosphate groups, sodium phosphate groups, potassium hydrogen sulfate groups, sodium bisulfate groups, potassium sulfate groups, sodium sulfate groups, etc. That is, A1 and A2 can each independently be hydrogen (H), sodium carboxylate groups, potassium carboxylate groups, potassium hydrogen phosphate groups, sodium hydrogen phosphate groups, potassium phosphate groups, sodium phosphate groups, potassium hydrogen sulfate groups, sodium bisulfate groups, potassium sulfate groups, sodium sulfate groups, etc., but A1 and A2 cannot both be hydrogen.

[0102] In general formula (I), n represents the number of methylene groups in the methylene chain. n can be a natural number from 0 to 12. In this disclosure, there is no particular limitation on the chain length of the methylene chain. However, in a preferred embodiment, n in the methylene chain can be a natural number from 0 to 8 or from 0 to 6, for example, a natural number from 0 to 4 or from 1 to 4. For example, n can be 0, 1, 2, 3, 4, 5, 6, 7, or 8. It should be understood that when n is 0... Indicates a directly connected key.

[0103] In general formula (I), [N] represents an amine side chain. In this disclosure, [N] in general formula (I) is preferably selected from tertiary amine groups and quaternary ammonium halide groups as shown below:

[0104]

[0105] Hal represents a halogen element selected from fluorine (F), chlorine (Cl), bromine (Br), and iodine (I). Hal is preferably chlorine or bromine.

[0106] For example, [N] can be a tertiary amine group or a quaternary ammonium bromide group:

[0107]

[0108] Here, R1, R2, and R3 are each independently selected from C1-C12 alkyl, C1-C12 alkoxy, and C1-C12 etheroxy groups. There are no particular limitations on R1, R2, and R3; in principle, alkyl, alkoxy, and etheroxy groups within the aforementioned carbon chain length range are all applicable. In some embodiments, R1, R2, and R3 are each independently selected from C1-C8 alkyl, C1-C8 alkoxy, and C1-C8 etheroxy groups, for example, they can be independently selected from C1-C4 alkyl, C1-C4 alkoxy, and C1-C4 etheroxy groups. In some specific embodiments, R1, R2, and R3 can be methyl, ethyl, propyl, butyl, and their homologues. For example, in some specific embodiments, R1 and R2 are both methyl if present. In other specific embodiments, R1 and R2 are methyl, and R3 is ethyl if present.

[0109] It should be understood that, among the groups described above, if there are If so, Indicates the connection position with adjacent groups.

[0110] In a more specific embodiment, the compounds of general formula (I) of this disclosure are selected from the following structural formulas, wherein the carboxylic acid group or phosphate group can form a salt with an alkali metal:

[0111]

[0112] In some specific embodiments, this disclosure provides compounds in which R1 and R2 are each methyl and n is 3, represented by one of formulas (1), (3), (5), (7), (9), (11), (13) to (15). In specific cases, this disclosure provides compounds in which R1, R2, and R3 are each methyl and n is 3, represented by one of formulas (2), (4), (6), (8), (10), (12), (14) to (16). In some specific embodiments, this disclosure also provides compounds in which R1 and R2 are each methyl, R3 is ethyl, and n is 3, represented by one of formulas (2), (4), (6), (8), (10), (12), (14) to (16). In some specific embodiments, this disclosure further provides compounds represented by one of formulas (1) to (8) wherein R1, R2 and R3 are methyl, n is 3 and one hydrogen atom of the carboxyl group is replaced by potassium or sodium.

[0113] In some specific embodiments, the hydrogen atoms of one or both carboxylic acid groups in formulas (1), (2), (9), and (10) can be replaced by potassium or sodium, thus forming potassium carboxylate or sodium carboxylate. In some specific embodiments, the hydrogen atoms of the carboxylic acid groups in formulas (3), (4), (11), and (12) can be replaced by potassium or sodium, thus forming potassium carboxylate or sodium carboxylate. In some specific embodiments, one, two, three, or four hydrogen atoms of the phosphate groups in formulas (5), (6), (13), and (14) can be replaced by potassium or sodium, thus forming the corresponding potassium carboxylate or sodium carboxylate. In some specific embodiments, one or two hydrogen atoms of the phosphate groups in formulas (7), (8), (15), and (16) can be replaced by potassium or sodium, thus forming potassium hydrogen phosphate or sodium hydrogen carboxylate, or dipotassium phosphate or disodium phosphate.

[0114] In a more specific embodiment, the compound of general formula I is selected from:

[0115]

[0116] This disclosure also discloses a method for preparing compounds of general formula (I), i.e., a method for preparing compounds of general formula (I) (i.e., amino-modified aromatic imide derivatives) or salts thereof, comprising:

[0117] (a) Compounds of general formula (II) (i.e., aromatic imide anhydrides) are hydrolyzed under alkaline conditions;

[0118] (b) Subsequently, a condensation reaction is carried out with a compound of general formula III under weakly acidic conditions; and

[0119] (c) Optionally, further reaction with a haloalkyl group R3-Hal.

[0120] Thus, compounds of general formula (I) are obtained.

[0121]

[0122] The definition of Ar in general formula (II) is the same as that in general formula (I).

[0123] In general formula (Ⅲ), the definitions of R1, R2 and n are the same as in general formula (I).

[0124] In the haloalkyl R3-Hal, the definition of R3 is the same as in general formula (I).

[0125] The alkaline conditions can be achieved by adding alkali metal hydroxides (such as potassium hydroxide, sodium hydroxide, etc.). The weakly acidic conditions can be achieved by adding acids such as phosphoric acid, acetic acid, sulfuric acid, etc.

[0126] In this method, the molar ratio of the compound of general formula (II) to the compound of general formula (III) can be 1:1 to 1:10, specifically about 1:1. The condensation reaction is preferably carried out under reflux. There is no particular limitation on the reaction time of the condensation reaction. In some embodiments, the reaction time can be about 1 to 72 hours, for example 8 to 60 hours or 12 to 50 hours, or even 24 to 48 hours.

[0127] The compound of general formula (I) disclosed herein is an aromatic imide derivative containing acidic functional groups, which can modify conventional electron transport layer materials (e.g., metal oxides, such as zinc oxide and / or tin dioxide) thin films to form a hybrid electron transport layer, and thus serve as an interface modification layer for thin film optoelectronic devices.

[0128] This hybrid interface modification layer can be prepared, for example, by the following method, where zinc oxide is only a specific example, and tin dioxide can be prepared using a substantially similar process:

[0129] (1) Dissolve an appropriate amount of zinc oxide precursor zinc acetate dihydrate and an appropriate amount of ethanolamine in an appropriate amount of dimethoxyethanol, stir overnight, and deposit it on top of ITO at a certain rate (e.g., 3000 rpm). Bake at 200°C for 40 minutes to 1 hour to obtain a zinc oxide film.

[0130] (2) Add the compound of general formula (I) to an appropriate amount of alcohol containing 2% by volume of ammonia to prepare a solution of 0.4 to 2 mg / ml, wherein the alcohol may be methanol or ethanol.

[0131] (3) Spin-coat the solution obtained in step (2) onto the zinc oxide film obtained in step (1) at a speed of 1000 to 5000 rpm.

[0132] (4) The resulting hybrid electron transport layer is baked at 120℃~180℃ for 10~30 minutes.

[0133] The resulting electron transport layer can be used in organic optoelectronic devices. That is, the optoelectronic device provided herein includes the above-described compound as an electron transport layer material. The electron transport layer is preferably a hybrid electron transport layer formed by combining the disclosed compound with a metal oxide such as zinc oxide / tin dioxide. The organic optoelectronic device can be, for example, an organic solar cell, a field-effect transistor, or an organic light-emitting diode. Preferably, the organic optoelectronic device is a flexible device.

[0134] Therefore, this disclosure also provides an organic solar cell comprising the compounds of this disclosure as an electron transport layer material, particularly comprising a hybrid electron transport layer formed by combining the compounds of this disclosure with zinc oxide / tin dioxide. It should be emphasized that the technical solution of this disclosure achieves one or more of the following advantages:

[0135] The n-type organic small-molecule semiconductor materials obtained by the preparation method disclosed herein are simple to synthesize, easy to purify, and have a well-defined structure. These aromatic imide derivatives containing acidic functional groups (compounds of general formula (I)) form a hybrid electron transport layer after modifying zinc oxide / tin dioxide thin films, resulting in organic optoelectronic devices with superior photoelectric performance. For example, their photoelectric conversion efficiency can reach over 18.20%. The stability of optoelectronic devices incorporating this hybrid electron transport layer is also significantly improved; for example, when tracking operational stability in MPP mode, they still maintain 95% of the initial PCE after 1500 hours of continuous illumination, with an equivalent actual lifespan of 5 years. This provides a feasible solution for the commercial application of organic solar cells.

[0136] Unwilling to be bound by theory, the inventors believe that compounds according to general formula (I) of this disclosure, when used to modify zinc oxide / tin dioxide and form a hybrid electron transport layer in a thin-film organic solar cell, can reduce the transport barrier between the electron transport layer and the active layer, and regulate the vertical phase separation of the active layer, thereby improving the photoelectric conversion efficiency of the organic solar cell. These compounds can suppress defect-state oxygen on the surface of the zinc oxide film, thereby suppressing the photocatalytic effect of zinc oxide on the active layer components under ultraviolet light, thus enhancing the photostability of the organic solar cell. More importantly, the hybrid electron transport layer formed by these compounds and zinc oxide / tin dioxide can synergistically improve the efficiency and stability of organic solar cells based on different active layers.

[0137] Example

[0138] The invention is further illustrated by the following examples. The examples below are non-limiting and represent various aspects of this disclosure only. In the following examples, unless otherwise specified, reagents and instruments are commercially available products, and unless explicitly stated otherwise, experimental conditions and procedures are generally the same.

[0139] Example 1: Preparation of dicarboxylated naphthimide (NMA) as shown in formula (1-1)

[0140]

[0141] At room temperature, 500 mg of compound (II-1) (1.86 mmol, purchased from Tianjin Xiens Opd Technology Co., Ltd.) was dissolved in 100 mL of water. 10 mL of 1 M potassium hydroxide aqueous solution was added dropwise, and the mixture was stirred overnight at room temperature. After the reaction was complete, 1 M phosphoric acid (H3PO4) was added dropwise to the system, and the pH was adjusted to 6.4. Then, N2 was added to the system. 1 N 1Dimethylpropane-1,3-diamine (190.1 mg, 1.86 mmol) was added dropwise to the system, and 1 M phosphoric acid was added dropwise to adjust the pH of the system to 6.4. The system was then heated and refluxed overnight. After the system cooled to room temperature, the reaction was filtered, and acetic acid was added to the filtrate until a solid precipitated completely. The resulting pale yellow solid was filtered and dried under vacuum, with a yield of 85%. It was confirmed to be a compound of formula (1-1).

[0142] The proton NMR spectrum of the product is as follows: Figure 3 As shown, the carbon spectrum is as follows Figure 4 As shown, the high-resolution mass spectrum is as follows: Figure 5 As shown, the characterization data is as follows:

[0143] 1 H NMR (400MHz, DMSO-d6) δ10.46(s,1H),8.52(d,J=7.5Hz,2H),8.15(d,J=7.5Hz,2H ),4.06(t,J=6.4Hz,2H),3.10(dt,J=10.1,5.2Hz,2H),2.65(d,J=4.8Hz,6H),2.07 -2.00(m,2H).

[0144] 13 C NMR (100MHz, DMSO-d6) δ168.38,163.02,136.68,129.85,128.96,128.59,125.46,124.50,54.56,42.05,36.83,22.81.

[0145] HRMS(m / z,ESI):C 19 H 18 N₂O₆[M+H] + Calculated value: 371.1238, Measured value: 371.1240

[0146] Example 2: Preparation of hybrid electron transport layer ZnO / NMA

[0147] (1) 100 mg of zinc acetate dihydrate, a zinc oxide precursor, and 28 μl of ethanolamine were dissolved in 4 ml of dimethoxyethanol. After stirring overnight, the mixture was deposited on top of ITO at 3000 rpm and baked at 200 °C for 1 hour to obtain a zinc oxide film.

[0148] (2) Add the compound of formula (1-1) (aromatic imide derivative) to an appropriate amount of methanol containing 2% ammonia water by volume to prepare a solution of 0.4 mg / ml.

[0149] (3) The solution obtained in step (2) is spin-coated onto the zinc oxide film obtained in step (1) at a rotation speed of 3000 rpm to obtain an n-type semiconductor film.

[0150] (4) The resulting hybrid electron transport layer was baked at 120°C for 10 minutes.

[0151] Figure 1 The absorption spectra of the n-type semiconductor thin film, zinc oxide thin film, and the hybrid electron transport layer formed by the two prepared in Example 2 are shown.

[0152] Figure 2 The photoelectron spectroscopy curves are shown for the n-type semiconductor thin film, zinc oxide thin film, and the hybrid electron transport layer formed by the two prepared in Example 2.

[0153] Example 3: Fabrication and Performance of Organic Optoelectronic Devices Based on ZnO / NMA Hybrid Electron Transport Layer and D18:N3 Active Layer

[0154] The optoelectronic device structure is ITO / ETL / donor material:acceptor material / MoO3 / Ag. The fabrication process is as follows: Pretreatment of ITO (indium tin oxide) glass: The ITO-sputtered glass substrate was sequentially ultrasonicated in deionized water, acetone, and isopropanol for 15 minutes each, dried by nitrogen purging, and then treated under UV-ozone for 20 minutes. On the ozone-treated ITO substrate, a ZnO film approximately 15 nm thick or a hybrid ZnO / NMA film approximately 19 nm thick was sequentially deposited. Then, an active layer of approximately 100 nm thick, D18:N3, was deposited. The preparation of the D18:N3 solution and the post-treatment of the film were performed according to the literature (J. Semicond. 42, 010502 (2021)). Then, under a vacuum degree less than 2 × 10⁻⁶… -4 A 6 nm layer of MoO3 was deposited as a hole transport layer under Pa conditions, and then, under the cover of a mask, the hole transport layer was deposited at a vacuum level of less than 2 × 10⁻⁶. -4 Under Pa conditions, 150 nm Ag is deposited as the anode, and the effective cell area is approximately 4 mm². 2 The device performance was tested under standard sunlight (AM 1.5G) irradiation conditions using a computer-controlled Keithley 2400 digital source meter.

[0155] Figure 6 The current density-voltage curves of solar cells in Example 3, with ZnO and ZnO / NMA as electron transport layers and D18:N3 as active layers, are shown.

[0156] Figure 7 The external quantum efficiency response spectra of solar cells in Example 3, with ZnO and ZnO / NMA as electron transport layers and D18:N3 as active layers, are shown.

[0157] Figure 8 The photostability curves of solar cells in Example 3, with ZnO and ZnO / NMA as electron transport layers and D18:N3 as active layers, are shown.

[0158] Table 1: Performance comparison of solar cells prepared with ZnO and ZnO / NMA as electron transport layers and D18:N3 as active layer, respectively.

[0159]

[0160] Example 4: Based on ZnO / NMA hybrid electron transport layer, PM6:Y6:PC 71 Fabrication and Performance of Organic Optoelectronic Devices with BM Active Layers

[0161] The optoelectronic device structure is ITO / ETL / donor material:acceptor material / MoO3 / Ag. The fabrication process is as follows: Pretreatment of the ITO (indium tin oxide) glass: The ITO-sputtered glass substrate is sequentially ultrasonicated in deionized water, acetone, and isopropanol for 15 minutes each, dried by nitrogen purging, and then treated under UV-ozone for 20 minutes. On the ozone-treated ITO substrate, a ZnO film approximately 15 nm thick or a hybrid ZnO / NMA film approximately 19 nm thick is sequentially deposited. Then, an active layer of approximately 100 nm thick, PM6:Y6:PC, is deposited. 71 BM, where PM6:Y6:PC 71 The preparation of the BM solution and the post-treatment of the thin film were carried out in accordance with the literature (J. Am. Chem. Soc. 142, 15246-15251 (2020)). Then, under a vacuum degree less than 2 × 10⁻⁶, the film was prepared. -4 A 6 nm layer of MoO3 was deposited as a hole transport layer under Pa conditions, and then, under the cover of a mask, the hole transport layer was deposited at a vacuum level of less than 2 × 10⁻⁶. -4 Under Pa conditions, 150 nm Ag is deposited as the anode, and the effective cell area is approximately 4 mm². 2 The device performance was tested under standard sunlight (AM 1.5G) irradiation conditions using a computer-controlled Keithley 2400 digital source meter.

[0162] Figure 9 The examples shown in Example 4 use ZnO and ZnO / NMA as electron transport layers, respectively, and PM6:Y6:PC. 71 The current density-voltage curve of a solar cell with BM as the active layer.

[0163] Figure 10 The examples shown in Example 4 use ZnO and ZnO / NMA as electron transport layers, respectively, and PM6:Y6:PC. 71 External quantum efficiency response spectrum of a solar cell with BM as the active layer.

[0164] Figure 11 The examples shown in Example 4 use ZnO and ZnO / NMA as electron transport layers, respectively, and PM6:Y6:PC. 71 BM represents the photostability curve of the active layer of the solar cell.

[0165] Table 2: Performance comparison of solar cells prepared with ZnO and ZnO / NMA as electron transport layers and PM6:Y6:PC71BM as active layers, respectively.

[0166]

[0167] Example 5: Fabrication and Performance of Organic Optoelectronic Devices Based on ZnO / NMA Hybrid Electron Transport Layer and PM6:L8-BO Active Layer

[0168] The optoelectronic device structure is ITO / ETL / donor material:acceptor material / MoO3 / Ag. The fabrication process is as follows: Pretreatment of ITO (indium tin oxide) glass: The ITO-sputtered glass substrate was sequentially ultrasonically treated in deionized water, acetone, and isopropanol for 15 minutes each, dried by nitrogen purging, and then treated under UV-ozone for 20 minutes. On the ozone-treated ITO substrate, a ZnO film approximately 15 nm thick or a hybrid ZnO / NMA film approximately 19 nm thick was sequentially deposited. Then, an active layer PM6:L8-BO approximately 100 nm thick was deposited, with the preparation of the PM6:L8-BO solution and the post-treatment of the film referring to the literature (Nat. Energy. 6, 605-613 (2021)). Then, under a vacuum degree less than 2 × 10⁻⁶… -4 A 6 nm layer of MoO3 was deposited as a hole transport layer under Pa conditions, and then, under the cover of a mask, the hole transport layer was deposited at a vacuum level of less than 2 × 10⁻⁶. -4 Under Pa conditions, 150 nm Ag is deposited as the anode, and the effective cell area is approximately 4 mm². 2 The device performance was tested under standard sunlight (AM 1.5G) irradiation conditions using a computer-controlled Keithley 2400 digital source meter.

[0169] Figure 12 The current density-voltage curves of solar cells in Example 5, which use ZnO and ZnO / NMA as electron transport layers and PM6:L8-BO as active layers, are shown.

[0170] Figure 13 The external quantum efficiency response spectra of solar cells in Example 5, which use ZnO and ZnO / NMA as electron transport layers and PM6:L8-BO as active layers, are shown.

[0171] Figure 14The photostability curves of solar cells in Example 5, which use ZnO and ZnO / NMA as electron transport layers and PM6:L8-BO as active layers, are shown.

[0172] Table 3: Performance comparison of solar cells prepared with ZnO and ZnO / NMA as electron transport layers and PM6:L8-BO as active layers, respectively.

[0173]

[0174] Example 6: Fabrication and Performance of Organic Optoelectronic Devices Based on ZnO / NMA Hybrid Electron Transport Layer and PM6:F-2Cl Active Layer

[0175] The optoelectronic device structure is ITO / ETL / donor material:acceptor material / MoO3 / Ag. The fabrication process is as follows: Pretreatment of ITO (indium tin oxide) glass: The ITO-sputtered glass substrate was sequentially ultrasonically treated in deionized water, acetone, and isopropanol for 15 minutes each, dried by nitrogen purging, and then treated under UV-ozone for 20 minutes. On the ozone-treated ITO substrate, a ZnO film approximately 15 nm thick or a hybrid ZnO / NMA film approximately 19 nm thick was sequentially deposited. Then, an active layer of approximately 100 nm thick PM6:F-2Cl was deposited, with the preparation of the PM6:F-2Cl solution and the post-treatment of the film referring to the literature (Adv. Energy Mater. 9, 1902688 (2019)). Then, under a vacuum degree less than 2 × 10⁻⁶… -4 A 6 nm layer of MoO3 was deposited as a hole transport layer under Pa conditions, and then, under the cover of a mask, the hole transport layer was deposited at a vacuum level of less than 2 × 10⁻⁶. -4 Under Pa conditions, 150 nm Ag is deposited as the anode, and the effective cell area is approximately 4 mm². 2 The device performance was tested under standard sunlight (AM 1.5G) irradiation conditions using a computer-controlled Keithley 2400 digital source meter.

[0176] Figure 15 The current density-voltage curves of solar cells in Example 6, which use ZnO and ZnO / NMA as electron transport layers and PM6:F-2Cl as active layers, are shown.

[0177] Figure 16 The external quantum efficiency response spectra of solar cells in Example 6, which use ZnO and ZnO / NMA as electron transport layers and PM6:F-2Cl as active layers, are shown.

[0178] Figure 17 The photostability curves of solar cells in Example 6, which used ZnO and ZnO / NMA as electron transport layers and PM6:F-2Cl as active layers, are shown.

[0179] Table 4: Performance comparison of solar cells prepared with ZnO and ZnO / NMA as electron transport layers and PM6:F-2Cl as active layers, respectively.

[0180]

[0181] Example 7: Based on ZnO / NMA hybrid electron transport layer, PCE10:PC 71 Fabrication and Performance of Organic Optoelectronic Devices with BM Active Layers

[0182] The optoelectronic device structure is ITO / ETL / donor material:acceptor material / MoO3 / Ag. The fabrication process is as follows: Pretreatment of the ITO (indium tin oxide) glass: The ITO-sputtered glass substrate is sequentially ultrasonicated in deionized water, acetone, and isopropanol for 15 minutes each, dried by nitrogen purging, and then treated under UV-ozone for 20 minutes. On the ozone-treated ITO substrate, a ZnO film approximately 15 nm thick or a hybrid ZnO / NMA film approximately 19 nm thick is sequentially deposited. Then, an active layer of approximately 100 nm thick, PCE10:PC, is deposited. 71 BM, where PCE10:PC 71 The preparation of the BM solution and the post-treatment of the thin film were carried out in accordance with the literature (Macromolecules 47, 4653-4659 (2014)). Then, under a vacuum degree less than 2 × 10⁻⁶... -4 A 6 nm layer of MoO3 was deposited as a hole transport layer under Pa conditions, and then, under the cover of a mask, the hole transport layer was deposited at a vacuum level of less than 2 × 10⁻⁶. -4 Under Pa conditions, 150 nm Ag is deposited as the anode, and the effective cell area is approximately 4 mm². 2 The device performance was tested under standard sunlight (AM 1.5G) irradiation conditions using a computer-controlled Keithley 2400 digital source meter.

[0183] Figure 18 The examples shown in Example 7 use ZnO and ZnO / NMA as electron transport layers, respectively, and PCE10:PC 71 The current density-voltage curve of a solar cell with BM as the active layer.

[0184] Figure 19 The examples shown in Example 7 use ZnO and ZnO / NMA as electron transport layers, respectively, and PCE10:PC 71 External quantum efficiency response spectrum of a solar cell with BM as the active layer.

[0185] Figure 20 The examples shown in Example 7 use ZnO and ZnO / NMA as electron transport layers, respectively, and PCE10:PC 71BM represents the photostability curve of the active layer of the solar cell.

[0186] Table 5: Using ZnO and ZnO / NMA as electron transport layers, respectively, PCE10:PC 71 Comparison of the performance of solar cells fabricated with BM as the active layer.

[0187]

[0188] Example 8: Fabrication and Performance of Organic Optoelectronic Devices Based on SnO2 / NMA Hybrid Electron Transport Layer and PM6:Y6 Active Layer

[0189] The optoelectronic device structure is ITO / ETL / donor material:acceptor material / MoO3 / Ag. The fabrication process is as follows: Pretreatment of ITO (indium tin oxide) glass: The ITO-sputtered glass substrate was sequentially ultrasonicated in deionized water, acetone, and isopropanol for 15 minutes each, dried by nitrogen purging, and then treated under UV-ozone for 20 minutes. On the ozone-treated ITO substrate, a SnO2 film approximately 15 nm thick or a hybrid SnO2 / NMA film approximately 19 nm thick was sequentially deposited. Then, an active layer PM6:Y6 approximately 100 nm thick was deposited. The preparation of the PM6:Y6 solution and the post-treatment of the film were performed according to the literature (Macromolecules 47, 4653-4659 (2014)). Finally, the film was deposited under a vacuum of less than 2 × 10⁻⁶. -4 A 6 nm layer of MoO3 was deposited as a hole transport layer under Pa conditions, and then, under the cover of a mask, the hole transport layer was deposited at a vacuum level of less than 2 × 10⁻⁶. -4 Under Pa conditions, 150 nm Ag is deposited as the anode, and the effective cell area is approximately 4 mm². 2 The device performance was tested under standard sunlight (AM 1.5G) irradiation conditions using a computer-controlled Keithley 2400 digital source meter.

[0190] Figure 21 The current density-voltage curves of the solar cells in Example 8, which use SnO2 and SnO2 / NMA as electron transport layers and PM6:Y6 as active layers, are shown.

[0191] Figure 22 The photostability curves of the solar cells in Example 8, which used SnO2 and SnO2 / NMA as electron transport layers and PM6:Y6 as active layers, are shown.

[0192] Table 6: Performance comparison of solar cells prepared with SnO2 and SnO2 / NMA as electron transport layers and PM6:Y6 as active layers, respectively.

[0193]

[0194] Example 9: Preparation of carboxylated perylene diimide (PMA) as shown in formula (9-1)

[0195]

[0196] 3.00 g of compound II-2 (purchased from Tianjin Xiens Opd Technology Co., Ltd.) was added to 240 ml of 5% (w / v) KOH aqueous solution. The mixture was stirred at 90 °C for 2 hours. Glacial acetic acid (0.26 mol, 15 ml) was added, and stirring was continued at 90 °C for 40 minutes. The mixture was cooled to room temperature, filtered, and the solid was washed three times successively with distilled water, methanol, and n-hexane. The solid was dried under vacuum at 40 °C for 3 hours. 2.88 g of a purplish-red powder was obtained, with a yield of 84.5%, which is the compound of formula IV.

[0197] 224.20 mg (0.50 mmol, 1 equivalent) of compound IV was dispersed in a small amount of distilled water. 205.75 mg (2.01 mmol, 4 equivalents) of H₂N(CH₂)₃N(CH₃)₂ was dissolved in a small amount of distilled water and added to the system. The mixture was stirred at room temperature for 3 hours. The reaction mixture was then poured into a large amount of acetone and allowed to stand overnight. The mixture was filtered, and the solid was washed three times with acetone (50 ml * 3). After vacuum drying at 40 °C, 12.62 mg of a brick-red product was obtained, with a yield of 50.16%. The compound was confirmed to be of formula (9-1).

[0198] The proton NMR, carbon NMR, and mass spectrometry characterization data of this product are as follows:

[0199] 1 H NMR (400MHz, deuterium oxide) δ8.41(d,J=7.9Hz,4H,Ar-H),7.81(d,J=7.8Hz,4H,Ar-H),3.02–2.94(m,2H,- CONCH2-),2.88(t,J=6.4Hz,2H,-CH2NMe2),2.70(s,6H,-CH3),2.01–1.87(m,2H,-CH2CH2CH2-).

[0200] 13 C NMR (101 MHz, deuterium oxide) δ 176.70, 137.73, 131.14, 128.31, 127.93, 127.79, 120.86, 54.01, 42.41, 36.17, 22.07.

[0201] HPLC-MS (m / z, ESI): ([C 29 H 22 N2O6] + H) + Calculated value: 495.1551, Measured value: 495.1546

[0202] Example 10: Preparation of hybrid electron transport layer ZnO / PMA

[0203] (1) 100 mg of zinc acetate dihydrate, a zinc oxide precursor, and 28 μl of ethanolamine were dissolved in 4 ml of dimethoxyethanol. After stirring overnight, the mixture was deposited on top of ITO at 3000 rpm and baked at 200 °C for 1 hour to obtain a zinc oxide film.

[0204] (2) Add the compound (aromatic imide derivative) shown in formula (9-1) to an appropriate amount of water:isopropanol mixed solution to prepare a solution of 0.5 mg / ml.

[0205] (3) The solution obtained in step (2) is spin-coated onto the zinc oxide film obtained in step (1) at a rotation speed of 3000 rpm to obtain an n-type semiconductor film.

[0206] (4) The resulting hybrid electron transport layer was baked at 130°C for 5 minutes.

[0207] Example 11: Fabrication and performance of organic optoelectronic devices based on hybrid electron transport layer ZnO / PMA hybrid electron transport layer and PM6:Y6 active layer.

[0208] The optoelectronic device structure is ITO / ETL / donor material:acceptor material / MoO3 / Ag. The fabrication process is as follows: Pretreatment of ITO (indium tin oxide) glass: The ITO-sputtered glass substrate is sequentially ultrasonicated in deionized water, acetone, and isopropanol for 15 minutes each, dried by nitrogen purging, and then treated under UV-ozone for 20 minutes. On the ozone-treated ITO substrate, a ZnO film approximately 15 nm thick or a hybrid ZnO / PMA film approximately 19 nm thick is sequentially deposited. Then, the active layer PM6:Y6 is deposited. The preparation of the PM6:Y6 solution and the post-treatment of the film are as follows: PM6:Y6 = 1:1.2, dissolved in chloroform solvent with 5% chloronaphthalene (v / v), total concentration 13.2 mg / mL. -1 Spin-coating at 2000 rpm for 30 seconds, followed by heat annealing at 120°C for 5 minutes. Then, under a vacuum of less than 2 × 10⁻⁶ ppm... -4 A 1.3 nm MoO3 layer was deposited as a hole transport layer under Pa conditions, and then, under the cover of a mask, the hole transport layer was deposited at a vacuum degree of less than 2 × 10⁻⁶. -4 Under Pa conditions, 150 nm Ag is deposited as the anode, and the effective cell area is approximately 4 mm². 2 The device performance was tested under standard sunlight (AM 1.5G) irradiation conditions using a computer-controlled Keithley 2400 digital source meter.

[0209] Figure 23The current density-voltage curves of PM6:Y6 solar cells with ZnO and ZnO / PMA as electron transport layers in Example 11 are shown.

[0210] Figure 24 The external quantum efficiency response spectra of PM6:Y6 solar cells with ZnO and ZnO / PMA as electron transport layers in Example 11 are shown.

[0211] Table 7: Performance comparison of solar cells prepared with ZnO and ZnO / PMA as electron transport layers and PM6:Y6 as active layers, respectively.

[0212]

[0213] Example 12: Preparation of hybrid electron transport layer SnO2 / PMA

[0214] (1) After diluting 15% SnO2 NPs hydrocolloid dispersion (purchased from Tianjin Xiens Opd Technology Co., Ltd.) to 20 mg / ml, it was dispersed by sonication for 30 minutes, deposited on ITO at 3000 rpm, and baked at 150℃ for 1 hour to obtain tin dioxide film.

[0215] (2) Add the compound of formula (9-1) (aromatic imide derivative) to an appropriate amount of water:isopropanol mixed solution to prepare a solution of 0.5 mg / ml.

[0216] (3) The solution obtained in step (2) is spin-coated onto the zinc oxide film obtained in step (1) at a rotation speed of 3000 rpm to obtain an n-type semiconductor film.

[0217] (4) The resulting hybrid electron transport layer was baked at 120°C for 10 minutes.

[0218] Example 13: Fabrication and Performance of Organic Optoelectronic Devices Based on SnO2 / PMA Hybrid Electron Transport Layer and PM6:L8-BO Active Layer

[0219] The optoelectronic device structure is ITO / ETL / donor material:acceptor material / MoO3 / Ag. The fabrication process is as follows: Pretreatment of ITO (indium tin oxide) glass: The ITO-sputtered glass substrate was sequentially ultrasonicated in deionized water, acetone, and isopropanol for 15 minutes each, dried by nitrogen purging, and then treated under UV-ozone for 20 minutes. On the ozone-treated ITO substrate, a SnO2 film approximately 15 nm thick or a hybrid SnO2 / PMA film approximately 19 nm thick was sequentially deposited. Then, an active layer of approximately 100 nm thick PM6:L8-BO was deposited, with the preparation of the PM6:L8-BO solution and the post-treatment of the film referring to the literature (Nat. Energy. 6, 605-613 (2021)). Then, under a vacuum degree less than 2 × 10⁻⁶… -4 A 1.3 nm MoO3 layer was deposited as a hole transport layer under Pa conditions, and then, under the cover of a mask, the hole transport layer was deposited at a vacuum degree of less than 2 × 10⁻⁶. -4 Under Pa conditions, 150 nm Ag is deposited as the anode, and the effective cell area is approximately 4 mm². 2 The device performance was tested under standard sunlight (AM 1.5G) irradiation conditions using a computer-controlled Keithley 2400 digital source meter.

[0220] Figure 25 The current density-voltage curves of PM6:L8-BO solar cells with SnO2 and SnO2 / PMA as electron transport layers in Example 13 are shown.

[0221] Figure 26 The external quantum efficiency response spectrum of the PM6:L8-BO solar cell with SnO2 / PMA as the electron transport layer in Example 13 is shown.

[0222] Table 8: Performance comparison of solar cells prepared with SnO2 and SnO2 / PMA as electron transport layers and PM6:L8-BO as active layers, respectively.

[0223]

[0224] Example 14: Preparation of the dicarboxylated naphthalene diimide (C2-NMA) shown in formula (1-2)

[0225]

[0226] At room temperature, 500 mg (1.86 mmol) of compound II-1 was dissolved in 100 mL of water, and 10 mL of 1 M potassium hydroxide aqueous solution was added dropwise, with stirring overnight at room temperature. After the reaction was complete, 1 M phosphoric acid was added dropwise to the system to adjust the pH to 6.4. Then, N2 was added to the system. 1 N 1Dimethylethane-1,3-diamine (163.9 mg, 1.86 mmol) was added dropwise to the system, followed by the addition of 1 M phosphoric acid to adjust the pH to 6.4. The system was then heated and refluxed overnight. After cooling to room temperature, the reaction was filtered, and acetic acid was added to the filtrate until a solid precipitated completely. The resulting pale yellow solid was filtered and dried under vacuum, with a yield of 87%. It was confirmed to be a compound of formula (1-2).

[0227] The characterization data of the product are as follows:

[0228] 1H NMR (400MHz, DMSO-d6) δ10.06(s,1H),8.46(d,J=7.6Hz,2H),8.09(d,J=7.6Hz,1H),4.29(t,J=5.4Hz,2H),3.39(d,J=4.9Hz,2H),2.78(d,J=4.3Hz,6H).

[0229] 13C NMR (101MHz, DMSO-d6): δ (ppm) 169.0, 163.9, 137.5, 130.7, 129.7, 129.2, 126.1, 125.1, 55.5, 43.3, 35.8

[0230] Example 15: Preparation of hybrid electron transport layer ZnO / C2-NMA

[0231] (1) Dissolve 100 mg of zinc acetate dihydrate, a zinc oxide precursor, and 28 μl of ethanolamine in 4 ml of dimethoxyethanol. After stirring overnight, deposit the solution on top of ITO at 3000 rpm and bake at 200 °C for 1 hour to obtain a zinc oxide film.

[0232] (2) Add the compound of formula (1-2) (aromatic imide derivative) to an appropriate amount of methanol containing 2% ammonia water by volume to prepare a solution of 0.4 mg / ml.

[0233] (3) Spin-coat the solution obtained in step (2) onto the zinc oxide film obtained in step (1) at a rotation speed of 3000 rpm to obtain an n-type semiconductor film.

[0234] (4) The resulting hybrid electron transport layer was baked at 120°C for 10 minutes.

[0235] Example 16: Fabrication and Performance of Organic Optoelectronic Devices Based on ZnO / C2-NMA Hybrid Electron Transport Layer and PM6:Y6 Active Layer

[0236] The optoelectronic device structure is ITO / ETL / donor material:acceptor material / MoO3 / Ag. The fabrication process is as follows: Pretreatment of ITO (indium tin oxide) glass: The ITO-sputtered glass substrate is sequentially ultrasonicated in deionized water, acetone, and isopropanol for 15 minutes each, dried by nitrogen purging, and then treated under UV-ozone for 20 minutes. On the ozone-treated ITO substrate, a ZnO film approximately 15 nm thick or a hybrid ZnO / C2-NMA film approximately 19 nm thick is sequentially deposited. Then, an active layer PM6:Y6 approximately 100 nm thick is deposited, wherein the preparation of the PM6:Y6 solution and the post-treatment of the film are the same as described in Example 11. Then, under a vacuum degree less than 2 × 10⁻⁶… -4 A 6 nm layer of MoO3 was deposited as a hole transport layer under Pa conditions, and then, under the cover of a mask, the hole transport layer was deposited at a vacuum level of less than 2 × 10⁻⁶. -4 Under Pa conditions, 150 nm Ag is deposited as the anode, and the effective cell area is approximately 4 mm². 2 The device performance was tested under standard sunlight (AM1.5G) irradiation conditions using a computer-controlled Keithley 2400 digital source meter.

[0237] Table 9: Performance comparison of solar cells prepared with ZnO and ZnO / C2-NMA electron transport layer PM6:Y6 as active layers.

[0238]

[0239] Example 17: Preparation of dicarboxylated naphthalene diimide (C4-NMA) as shown in formula (1-3)

[0240]

[0241] At room temperature, 500 mg (1.86 mmol) of compound II-1 was dissolved in 100 mL of water, and 10 mL of 1 M potassium hydroxide aqueous solution was added dropwise, with stirring overnight at room temperature. After the reaction was complete, 1 M phosphoric acid was added dropwise to the system to adjust the pH to 6.4. Then, N2 was added to the system. 1 N 1 Dimethylbutane-1,3-diamine (216.0 mg, 1.86 mmol) was added dropwise to the system, followed by the addition of 1 M phosphoric acid to adjust the pH to 6.4. The system was then heated and refluxed overnight. After cooling to room temperature, the reaction was filtered, and acetic acid was added to the filtrate until a complete solid precipitated. The resulting pale yellow solid was filtered and dried under vacuum, with a yield of 83%. It was confirmed to be a compound of formula (1-3).

[0242] The characterization data of the product are as follows:

[0243] 1H NMR(400MHz, DMSO-d6)δ10.35(s,1H),8.50(d,J=7.5Hz,2H),8.13(d,J=7.5Hz,2H), 3.99(t,J=6.6Hz,2H),3.06–2.96(m,2H),2.65(d,J=4.8Hz,6H),1.70–1.57(m,4H).

[0244] 13C NMR (101MHz, DMSO-d6): δ (ppm) 169.1, 163.5, 137.3, 130.6, 129.7, 129.2, 126.1, 125.1, 57.1, 42.8, 25.0, 22.0

[0245] Example 18: Preparation of hybrid electron transport layer ZnO / C4-NMA

[0246] (1) Dissolve 100 mg of zinc acetate dihydrate, a zinc oxide precursor, and 28 μl of ethanolamine in 4 ml of dimethoxyethanol. After stirring overnight, deposit the solution on top of ITO at 3000 rpm and bake at 200 °C for 1 hour to obtain a zinc oxide film.

[0247] (2) Add the compound of formula (1-3) (aromatic imide derivative) to an appropriate amount of methanol containing 2% ammonia water by volume to prepare a solution of 0.4 mg / ml.

[0248] (3) Spin-coat the solution obtained in step (2) onto the zinc oxide film obtained in step (1) at a rotation speed of 3000 rpm to obtain an n-type semiconductor film.

[0249] (4) The resulting hybrid electron transport layer was baked at 120°C for 10 minutes.

[0250] Example 19: Fabrication and Performance of Organic Optoelectronic Devices Based on ZnO / C4-NMA Hybrid Electron Transport Layer and PM6:Y6 Active Layer

[0251] The optoelectronic device structure is ITO / ETL / donor material:acceptor material / MoO3 / Ag. The fabrication process is as follows: Pretreatment of ITO (indium tin oxide) glass: The ITO-sputtered glass substrate is sequentially ultrasonicated in deionized water, acetone, and isopropanol for 15 minutes each, dried by nitrogen purging, and then treated under UV-ozone for 20 minutes. On the ozone-treated ITO substrate, a ZnO film approximately 15 nm thick or a hybrid ZnO / C4-NMA film approximately 19 nm thick is sequentially deposited. Then, an active layer PM6:Y6 approximately 100 nm thick is deposited, wherein the preparation of the PM6:Y6 solution and the post-treatment of the film are the same as described in Example 11. Then, under a vacuum degree less than 2 × 10⁻⁶… -4A 6 nm layer of MoO3 was deposited as a hole transport layer under Pa conditions, and then, under the cover of a mask, the hole transport layer was deposited at a vacuum level of less than 2 × 10⁻⁶. -4 Under Pa conditions, 150 nm Ag is deposited as the anode, and the effective cell area is approximately 4 mm². 2 The device performance was tested under standard sunlight (AM1.5G) irradiation conditions using a computer-controlled Keithley 2400 digital source meter.

[0252] Table 10: Performance comparison of solar cells prepared with ZnO and ZnO / C4-NMA electron transport layer PM6:Y6 as active layers, respectively.

[0253]

[0254] Example 20: Preparation of dicarboxylated naphthalene diimide (CO-NMA) as shown in formulas (1-4)

[0255]

[0256] At room temperature, 500 mg (1.86 mmol) of compound II-1 was dissolved in 100 mL of water, and 10 mL of 1 M potassium hydroxide aqueous solution was added dropwise, with stirring overnight at room temperature. After the reaction was complete, 1 M phosphoric acid was added dropwise to the system to adjust the pH to 6.4. Then, N2 was added to the system. 1 N 1 Dimethylbutane-1,3-diamine (111.7 mg, 1.86 mmol) was added dropwise to the system, followed by the addition of 1 M phosphoric acid to adjust the pH to 6.4. The system was then heated and refluxed overnight. After cooling to room temperature, the reaction was filtered, and acetic acid was added to the filtrate until a complete solid precipitated. The resulting pale yellow solid was filtered and dried under vacuum, with a yield of 77%. It was confirmed to be a compound of formula (1-4).

[0257] The characterization data are as follows:

[0258] 1H NMR (400MHz, DMSO-d6) δ13.54 (s, 2H), 8.53 (d, J = 5.7Hz, 2H), 8.18 (d, J = 5.7Hz, 2H), 2.95 (s, 6H).

[0259] 13 C NMR (100MHz, DMSO-d6) δ169.0,163.9,137.5,130.7,129.7,129.2,126.1,125.1,54.56.

[0260] Example 21: Preparation of hybrid electron transport layer ZnO / CO-NMA

[0261] (1) Dissolve 100 mg of zinc acetate dihydrate, a zinc oxide precursor, and 28 μl of ethanolamine in 4 ml of dimethoxyethanol. After stirring overnight, deposit the solution on top of ITO at 3000 rpm and bake at 200 °C for 1 hour to obtain a zinc oxide film.

[0262] (2) Add the compound of formula (1-4) (aromatic imide derivative) to an appropriate amount of methanol containing 2% ammonia water by volume to prepare a solution of 0.4 mg / ml.

[0263] (3) Spin-coat the solution obtained in step (2) onto the zinc oxide film obtained in step (1) at a rotation speed of 3000 rpm to obtain an n-type semiconductor film.

[0264] (4) The resulting hybrid electron transport layer was baked at 120°C for 10 minutes.

[0265] Example 22: Fabrication and Performance of Organic Optoelectronic Devices Based on ZnO / CO-NMA Hybrid Electron Transport Layer and PM6:Y6 Active Layer

[0266] The optoelectronic device structure is ITO / ETL / donor material:acceptor material / MoO3 / Ag. The fabrication process is as follows: Pretreatment of ITO (indium tin oxide) glass: The ITO-sputtered glass substrate is sequentially ultrasonicated in deionized water, acetone, and isopropanol for 15 minutes each, dried by nitrogen purging, and then treated under UV-ozone for 20 minutes. On the ozone-treated ITO substrate, a ZnO film approximately 15 nm thick or a hybrid ZnO / CO-NMA film approximately 19 nm thick is sequentially deposited. Then, an active layer PM6:Y6 approximately 100 nm thick is deposited, wherein the preparation of the PM6:Y6 solution and the post-treatment of the film are the same as described in Example 11. Then, under a vacuum degree less than 2 × 10⁻⁶… -4 A 6 nm layer of MoO3 was deposited as a hole transport layer under Pa conditions, and then, under the cover of a mask, the hole transport layer was deposited at a vacuum level of less than 2 × 10⁻⁶. -4 Under Pa conditions, 150 nm Ag is deposited as the anode, and the effective cell area is approximately 4 mm². 2 The device performance was tested under standard sunlight (AM1.5G) irradiation conditions using a computer-controlled Keithley 2400 digital source meter.

[0267] Table 11: Performance comparison of solar cells prepared with ZnO and ZnO / CO-NMA as electron transport layers and PM6:Y6 as active layers, respectively.

[0268]

[0269] Example 23: Preparation of dicarboxylated naphthalene (NMA-Br) as shown in formula (2-1)

[0270]

[0271] At room temperature, 30 mg of formula (1-1) (0.08 mmol) obtained in Example 1 was dissolved in 4 ml of water, and 1.25 g (8 mmol) of bromoethane was added. The mixture was stirred at room temperature for two days. After the reaction was completed, the reaction was filtered, and diethyl ether was added to the filtrate until a solid was completely precipitated. The resulting pale yellow solid was filtered and dried under vacuum to give 26.31 mg of the product (yield 62.6%), which is formula (2-1).

[0272] Organic optoelectronic devices based on a hybrid electron transport layer SnO2 / NMA-Br as the electron transport layer and different active layers were fabricated, and their performance was tested according to the embodiments described above. The results showed that the hybrid electron transport layer of this embodiment could exhibit a higher fill factor and photoelectric conversion efficiency.

[0273] The above results demonstrate that the aromatic imide derivatives containing acidic functional groups described in this disclosure form a hybrid electron transport layer after modifying zinc oxide thin films, thereby producing organic optoelectronic devices with superior photoelectric performance and improved long-term operational stability. This hybrid electron transport layer is universally applicable to different active layer systems. Various flexible and large-area devices can be fabricated based on this hybrid interface layer.

[0274] The disclosed compound, as an organic material, possesses excellent electrochemical performance. When used as an active positive or negative electrode material in lithium-ion batteries, it exhibits high specific capacity and charge-discharge cycle stability. In other words, all-organic symmetric lithium-ion batteries using this compound as both active positive and negative electrode materials can exhibit high specific capacity and charge-discharge cycle stability. Furthermore, this material can also be used to prepare various high-performance flexible lithium-ion batteries.

[0275] The above content is merely an example of this disclosure and is not intended to limit the scope of this disclosure. Any modifications, equivalent substitutions, improvements, etc., made within the concept and principles of this disclosure are included within the protection scope of this disclosure.

Claims

1. Applications of compounds with the structure of general formula (I) or their salts in optoelectronic devices: General Formula (I) in, Ar is an aromatic fused ring selected from the following, optionally substituted with deuterium, halogen or C1-C12 alkyl: or in, Indicates the connection position with adjacent groups; A1 and A2 are each independently selected from hydrogen, carboxylic acid group, and phosphate group, and A1 and A2 are not both hydrogen; n is a natural number from 0 to 12; and [N] represents a tertiary amine group. The carboxylic acid group and phosphate group optionally form a salt with an alkali metal, and / or the tertiary amine group optionally forms an ammonium salt with a halogen; and The substitution mentioned therein refers to substitution by a substituent selected from deuterium, halogen, cyano, C1-C12 alkyl, C1-C12 alkoxy, C1-C12 etheroxy and C6-C20 aryl.

2. The application according to claim 1, wherein, n is a natural number from 1 to 4.

3. The application according to claim 1, wherein, A1 and A2 are each independently selected from: and A1 and A2 may optionally form salts with lithium, sodium, or potassium, and in, Indicates the connection position with adjacent groups.

4. The application according to claim 1, wherein, [N] indicates that the selection is from: and R1, R2, and R3 are each independently selected from C1-C12 alkyl, C1-C12 alkoxy, and C1-C12 etheroxy groups. Hal indicates fluorine, chlorine, bromine, or iodine; in, Indicates the connection position with adjacent groups.

5. The application according to claim 4, wherein, R1, R2, and R3 are each independently selected from C1-C8 alkyl, C1-C8 alkoxy, and C1-C8 etheroxy groups.

6. The application according to claim 5, wherein, R1, R2, and R3 are each independently selected from C1-C4 alkyl, C1-C4 alkoxy, and C1-C4 etheroxy groups.

7. The application according to claim 1, wherein the general formula (I) is selected from any one of formulas (1) to (16): in, In formulas (1), (3), (5), (7), (9), (11), (13) to (15), R1 and R2 are methyl groups and n is 0, 1, 2 or 3. In formulas (2), (4), (6), (8), (10), (12), (14) to (16), R1, R2, and R3 are methyl groups and n is 0, 1, 2, or 3; or In formulas (2), (4), (6), (8), (10), (12), (14) to (16), R1 and R2 are methyl, R3 is ethyl, and n is 0, 1, 2 or 3.

8. The application according to claim 7, wherein, The hydrogen atoms of one or both carboxylic acid groups in formulas (1), (2), (9) and (10) are replaced by potassium or sodium to form salts; The hydrogen atoms of the carboxylic acid groups in formulas (3), (4), (11) and (12) are replaced by potassium or sodium to form salts; In formulas (5), (6), (13), and (14), one or two hydrogen atoms of one or two phosphate groups are replaced by potassium or sodium to form a salt; or One or both hydrogen atoms in the phosphate groups of formulas (7), (8), (15) and (16) are replaced by potassium or sodium to form salts.

9. The application according to claim 1, wherein, The compound is selected from:

10. The application according to any one of claims 1 to 9, wherein the method for preparing the compound or a salt thereof comprises: (a) A compound having the structure of general formula (II) is hydrolyzed under alkaline conditions to obtain the hydrolysis product; (b) The hydrolysis product is subjected to a condensation reaction with a compound having the structure of general formula (Ⅲ) under weakly acidic conditions; The definition of Ar in general formula (II) is the same as that in general formula (I); In general formula (Ⅲ), R1, R2, and n are defined in the same way as in general formula (I); and In the haloalkyl R3-Hal, the definitions of R3 and Hal are the same as in general formula (I).

11. The application according to claim 10, wherein, The preparation method further includes reacting the condensation product with a haloalkyl group R3-Hal.

12. The application according to claim 10, wherein, In the preparation method, the molar ratio of the compound of general formula (II) to the compound of general formula (III) is 1:1 to 1:

10.

13. The application according to claim 10, wherein, In the preparation method, the molar ratio of the compound of general formula (II) to the compound of general formula (III) is 1:

1.

14. An optoelectronic device comprising an anode, and a hole transport layer, a light-emitting layer, an electron transport layer and a cathode sequentially disposed on the anode, wherein the electron transport layer is a composite layer comprising any one of claims 1 to 13 or a salt thereof and a metal oxide.

15. The optoelectronic device according to claim 14, wherein the metal oxide is selected from zinc oxide, tin dioxide, or a combination thereof.

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