CN113816862A

CN113816862A - Aromatic amine compound, mixture, composition and organic electronic device

Info

Publication number: CN113816862A
Application number: CN202110058308.1A
Authority: CN
Inventors: 谭甲辉; 胡洁; 董泽斌
Original assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Current assignee: Guangzhou Chinaray Optoelectronic Materials Ltd
Priority date: 2020-06-19
Filing date: 2021-01-15
Publication date: 2021-12-21

Abstract

The invention relates toAromatic amine compounds, mixtures, compositions and organic electronic devices. The aromatic amine compound has the structure shown in the formula (1), shows excellent hole transport property and stability, can be used as a hole transport layer material in an organic electroluminescent device, can reduce the driving voltage, can improve the electroluminescent efficiency, and can prolong the service life of the device.

Description

Aromatic amine compound, mixture, composition and organic electronic device

The present application claims priority from chinese patent application entitled "an aromatic amine compound and its use in organic electronic devices" filed by the chinese patent office on 19/6/2020, application No. 202010566378.3, the entire contents of which are incorporated herein by reference.

Technical Field

The invention relates to the technical field of organic electroluminescence, in particular to an aromatic amine compound, a mixture, a composition and an organic electronic device.

Background

Organic Light Emitting Diodes (OLEDs) have great potential for applications in optoelectronic devices, such as flat panel displays and lighting, due to their advantages of being versatile, low cost to manufacture, and good in optical and electrical performance.

The organic electroluminescence phenomenon refers to a phenomenon of converting electric energy into light energy using an organic substance. An organic electroluminescent element utilizing an organic electroluminescent phenomenon generally has a structure including a positive electrode and a negative electrode and an organic layer therebetween. In order to improve the efficiency and lifetime of the organic electroluminescent element, the organic layer has a multi-layer structure, each layer containing a different organic substance. Specifically, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like may be included. In such an organic electroluminescent element, when a voltage is applied between the two electrodes, holes are injected from the positive electrode into the organic layer, electrons are injected from the negative electrode into the organic layer, excitons are formed when the injected holes and electrons meet, and light is emitted when the excitons transition back to the ground state. The organic electroluminescent element has the characteristics of self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, high responsiveness and the like.

However, OLED devices are still required to be further improved in light-emitting efficiency and service life because OLED devices are operated in a high current density state as current-driven devices, and the materials are prone to joule heat, resulting in device degradation, especially between the anode and the hole transport layer. The commonly used hole transport material has low glass transition temperature, the appearance of the film is changed due to accumulation of Joule heat, and meanwhile, the material decomposition is accelerated, so that the service life of the device is influenced. In addition, the hole mobility of the organic semiconductor material is generally higher than the electron mobility, so that the hole-electron transport imbalance is caused to influence the light emitting efficiency of the device.

Although a large amount of hole transport materials have been developed at present, many problems still exist, and how to design a new material with better performance for adjustment, so as to achieve the effects of reducing the voltage of the device and improving the efficiency and the service life of the device, which is always a problem to be solved by the technical staff in the field.

Disclosure of Invention

Based on this, it is an object of the present invention to provide an aromatic amine compound, a mixture, a composition and an organic electronic device, which improve the efficiency and lifetime of the device.

The technical scheme is as follows:

an aromatic amine compound having a structure represented by general formula (1):

wherein:

w is selected from O or S;

L₁-L₆independently selected from a single bond, or a substituted or unsubstituted aromatic or heteroaromatic group having 6 to 40 ring atoms;

Ar₁-Ar₄independently selected from a substituted or unsubstituted aromatic group having 6 to 40 ring atoms, or a substituted or unsubstituted aromatic group having 5 to 40 ring atomsHeteroaromatic groups or non-aromatic ring systems.

The invention also provides a mixture, which comprises the aromatic amine compound and at least one other organic functional material, wherein the other organic functional material is at least one selected from a hole injection material, a hole transport material, an electron injection material, an electron blocking material, a hole blocking material, a light emitting material, a host material and an organic dye.

The invention also provides a composition which comprises the aromatic amine compound or the mixture and at least one organic solvent.

The invention also provides an organic electronic device, which at least comprises the aromatic amine compound, the high polymer, the mixture or the composition.

Compared with the prior art, the invention has the following beneficial effects:

the aromatic amine compound provided by the invention is of an asymmetric structure, and has excellent hole transport property when being used as a hole transport material for an OLED device, the OLED device with high luminous efficiency and long service life can be obtained. Meanwhile, the aromatic amine compound of the present invention has weak EA (electron affinity) to have an effect of blocking electrons from adjacent layers of the electron transport layer, and has high electrochemical stability, so that recombination efficiency is improved, luminous efficiency is improved, the lifetime of the device is prolonged, and driving voltage can be reduced.

Detailed Description

The present invention will be described in further detail with reference to specific examples. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.

Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. As used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.

In the present invention, the composition and the printing ink, or ink, have the same meaning and may be interchanged.

In the present invention, the aromatic groups, aromatic groups and aromatic ring systems have the same meaning and are interchangeable.

In the context of the present invention, heteroaromatic groups, heteroaromatic and heteroaromatic ring systems have the same meaning and are interchangeable.

In the present invention, "substituted" means that a hydrogen atom in a substituent is substituted by a substituent.

In the present invention, "substituted or unsubstituted" means that the defined group may or may not be substituted. When a defined group is substituted, it is understood to be optionally substituted with art-acceptable groups including, but not limited to: c_1-30An alkyl group, a cycloalkyl group having 3 to 20 ring atoms, a heterocyclic group having 3 to 20 ring atoms, an aryl group having 5 to 20 ring atoms, a heteroaryl group having 5 to 20 ring atoms, a silane group, a carbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carbamoyl group, a haloformyl group, a formyl group, -NRR', a cyano group, an isocyano group, an isocyanate group, a thiocyanate group, an isothiocyanate group, a hydroxyl group, a trifluoromethyl group, a nitro group or a halogen, and the above groups may be further substituted with a substituent acceptable in the art; it is understood that R and R 'in-NRR' are each independently substituted with art-acceptable groups including, but not limited to, H, C₁-₆An alkyl group, a cycloalkyl group having 3 to 8 ring atoms, a heterocyclic group having 3 to 8 ring atoms, an aryl group having 5 to 20 ring atoms, or a heteroaryl group having 5 to 10 ring atoms; said C is_1-6Alkyl, cycloalkyl containing 3 to 8 ring atoms, heterocyclyl containing 3 to 8 ring atoms, aryl containing 5 to 20 ring atoms or heteroaryl containing 5 to 10 ring atoms are optionally further substituted by one or more of the following: c₁-₆Alkyl, cycloalkyl having 3 to 8 ring atoms, heterocyclyl having 3 to 8 ring atoms,Halogen, hydroxyl, nitro or amino.

In the present invention, the "number of ring atoms" represents the number of atoms among atoms constituting the ring itself of a structural compound (for example, a monocyclic compound, a condensed ring compound, a crosslinked compound, a carbocyclic compound, and a heterocyclic compound) in which atoms are bonded in a ring shape. When the ring is substituted with a substituent, the atoms contained in the substituent are not included in the ring-forming atoms. The "number of ring atoms" described below is the same unless otherwise specified. For example, the number of ring atoms of the benzene ring is 6, the number of ring atoms of the naphthalene ring is 10, and the number of ring atoms of the thienyl group is 5.

"aryl or aromatic group" means an aromatic hydrocarbon group derived by removing one hydrogen atom from an aromatic ring compound, and may be a monocyclic aromatic group, or a fused ring aromatic group, or a polycyclic aromatic group, at least one of which is an aromatic ring system for polycyclic ring species. For example, "substituted or unsubstituted aryl group having 6 to 40 ring atoms" means an aryl group containing 6 to 40 ring atoms, preferably a substituted or unsubstituted aryl group having 6 to 30 ring atoms, more preferably a substituted or unsubstituted aryl group having 6 to 18 ring atoms, particularly preferably a substituted or unsubstituted aryl group having 6 to 14 ring atoms, and the aryl group is optionally further substituted; suitable examples include, but are not limited to: benzene, biphenyl, terphenyl, naphthalene, anthracene, fluoranthene, phenanthrene, triphenylene, perylene, tetracene, pyrene, benzopyrene, acenaphthylene, fluorene and derivatives thereof. It will be appreciated that a plurality of aryl groups may also be interrupted by short non-aromatic units (e.g. < 10% of non-H atoms, such as C, N or O atoms), such as in particular acenaphthene, fluorene, or 9, 9-diarylfluorene, triarylamine, diarylether systems should also be included in the definition of aryl groups.

"heteroaryl or heteroaromatic group" means that on the basis of an aryl group at least one carbon atom is replaced by a non-carbon atom which may be a N atom, an O atom, an S atom, etc. For example, "substituted or unsubstituted heteroaryl having 5 to 40 ring atoms" refers to heteroaryl having 5 to 40 ring atoms, preferably substituted or unsubstituted heteroaryl having 6 to 30 ring atoms, more preferably substituted or unsubstituted heteroaryl having 6 to 18 ring atoms, particularly preferably substituted or unsubstituted heteroaryl having 6 to 14 ring atoms, and heteroaryl is optionally further substituted, suitable examples including but not limited to: triazines, pyridines, pyrimidines, imidazoles, furans, thiophenes, benzofurans, benzothiophenes, indoles, carbazoles, pyrroloimidazoles, pyrrolopyrroles, thienopyrroles, thienothiophenes, furopyrroles, furofurans, thienofurans, benzisoxazoles, benzisothiazoles, benzimidazoles, quinolines, isoquinolines, phthalazines, quinoxalines, phenanthridines, primates, quinazolines, quinazolinones, dibenzothiophenes, dibenzofurans, carbazoles, and derivatives thereof.

In the present invention, "alkyl" may mean a linear, branched and/or cyclic alkyl group. The carbon number of the alkyl group may be 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-methylcyclohexyl, 4-tert-butylcyclohexyl, n-heptyl, 1-methylheptyl, 2-dimethylheptyl, 2-ethylheptyl, 2-butylheptyl, n-octyl, tert-octyl, 2-ethyloctyl, 2-butyloctyl, 2-hexyloctyl, tert-butyl, 2-isobutyl, 2-ethylbutyl, 3-dimethylbutyl, 2-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, 4-butylcyclohexyl, 2-butylheptyl, 2-methylheptyl, 2-ethylheptyl, 2-ethyloctyl, 2-tert-butylhexyl, 2-butylhexyl, or a, 3, 7-dimethyloctyl, cyclooctyl, n-nonyl, n-decyl, adamantyl, 2-ethyldecyl, 2-butyldecyl, 2-hexyldecyl, 2-octyldecyl, n-undecyl, n-dodecyl, 2-ethyldodecyl, 2-butyldodecyl, 2-hexyldodecyl, 2-octyldodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, 2-ethylhexadecyl, 2-butylhexadecyl, 2-hexylhexadecyl, 2-octylhexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, 2-ethyleicosyl, 2-butyleicosyl, 2-hexyleicosyl, 2-octyleicosyl, N-heneicosyl, n-docosyl, n-tricosyl, n-tetracosyl, n-pentacosyl, n-hexacosyl, n-heptacosyl, n-octacosyl, n-nonacosyl, n-triacontyl, and the like.

"halogen" or "halo" refers to F, Cl, Br, or I.

"alkylamino" refers to an amino group substituted with at least one alkyl group. Suitable examples include, but are not limited to: -NH₂、-NH(CH₃)、-N(CH₃)₂、-NH(CH₂CH₃)、-N(CH₂CH₃)₂。

"arylalkyl" refers to a hydrocarbyl radical derived from an alkyl radical having at least one hydrogen atom bonded to a carbon atom replaced by an aryl radical. Wherein the aryl moiety may include 5 to 20 carbon atoms and the alkyl moiety may include 1 to 9 carbon atoms. Suitable examples include, but are not limited to: benzyl, 2-phenyleth-1-yl, naphthylmethyl, 2-naphthyleth-1-yl, naphthobenzyl and 2-naphthophenyleth-1-yl.

The term "alkoxy" refers to a group having an-O-alkyl group, i.e., an alkyl group as defined above attached to the parent core structure via an oxygen atom. Phrases encompassing this term, suitable examples include, but are not limited to: methoxy (-O-CH)₃or-OMe), ethoxy (-O-CH)₂CH₃or-OEt) and tert-butoxy (-O-C (CH)₃)₃or-OtBu).

In the present invention, "-" denotes a connection site.

In the present invention, when the same group contains a plurality of substituents of the same symbol, the substituents may be the same or different from each other, for example

6R on the benzene ring¹May be the same as or different from each other.

In the context of the present invention, a single bond to which a substituent is attached extends through the corresponding ring, meaning that the substituent may be attached at an optional position on the ring, for example

Wherein R is attached to any substitutable site of the phenyl ring.

Represents that the naphthalene ring has 7 substitution sites, and R can be connected with any substitution site.

In the embodiment of the present invention, the energy level structure of the organic material, the triplet state energy level E_THOMO, LUMO play a key role. These energy levels are described below.

The HOMO and LUMO energy levels can be measured by the photoelectric effect, for example XPS (X-ray photoelectron spectroscopy) and UPS (ultraviolet photoelectron spectroscopy) or by cyclic voltammetry (hereinafter referred to as CV). Recently, quantum chemical methods, such as the density functional theory (hereinafter abbreviated as DFT), have become effective methods for calculating the molecular orbital level.

Triplet energy level E of organic material_T1Can be measured by low temperature Time resolved luminescence spectroscopy, or can be obtained by quantum simulation calculations (e.g., by Time-dependent DFT), such as by commercial software Gaussian 09W (Gaussian Inc.), specific simulation methods can be found in WO2011141110 or as described in the examples below.

Note that HOMO, LUMO, E_T1The absolute value of (c) depends on the measurement method or calculation method used, and even for the same method, different methods of evaluation, for example starting point and peak point on the CV curve, can give different HOMO/LUMO values. Thus, a reasonably meaningful comparison should be made with the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, HOMO, LUMO, E_T1Is based on the simulation of the Time-dependent DFT but does not affect the application of other measurement or calculation methods.

In the present invention, (HOMO-1) is defined as the second highest occupied orbital level, (HOMO-2) is defined as the third highest occupied orbital level, and so on. (LUMO +1) is defined as the second lowest unoccupied orbital level, (LUMO +2) is the third lowest occupied orbital level, and so on.

The invention aims to provide an aromatic amine compound and application thereof, which improve the efficiency and the service life of a device.

The technical scheme is as follows:

wherein:

w is selected from O or S;

Ar₁-Ar₄independently selected from a substituted or unsubstituted aromatic group having 6 to 40 ring atoms, or a substituted or unsubstituted heteroaromatic group or non-aromatic ring system having 5 to 40 ring atoms.

In one embodiment, L₅-L₆Selected from single bond, benzene, naphthalene, anthracene, phenanthrene, pyrene, pyridine, pyrimidine, triazine, fluorene, dibenzothiophene, silafluorene, carbazole, thiophene, furan, thiazole, triphenylamine, triphenyl phosphine oxide, tetraphenyl silicon, spirofluorene and the like.

Further, L₅-L₆Selected from single bonds or having a benzene, naphthalene, pyridine, pyrimidine or triazine structure.

In one embodiment, L₅-L₆Selected from the same group.

Further, L₅-L₆Selected from single bond or benzene and naphthalene structure, the aromatic amine compound has a structure shown by any one of general formulas (2-1) to (2-3):

more preferably, L₅-L₆Are all selected from single bonds, and the aromatic amine compound has a structure shown in a general formula (2-1).

In one embodiment, Ar in formula (1) or formulas (2-1) - (2-3)₁And Ar₃Selected from the same structures; further, the general formula (1) or the general formulae (2-1) to (2-3) — L₁-Ar₁And₃-Ar₃selected from the same structures.

In one embodiment, Ar in formula (1) or formula (2-1)₁And Ar₃Selected from the same structures, and Ar₂And Ar₄Selected from the same structures.

In one embodiment, x-L in formula (1) or formula (2)₁-Ar₁And₃-Ar₃selected from the same structures; further,. about. -L₂-Ar₂And₄-Ar₄selected from the same structures.

In the present invention, it is to be noted that₁-Ar₁And₃-Ar₃not forming a ring; all of₂-Ar₂And₄-Ar₄no ring is formed.

In one embodiment, Ar is₁-Ar₄Independently selected from any one of the structures shown below:

wherein:

x is selected from N or CR₁；

Y is selected from O, S, S ═ O, SO₂、NR₂、PR₂、CR₂R₃Or SiR₂R₃；

R₁-R₃At each occurrence, is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanato, thiocyanate, isothiocyanate, hydroxyformyl, haloformyl, formyl, isocyano, isocyanato, thiocyanate, isothiocyanateNitro, CF₃Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.

Preferably, R is₁-R₃Selected from hydrogen, D, or a straight chain alkyl group having 1 to 10C atoms, or a branched alkyl group having 3 to 10C atoms, or a cycloalkyl group having 3 to 10C atoms, Cl, Br, F, cyano or phenyl.

Further, Ar in the general formula (1) or the general formulae (2-1) to (2-3)₁-Ar₄Each independently selected from one of the following groups:

n is selected from 0, 1,2,3 or 4.

Further, Ar in the general formula (1)₁-Ar₄Each independently selected from any one of the following groups:

in one embodiment, Ar₁-Ar₄Each is independently selected from

Or

(ii) a Further, n is selected from 0.

In one embodiment, Ar₁-Ar₄At least one of them is selected from

. Further, Ar₁-Ar₄At least two of which are selected from

Further, in the present invention,

is selected from

In one embodiment, Ar₁-Ar₄At least one of them is selected from

. Further, Ar₁-Ar₄At least two of which are selected from

. Further, in the present invention,

is selected from

In a preferred embodiment, Ar₁-Ar₄At least two of which are selected from

(ii) a Further Ar₁-Ar₄Are all selected from

In one embodiment, formula (1) is selected from structures represented by any one of formulae (3-1) to (3-4):

in one embodiment, L₁-L₄Independently selected from a single bond, or a substituted or unsubstituted aromatic or heteroaromatic group having 6 to 20 ring atoms; further, L₁-L₄Independently selected from a single bond, or an aromatic group with 6 to 12 ring atoms;

further, L₁-L₄Each occurrence is independently selected from a single bond or any one of the following groups:

in one embodiment, L₁-L₄Each occurrence is independently selected from the group consisting of a single bond and phenyl.

Preferably of the formula (1)

And

each independently selected from any one of the following groups:

in one embodiment, formula (1) is selected from any one of formulae (4-1) to (4-6):

preferably, R is as described in the general formula₁Selected from hydrogen, D, or a straight chain alkyl group having 1 to 8C atoms, or a branched alkyl group having 3 to 8C atoms, or a cycloalkyl group having 3 to 8C atoms, Cl, Br, F, cyano or phenyl.

A compound according to the present invention is preferably selected from, but not limited to, the following structures:

the aromatic amine compound according to the present invention can be used as a functional material in an organic functional layer of an electronic device. The organic functional layer includes, but is not limited to, a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), an Electron Blocking Layer (EBL), a Hole Blocking Layer (HBL), and an emission layer (EML).

In one embodiment, the aromatic amine compound according to the present invention is used in a hole transport layer.

The invention further relates to a mixture comprising at least one aromatic amine compound as described above, and at least one further organic functional material, which may be selected from the group consisting of Hole Injection Materials (HIM), Hole Transport Materials (HTM), Electron Transport Materials (ETM), Electron Injection Materials (EIM), Electron Blocking Materials (EBM), Hole Blocking Materials (HBM), light emitting materials (Emitter), Host materials (Host) and organic dyes. Various organic functional materials are described in detail, for example, in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of this 3 patent document being hereby incorporated by reference.

In one embodiment, the further organic functional material is selected from electron transport materials, which are used as co-hosts in electronic devices.

The invention also relates to a composition comprising at least one aromatic amine compound or mixture as described above, and at least one organic solvent; the at least one organic solvent is selected from aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic compound, or boric acid ester or phosphoric acid ester compound, or a mixture of two or more solvents.

In a preferred embodiment, a composition according to the invention is characterized in that said at least one organic solvent is chosen from aromatic or heteroaromatic-based solvents.

Examples of aromatic or heteroaromatic based solvents suitable for the present invention are, but not limited to: p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1, 4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentyltoluene, o-diethylbenzene, m-diethylbenzene, p-diethylbenzene, 1,2,3, 4-tetramethylbenzene, 1,2,3, 5-tetramethylbenzene, 1,2,4, 5-tetramethylbenzene, butylbenzene, dodecylbenzene, dihexylbenzene, dibutylbenzene, p-diisopropylbenzene, cyclohexylbenzene, benzylbutylbenzene, dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, 1-methylnaphthalene, 1,2, 4-trichlorobenzene, 4-difluorodiphenylmethane, 1, 2-dimethoxy-4- (1-propenyl) benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α -dichlorodiphenylmethane, 4- (3-phenylpropyl) pyridine, benzyl benzoate, 1-bis (3, 4-dimethylphenyl) ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furancarboxylate, ethyl 2-furancarboxylate, and the like;

examples of aromatic ketone-based solvents suitable for the present invention are, but not limited to: 1-tetralone, 2- (phenylepoxy) tetralone, 6- (methoxy) tetralone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, and the like;

examples of aromatic ether-based solvents suitable for the present invention are, but not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethylacetal, tetrahydro-2-phenoxy-2H-pyran, 1, 2-dimethoxy-4- (1-propenyl) benzene, 1, 4-benzodioxan, 1, 3-dipropylbenzene, 2, 5-dimethoxytoluene, 4-ethylphenetole, 1, 3-dipropoxybenzene, 1,2, 4-trimethoxybenzene, 4- (1-propenyl) -1, 2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-t-butylanisole, trans-p-propenylanisole, 1, 2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, methyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether;

in some preferred embodiments, the at least one organic solvent may be selected from: aliphatic ketones such as 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2, 5-hexanedione, 2,6, 8-trimethyl-4-nonanone, fenchylone, phorone, isophorone, di-n-amyl ketone, etc.; or aliphatic ethers such as amyl ether, hexyl ether, dioctyl ether, ethylene glycol dibutyl ether, diethylene glycol diethyl ether, diethylene glycol butyl methyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol ethyl methyl ether, triethylene glycol butyl methyl ether, tripropylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, and the like.

In other preferred embodiments, the at least one organic solvent may be selected from ester-based solvents: alkyl octanoates, alkyl sebacates, alkyl stearates, alkyl benzoates, alkyl phenylacetates, alkyl cinnamates, alkyl oxalates, alkyl maleates, alkyl lactones, alkyl oleates, and the like. Octyl octanoate, diethyl sebacate, diallyl phthalate, isononyl isononanoate are particularly preferred.

The solvents mentioned may be used alone or as a mixture of two or more organic solvents.

In certain preferred embodiments, a composition according to the invention is characterized by comprising at least one organic compound or polymer or mixture as described above and at least one organic solvent, and may further comprise another organic solvent. Examples of another organic solvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, methylene chloride, chloroform, chlorobenzene, o-dichlorobenzene, tetrahydrofuran, anisole, morpholine, toluene, o-xylene, m-xylene, p-xylene, 1, 4-dioxane, acetone, methyl ethyl ketone, 1, 2-dichloroethane, 3-phenoxytoluene, 1,1, 1-trichloroethane, 1,1,2, 2-tetrachloroethane, ethyl acetate, butyl acetate, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, tetrahydronaphthalene, decalin, indene, and/or mixtures thereof.

In some preferred embodiments, particularly suitable solvents for the present invention are those having Hansen (Hansen) solubility parameters within the following ranges:

delta d (dispersion force) is within the range of 17.0-23.2 MPa1/2, especially within the range of 18.5-21.0 MPa 1/2;

δ p (polar force) is in the range of 0.2-12.5 MPa1/2, especially in the range of 2.0-6.0 MPa 1/2;

delta h (hydrogen bonding force) is in the range of 0.9-14.2 MPa1/2, especially in the range of 2.0-6.0 MPa 1/2.

The compositions according to the invention, in which the organic solvent is selected taking into account its boiling point parameter. In the invention, the boiling point of the organic solvent is more than or equal to 150 ℃; preferably equal to or more than 180 ℃; more preferably more than or equal to 200 ℃; more preferably more than or equal to 250 ℃; most preferably at least 300 ℃. Boiling points in these ranges are beneficial for preventing nozzle clogging in inkjet print heads. The organic solvent may be evaporated from the solvent system to form a thin film comprising the functional material.

In a preferred embodiment, the composition according to the invention is a solution.

In another preferred embodiment, the composition according to the invention is a suspension.

The compositions of the embodiments of the present invention may comprise from 0.01 wt% to 10 wt% of the compound or mixture according to the present invention, preferably from 0.1 wt% to 15 wt%, more preferably from 0.2 wt% to 5 wt%, and most preferably from 0.25 wt% to 3 wt%.

The invention also relates to the use of said composition as a coating or printing ink for the production of organic electronic devices, particularly preferably by a printing or coating production process.

Suitable Printing or coating techniques include, but are not limited to, ink jet Printing, letterpress, screen Printing, dip coating, spin coating, doctor blade coating, roll Printing, twist roll Printing, lithographic Printing, flexographic Printing, rotary Printing, spray coating, brush or pad Printing, slot die coating, and the like. Gravure printing, jet printing and ink jet printing are preferred. The solution or suspension may additionally include one or more components such as surface active compounds, lubricants, wetting agents, dispersants, hydrophobing agents, binders, and the like, for adjusting viscosity, film forming properties, enhancing adhesion, and the like. The printing technology and the requirements related to the solution, such as solvent and concentration, viscosity, etc.

The present invention also provides a use of the aromatic amine compound, mixture or composition as described above in an Organic electronic device selected from, but not limited to, Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (fets), Organic lasers, Organic spintronic devices, Organic sensors, and Organic Plasmon Emitting diodes (Organic plasma Emitting diodes), etc., particularly preferably OLEDs. In the embodiment of the present invention, the aromatic amine compound is preferably used for a hole transport layer of an OLED device.

The invention further relates to an organic electronic device comprising at least one functional layer comprising an aromatic amine compound, mixture or prepared from a composition as described above. Further, the organic electronic device comprises a cathode, an anode and at least one functional layer, wherein the functional layer comprises one aromatic amine compound or a mixture thereof or is prepared from the composition. The functional layer is selected from a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL) and a Hole Blocking Layer (HBL); preferably, the functional layer is selected from hole transport layers.

In one embodiment, the organic electroluminescent device according to the present invention comprises an organic functional layer comprising a hole injection layer, a first hole transport layer, a second hole transport layer, a light emitting layer, and an electron transport layer; the first hole transport layer is above the hole injection layer, the second hole transport layer is above the first hole transport layer, the light emitting layer is above the second hole transport layer, and the electron transport layer is above the light emitting layer; the second hole transport layer contains an arylamine compound represented by formula (1).

The Organic electronic device can be selected from, but not limited to, Organic Light Emitting Diodes (OLEDs), Organic photovoltaic cells (OPVs), Organic light Emitting cells (OLEECs), Organic Field Effect Transistors (OFETs), Organic light Emitting field effect transistors (fets), Organic lasers, Organic spintronic devices, Organic sensors, Organic Plasmon Emitting diodes (Organic Plasmon Emitting diodes), and the like, and particularly preferred are Organic electroluminescent devices such as OLEDs, OLEECs, Organic light Emitting field effect transistors.

In the above-mentioned light emitting device, especially an OLED, it comprises a substrate, an anode, at least one light emitting layer, and a cathode.

The substrate may be opaque or transparent. A transparent substrate may be used to fabricate a transparent light emitting device. See, for example, Bulovic et al Nature 1996,380, p29, and Gu et al, appl.Phys.Lett.1996,68, p 2606. The substrate may be rigid or flexible. The substrate may be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. A substrate free of surface defects is a particularly desirable choice. In a preferred embodiment, the substrate is flexible, and may be selected from polymeric films or plastics having a glass transition temperature Tg of 150 deg.C or greater, preferably greater than 200 deg.C, more preferably greater than 250 deg.C, and most preferably greater than 300 deg.C. Examples of suitable flexible substrates are poly (ethylene terephthalate) (PET) and polyethylene glycol (2, 6-naphthalene) (PEN).

The anode may comprise a conductive metal or metal oxide, or a conductive polymer. The anode can easily inject holes into a Hole Injection Layer (HIL) or a Hole Transport Layer (HTL) or an emission layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or valence band level of the emitter in the light emitting layer or the p-type semiconductor material acting as a HIL or HTL or Electron Blocking Layer (EBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. Examples of anode materials include, but are not limited to: al, Cu, Au, Ag, Mg, Fe, Co, Ni, Mn, Pd, Pt, ITO, aluminum-doped zinc oxide (AZO), and the like. Other suitable anode materials are known and can be readily selected for use by one of ordinary skill in the art. The anode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is pattern structured. Patterned ITO conductive substrates are commercially available and can be used to prepare devices according to the present invention.

The cathode may comprise a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the light emitting layer. In one embodiment, the absolute value of the difference between the work function of the cathode and the LUMO level or conduction band level of the emitter in the light-emitting layer or of the n-type semiconductor material as Electron Injection Layer (EIL) or Electron Transport Layer (ETL) or Hole Blocking Layer (HBL) is less than 0.5eV, preferably less than 0.3eV, most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes in OLEDs are possible as cathode materials for the device according to the invention. Examples of cathode materials include, but are not limited to: al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF2/Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, etc. The cathode material may be deposited using any suitable technique, such as a suitable physical vapor deposition method, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may also comprise further functional layers, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an Electron Blocking Layer (EBL), an Electron Injection Layer (EIL), an Electron Transport Layer (ETL), a Hole Blocking Layer (HBL). Suitable materials for use in these functional layers are described in detail above and in WO2010135519a1, US20090134784a1 and WO2011110277a1, the entire contents of these 3 patent documents being hereby incorporated by reference.

The light-emitting device according to the present invention emits light at a wavelength of 550 to 700nm, preferably 600 to 650nm, more preferably 600 to 640 nm.

The invention also relates to the use of the electroluminescent device according to the invention in various electronic devices, including, but not limited to, display devices, lighting devices, light sources, sensors, etc.

The present invention will be described in connection with preferred embodiments, but the present invention is not limited to the following embodiments, and it should be understood that the appended claims outline the scope of the present invention and those skilled in the art, guided by the inventive concept, will appreciate that certain changes may be made to the embodiments of the invention, which are intended to be covered by the spirit and scope of the appended claims.

DETAILED DESCRIPTION OF EMBODIMENT (S) OF INVENTION

1. Synthesis of Compounds

Example 1: synthesis of Compound A

Mixing the compound 1(0.1mol), the compound 2(0.2mol), Pd (dba)₂ 1.72g(0.003mol)，t-Bu₃P17.2mL (0.009mol) and NatOBu 38.44g (0.4mol) were dissolved in 500mL of anhydrous toluene, and the reaction was stirred at 90 ℃ for 3 hours. Cooling to room temperature, adding water to terminate the reaction, adding ethyl acetate to extract, collecting organic phase, drying the organic phase with anhydrous magnesium sulfateFiltration, spin-drying of the solvent, and purification by silica gel chromatography with the mobile phase being petroleum ether gave 72.6g of example A in 87% yield. MS: the m/z test value is 835.08 g/mol.

Example 2: synthesis of Compound B

(1) Synthesis of intermediate 5

Mixing the compound 3(0.1mol), the compound 4(0.1mol), Pd (dba)₂ 1.72g(0.003mol)，t-Bu₃P17.2mL (0.009mol) and NatOBu 19.22g (0.2mol) were dissolved in 500mL of anhydrous toluene, and the reaction was stirred at 90 ℃ for 3 hours. Cooling to room temperature, adding water to terminate the reaction, extracting with ethyl acetate, collecting organic phase, drying with anhydrous magnesium sulfate, filtering, spin-drying the solvent, and separating and purifying by silica gel chromatography with petroleum ether/dichloromethane mixed solvent as mobile phase (V)_PE:V_DCM10:1) to yield 20.9g of intermediate 5 in 58% yield. MS: the m/z test value is 259.31 g/mol.

(2) Synthesis of Compound B

Analogous to the synthetic procedure for compound a, except that compound 2 was replaced with intermediate 5, resulting in compound B. MS: the m/z test value is 863.05 g/mol.

Example 3: synthesis of Compound C

(1) Synthesis of intermediate 6

Compound A (0.1mol), NBS (0.2mol) was dissolved in 200mL of anhydrous DMF and the reaction was stirred at room temperature overnight. And after the reaction is finished, adding 1L of deionized water to precipitate a solid, stirring for 30min, filtering, washing filter residues with the deionized water for three times, and drying to obtain 72.5g of intermediate 6 with the yield of 73%. MS: the m/z test value is 992.87 g/mol.

(2) Synthesis of intermediate 7

Adding the intermediate 6(0.05mol) and anhydrous THF100ml into a 250ml double-mouth reaction bottle, replacing the nitrogen five times, slowly adding n-butyl lithium (50ml, 0.12mol) dropwise under the protection of nitrogen at-78 ℃, stirring at-78 ℃ for reaction for 1.5h, then adding trimethyl borate (0.14mol) dropwise, returning to room temperature for reaction overnight, adding diluted hydrochloric acid, stirring for 30min, extracting the reaction solution with ethyl acetate, collecting an organic phase, washing with water, collecting the organic phase, drying, concentrating under reduced pressure, eluting with a rapid silica gel column by PE to remove impurities, eluting with EA to remove products, evaporating to dryness under reduced pressure to obtain 25.3g of the intermediate 7, wherein the yield is 55%. MS: the m/z test value is 922.71 g/mol.

(3) Synthesis of Compound C

Intermediate 7(0.05mol), Compound 8(0.12mol), sodium carbonate 42.4g (0.4mol), and palladium tetratriphenylphosphine 6.93g (0.006mol) were dissolved in 500mL of a mixed solvent (V)_{Water (W)}：V_Toluene1: 3) middle, 90 ℃ N₂The reaction was stirred under ambient overnight. Cooling to room temperature after reaction, adding ethyl acetate for dilution and extraction, collecting organic phase, drying the organic phase with anhydrous magnesium sulfate, vacuum filtering, spin drying the solvent, separating and purifying by silica gel chromatography, wherein the mobile phase is petroleum ether/dichloromethane mixed solvent (V)_PE:V_DCM5:1) to yield 24.9g of compound C in 50% yield. MS: the m/z test value is 997.34 g/mol.

Example 4: synthesis of Compound D

(1) Synthesis of intermediate 11

Analogous to the synthetic procedure for intermediate 5, except that compound 3 was replaced with compound 9 and compound 4 was replaced with compound 10, to give intermediate 11. MS: the m/z test value is 361.49 g/mol.

(2) Synthesis of intermediate 12

Analogous to the synthetic procedure of example a, except that compound 2 was replaced with intermediate 11, the equivalent weight of intermediate 11 was the same as compound 1, to give intermediate 12. MS: the m/z test value is 786.83 g/mol.

(3) Synthesis of Compound D

Similar to the synthetic procedure for compound a, except that compound 1 was replaced with intermediate 12, compound 2 was replaced with compound 13, and the equivalents of intermediate 12 and compound 13 were the same, to give compound D. MS: the m/z test value is 875.15 g/mol.

Example 5: synthesis of Compound E

(1) Synthesis of intermediate 15

Analogous to the synthetic procedure for intermediate 5, except that compound 4 was replaced with compound 14, resulting in intermediate 15. MS: the m/z test value is 259.31 g/mol.

(2) Synthesis of intermediate 16

Analogous to the synthetic procedure of example a, except that compound 2 was replaced with intermediate 15, the equivalents of compound 1 and intermediate 15 were the same, giving intermediate 16. MS: the m/z test value is 684.65 g/mol.

(3) Synthesis of Compound E

Similar to the synthetic procedure for compound a, except that compound 1 was replaced with intermediate 16, the equivalent weights of compound 1 and intermediate 16 were the same, and compound E was obtained. MS: the m/z test value is 849.06 g/mol.

Example 6: synthesis of Compound F

(1) Synthesis of intermediate 18

Analogous to the synthetic procedure for intermediate 5, except that compound 4 was replaced with compound 17, resulting in intermediate 18. MS: the m/z test value is 334.42 g/mol.

(2) Synthesis of intermediate 19

Analogous to the synthetic procedure of example a, except that compound 2 was replaced with intermediate 18, the equivalents of compound 1 and intermediate 18 were the same, giving intermediate 19. MS: the m/z test value is 759.77 g/mol.

(3) Synthesis of Compound F

Similar to the synthetic procedure for compound a, except that compound 1 was replaced with intermediate 19, the equivalent weight of compound 2 and intermediate 19 was the same, and compound F was obtained. MS: the m/z test value is 924.18 g/mol.

Example 7: synthesis of Compound G

(1) Synthesis of intermediate 21

Analogous to the synthetic procedure for intermediate 5, except that compound 4 was replaced with compound 20, resulting in intermediate 21. MS: the m/z test value is 295.39 g/mol.

(2) Synthesis of Compound G

Similar to the synthetic procedure for compound a, except that compound 2 was replaced with intermediate 21 and compound 1 was replaced with compound 22 to give compound G. MS: the m/z test value is 919.14 g/mol.

Example 8: synthesis of Compound H

(1) Synthesis of intermediate 25

Analogous to the synthetic procedure for intermediate 5, except that compound 3 was replaced with compound 23 and compound 4 was replaced with compound 24, to give intermediate 25. MS: the m/z test value is 273.38 g/mol.

(2) Synthesis of Compound H

Analogous to the synthetic procedure for compound a, except that compound 2 was replaced with intermediate 25 and compound 1 was replaced with compound 22 to give compound H. MS: the m/z test value is 875.13 g/mol.

Example 9: synthesis of Compound I

(1) Synthesis of intermediate 28

Compound 1(10mmol), compound 27(20mmol), sodium carbonate (40mmol), and tetrakistriphenylphosphine palladium 6.93g (0.2mmol) were dissolved in 500mL of a mixed solvent (V)_{Water (W)}：V_Toluene1: 3) middle, 90 ℃ N₂The reaction was stirred under ambient overnight. Cooling to room temperature after reaction, adding ethyl acetate for dilution and extraction, collecting organic phase, drying the organic phase with anhydrous magnesium sulfate, vacuum filtering, spin drying the solvent, separating and purifying by silica gel chromatography, wherein the mobile phase is petroleum ether/dichloromethane mixed solvent (V)_PE:V_DCM1) to yield 7.93mmol of intermediate 28 in 79.3% yield. MS: the m/z test value is 655.26 g/mol.

(2) Synthesis of Compound I

Intermediate 28(10mmol), Compound 29(20mmol), Pd (dba)₂(0.3mmol)，t-Bu₃P (0.6mmol) and NatOBu (40mmol) were dissolved in 500mL of anhydrous toluene and the reaction was stirred at 90 ℃ for 3 hours. Cooling to room temperature, adding water to terminate the reaction, extracting with ethyl acetate, collecting organic phase, drying with anhydrous magnesium sulfate, filtering, spin-drying the solvent, and separating and purifying by silica gel chromatography with petroleum ether/dichloromethane mixed solvent as mobile phase (V)_PE:V_DCM10:1) to give compound I4.38 mmol, 43.8% yield. MS: the m/z test value is 1138.34 g/mol.

Example 10: synthesis of Compound J

(1) Synthesis of intermediate 31

Compound 22(10mmol), compound 30(20mmol), sodium carbonate (40mmol), and tetrakistriphenylphosphine palladium (6.93 g, 0.2mmol) were dissolved in 500mL of a mixed solvent (V)_{Water (W)}：V_Toluene1: 3) middle, 90 ℃ N₂The reaction was stirred under ambient overnight. Cooling to room temperature after reaction, adding ethyl acetate to dilute and extract, collecting organic phase, drying the organic phase with anhydrous magnesium sulfate, suction filtering, spin drying solvent, separating and purifying by silica gel chromatography, and flowingThe phase is petroleum ether/dichloromethane mixed solvent (V)_PE:V_DCM1) to give 6.26mmol of intermediate 31 in 62.6% yield. MS: m/z test value 740..3 g/mol.

(2) Synthesis of Compound J

Intermediate 31(10mmol), Compound 13(20mmol), Pd (dba)₂(0.3mmol)，t-Bu₃P (0.6mmol) and NatOBu (40mmol) were dissolved in 500mL of anhydrous toluene and the reaction was stirred at 90 ℃ for 3 hours. Cooling to room temperature, adding water to terminate the reaction, extracting with ethyl acetate, collecting organic phase, drying with anhydrous magnesium sulfate, filtering, spin-drying the solvent, and separating and purifying by silica gel chromatography with petroleum ether/dichloromethane mixed solvent as mobile phase (V)_PE:V_DCM10:1) to give compound J2.68 mmol, 26.8% yield. MS: the m/z test value is 918.36 g/mol.

2. Preparation and characterization of OLED device

The following describes in detail the preparation process of the above-mentioned OLED device by using specific examples, and the structure of the red OLED device is: ITO/HI/HT-1/HT-2/EML/ET Liq/Liq/Al.

Device example 1:

a. cleaning an ITO (indium tin oxide) conductive glass substrate: washing with various solvents (such as one or more of chloroform, acetone or isopropanol), and performing ultraviolet ozone treatment;

b. evaporation: moving the ITO substrate into a vacuum vapor deposition apparatus under high vacuum (1X 10)^-6Mbar), a hole injection layer (material is compound HI) having a thickness of 30nm was formed using a resistance-heated evaporation source, a first hole transport layer (material is HT-1) having a thickness of 60nm was formed on the hole injection layer by heating in sequence, and then compound a was evaporated on the first hole transport layer to form a second hole transport layer having a thickness of 10 nm. Then RH is placed in one evaporation cell and compound RD is placed in the other evaporation cell as a dopant, allowing the material to vaporize at different rates such that RH: the weight ratio of RD is 100:and 3, forming a 40nm light-emitting layer on the second hole transport layer. Then ET and Liq were put in different evaporation units and co-deposited at a ratio of 50 wt% respectively to form an electron transport layer of 30nm on the light emitting layer, and subsequently Liq of 1nm was deposited as an electron injection layer on the electron transport layer, and finally an Al cathode having a thickness of 100nm was deposited on the electron injection layer.

c. Encapsulation the devices were encapsulated with uv curable resin in a nitrogen glove box.

Device examples 2-8, comparative examples 1-4 were performed as in device example 1, with the HT-2 layer materials selected as shown in table 1.

The device performances of the above examples and comparative examples were tested, wherein the driving voltage, current efficiency were 10mA/cm²Testing under current density; device lifetime of T95 refers to 50mA/cm at constant current density²The brightness decayed to 95% of the time. The results are shown in table 1:

TABLE 1

Compared with comparative examples 1 to 5, the current efficiency and the service life of the devices of examples 1 to 10 are obviously improved, and the application of the compound of the invention in an OLED device can improve the current efficiency and the service life of the device and simultaneously reduce the driving voltage of the device.

The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.

The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims

1. An aromatic amine compound characterized by having a structure represented by general formula (1):

wherein:

w is selected from O or S;

2. The aromatic amine compound according to claim 1, having a structure represented by any one of general formulae (2-1) to (2-3):

3. the aromatic amine compound according to claim 1 or 2, wherein Ar is Ar₁-Ar₄Independently selected from any one of the structures shown:

wherein:

x is selected from N or CR₁；

R₁-R₃At each occurrence, is independently selected from: hydrogen, D, straight-chain alkyl having 1 to 20C atoms, straight-chain alkoxy having 1 to 20C atoms, straight-chain thioalkoxy having 1 to 20C atoms, branched or cyclic alkyl having 3 to 20C atoms, branched or cyclic alkoxy having 3 to 20C atoms, branched or cyclic thioalkoxy having 3 to 20C atoms, silyl, keto having 1 to 20C atoms, alkoxycarbonyl having 2 to 20C atoms, aryloxycarbonyl having 7 to 20C atoms, cyano, carbamoyl, haloformyl, formyl, isocyano, isocyanato, thiocyanate, isothiocyanate, hydroxyl, nitro, CF, and isocyano₃Cl, Br, F, a crosslinkable group, a substituted or unsubstituted aromatic group having 5 to 60 ring atoms, a substituted or unsubstituted heteroaromatic group having 5 to 60 ring atoms, an aryloxy group having 5 to 60 ring atoms, a heteroaryloxy group having 5 to 60 ring atoms, or a combination of these groups.

4. The aromatic amine compound according to claim 3, wherein Ar in the general formula (1)₁-Ar₄Each independently selected from one of the following groups:

n is selected from 0, 1,2,3 or 4.

5. The aromatic amine compound according to claim 4, wherein the general formula (1) is selected from structures represented by any one of general formulae (3-1) to (3-4):

6. the aromatic amine compound according to claim 5, wherein L in the formula (1)₁-L₄At each occurrence, independently selected from a single bond or the following groups:

7. the aromatic amine compound according to claim 6, wherein the aromatic amine compound represented by the general formula (1)

Each independently selected from any one of the following groups:

8. the aromatic amine compound according to claim 4, wherein the general formula (1) is selected from structures represented by any one of general formulae (4-1) to (4-6):

9. the aromatic amine compound of claim 8, wherein R is₁Selected from hydrogen, D, or a straight chain alkyl group having 1 to 8C atoms, or a branched chain alkyl group having 3 to 8C atoms, orCycloalkyl having 3 to 8C atoms, Cl, Br, F, cyano or phenyl.

10. A mixture comprising an aromatic amine compound according to any one of claims 1 to 9, and at least another organic functional material selected from at least one of a hole injecting material, a hole transporting material, an electron injecting material, an electron blocking material, a hole blocking material, a light emitting material, a host material, and an organic dye.

11. A composition comprising at least one aromatic amine compound according to any one of claims 1 to 9, or a mixture according to claim 10, and at least one organic solvent.

12. An organic electronic device comprising a functional layer, characterized in that the functional layer comprises an aromatic amine compound according to any one of claims 1 to 9, or a mixture according to claim 10, or is prepared from a composition according to claim 11.