An arylamine organic compound, mixture, composition and organic electronic device

Abstract

The application discloses an arylamine organic compound, a mixture, a composition and an organic electronic device. The structure of the arylamine organic compound is represented by a general formula (1), and the arylamine organic compound can be used as a light-emitting auxiliary material for preparing the organic electronic device. The compound can significantly improve the light-emitting efficiency and service life of the device, and can maintain a low driving voltage during use. The general formula (1) is shown in the description.

Description

Technical Field

[0001] This application relates to the technical field of organic electroluminescence, specifically to an aromatic amine organic compound, mixture, composition, and organic electronic device. Background Technology

[0002] Organic electroluminescence (OEL) technology utilizes the photoelectric properties of organic materials to directly convert electrical energy into light energy. Organic light-emitting devices based on this technology typically consist of a positive electrode, a negative electrode, and multiple layers of organic functional layers. These functional layers include hole injection layers, transport layers, light-emitting auxiliary layers, light-emitting layers, electron transport layers, and injection layers, each containing specific organic materials designed to enhance the overall performance of the device.

[0003] When a voltage is applied between the electrodes, holes are injected into the positive electrode and electrons are injected into the negative electrode. The two combine to form excitons, which release light energy as they return to their ground state. As a typical representative of OEL technology, OLED has shone brightly in the fields of flat panel displays and lighting due to its many advantages, such as self-emissiveness, high brightness, high efficiency, low voltage, wide viewing angle, and high contrast. Its wide viewing angle, fast response, low voltage requirement, and ultra-thin design fully demonstrate the enormous potential and broad application prospects of OLED technology in the future.

[0004] Luminescent auxiliary materials can effectively balance carrier transport in OLED devices, strongly suppress electron back migration, and promote electron-hole recombination mainly in the central region of the emissive layer, reducing nonradiative recombination of excitons, thereby improving luminous efficiency and extending lifespan. Therefore, with the further development of OLED devices, the requirements for luminous efficiency and lifespan are becoming increasingly stringent, necessitating the development of more efficient novel luminescent auxiliary materials to further optimize the balance of hole and electron transport within the device, improve device efficiency and lifespan, and maintain a lower driving voltage. Summary of the Invention

[0005] This application provides an aromatic amine organic compound, mixture, composition, and organic electronic device, aiming to solve the technical problem of further optimizing the hole and electron transport balance inside the device, improving device efficiency and lifespan, and maintaining a low driving voltage.

[0006] This application provides an aromatic amine organic compound, which is shown in general formula (1):

[0007] General formula (1);

[0008] in,

[0009] L1 is independently selected from one of phenyl, biphenyl, and naphthyl;

[0010] L2 is independently selected from one of phenyl, naphthyl, biphenyl, benzofuranyl, and dimethylfluorenyl;

[0011] Ar1 is independently selected from phenyl and biphenyl;

[0012] Ar2 is independently selected from one of phenyl, naphthyl, biphenyl, benzofuranyl, and dimethylfluorenyl.

[0013] Optionally, in some embodiments of this application, Ar1 is independently selected from phenyl, biphenyl, or...

[0014] Ar2 is independently selected from one of phenyl, naphthyl, biphenyl, benzofuranyl, and dimethylfluorenyl.

[0015] Optionally, in some embodiments of this application, Ar1 and Ar2 may appear the same or different each time, and are independently selected from any one of the following groups: hydrogen atoms, substituted or unsubstituted groups:

[0016]

[0017]

[0018]

[0019]

[0020]

[0021] “ "" indicates a connection point.

[0022] Optionally, in some embodiments of this application, the substituted or unsubstituted substituents in L1, L2, Ar1, and Ar2 are independently selected from deuterium, methyl, tert-butyl, adamantyl, phenyl, biphenyl, naphthyl, dibenzofuranyl, dibenzothiophene, fluorenyl, or carbazoyl.

[0023] Optionally, in some embodiments of this application, the organic compound is selected from the following structures:

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031]

[0032]

[0033]

[0034]

[0035]

[0036]

[0037]

[0038]

[0039]

[0040]

[0041]

[0042]

[0043]

[0044]

[0045]

[0046] .

[0047] Secondly, this application also provides a mixture comprising at least the organic compound as described above, and at least one organic functional material selected from hole injection materials, hole transport materials, light-emitting auxiliary materials, electron transport materials, electron injection materials, electron blocking materials, hole blocking materials, organic light-emitting guest materials, or organic host materials.

[0048] Thirdly, this application also provides a composition comprising at least one organic solvent and at least one organic compound as described above, or the composition comprising at least one of the organic solvents and a mixture as described above.

[0049] Fourthly, this application also provides an organic electronic device comprising at least one organic compound as described above, or a mixture as described above, or prepared from the aforementioned composition.

[0050] The aromatic amine organic compounds used in the embodiments of this application can be used as luminescent auxiliary materials for green light to prepare organic electronic devices, which can significantly improve the luminous efficiency and lifespan of the devices, and can also maintain a low driving voltage during use. Attached Figure Description

[0051] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0052] Figure 1 This is a schematic cross-sectional view of an organic electronic device provided in an embodiment of this application;

[0053] In the figure, 10 is the substrate; 20 is the anode; 30 is the hole injection layer; 40 is the hole transport layer; 50 is the light-emitting auxiliary layer; 60 is the light-emitting layer; 70 is the electron transport layer; 80 is the electron injection layer; and 90 is the cathode. Detailed Implementation

[0054] The technical solutions in the embodiments of this application will be clearly and completely described below with reference to the embodiments of this application. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application.

[0055] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art.

[0056] As used herein, the term "and / or" includes any and all combinations of one or more of the related listed items.

[0057] In this application, hydrogen atoms include isotopes with different numbers of neutrons, namely protium, deuterium, and tritium.

[0058] In this application, "substitution" means that the hydrogen atom in the substituent is replaced by the substituent.

[0059] In this application, "substituted or unsubstituted" means that the defined group may or may not be substituted. When the defined group is substituted, it should be understood that it may be substituted by a group acceptable in the art, including but not limited to: deuterium atom, cyano, isocyano, nitro, halogen atom, C 1-10 alkyl, C 1-10 alkoxy, C 1-10 alkylthio group, C 6-30 aryl, C 6-30 aryloxy group, C 6-30 aryl thiols, C 3-30 heteroaryl, C 1-30 silane, C 2-10 alkylamine group, C 6-30 Aromatic amino groups, or combinations thereof, etc.

[0060] In this invention, "alkyl" can refer to straight-chain, branched, and / or cyclic alkyl groups. The number of carbon atoms in an alkyl group can be 1 to 15. Phrases containing this term, such as "C 1-9 "Alkyl" refers to an alkyl group containing 1 to 9 carbon atoms, and each time it appears, it can independently be C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl, C6 alkyl, C7 alkyl, C8 alkyl, or C9 alkyl. Non-limiting examples of alkyl groups include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, isobutyl, 2-ethylbutyl, 3,3-dimethylbutyl, n-pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, 1-methylpentyl, 3-methylpentyl, 2-ethylpentyl, 4-methyl-2-pentyl, n-hexyl, 1-methylhexyl, 2-ethylhexyl, 2-butylhexyl, cyclohexyl, adamantane, etc.

[0061] "Aryl or aromatic group" refers to an aromatic hydrocarbon group derived from an aromatic ring compound by removing one hydrogen atom. It can be a monocyclic aryl, a fused-ring aryl, or a polycyclic aryl. For polycyclic compounds, at least one must be an aromatic ring system. For example, "substituted or unsubstituted C..." 6~30 "Aryl group" refers to an aryl group containing 6 to 30 carbon atoms, with optional further substitutions; suitable examples include, but are not limited to: benzene, biphenyl, terphenyl, naphthalene, anthracene, fluoranthene, phenanthrene, benzo[a]phenanthrene, dinaphthalene-based phenylene, tetraphenyl, pyrene, benzo[a]pyrene, acenaphthene, fluorene, and their derivatives. Understandably, multiple aryl groups may also be interrupted by short non-aromatic units (e.g., <10% non-H atoms, such as C, N, or O atoms), specifically acenaphthene, fluorene, or 9,9-diarylfluorene, triarylamines, and diaryl ether systems should also be included in the definition of aryl.

[0062] In this article, "substituted or unsubstituted C" is used. 5~30 "Heteroaromatic group" refers to a monovalent group comprising a carbocyclic heteroaromatic system having at least one heteroatom selected from nitrogen, oxygen, phosphorus, sulfur, or silicon as a cyclic atom and 5 to 30 carbon atoms. Non-limiting examples of heteroaromatic groups containing 5 to 30 carbon atoms may include furanyl, thiopheneyl, pyrroleyl, pyrazolyl, imidazoleyl, triazolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1,2,3 Oxadiazolyl, 1,2,4 Oxadiazolyl, 1,3,4 Oxadiazolyl, 1,2,5 Oxadiazolyl, 1,2,3 Thiadiazolyl, 1,2,4 Thiadiazolyl, 1,3,4 Thiadiazolyl, 1,2,5 Thiadiazolyl, tetrazolyl, pyridyl, pyrimidinyl, pyridazinyl, 1,2,3 Triazinyl, 1,2,4 Triazine, 1,3,5 Triazinyl, benzofuranyl, benzoisofuranyl, benzothiophenyl, benzoisothiophenyl, indoleyl, isoindoleyl, indazoleyl, benzimidazolyl, benzoxazolyl, benzoisoxazolyl, benzothiazolyl, 2,1,3 Benzoxadiazole, quinolinyl, isoquinolinyl, terolinyl, phthalazinyl, quinazolinyl, quinolinyl, naphridinyl, benzotriazinyl, benzooxazinyl, purine, pteridinyl, indazinyl, benzothiazinyl, acridineyl, benzazinyl, benzthiazinyl, benzoxazinyl, dibenzofuranyl, dibenzothiophenyl, carbazoleyl, naphridinyl, quinolinyl, isoquinolinyl, indole [1,2] f]Phenyridyl, imidazo[2,1] a]Isoquinolinyl, imidazo[1,2] a] Quinolinyl, benzo[4,5]imidazo[1,2] a]pyridyl, imidazo[1,2] a]pyridyl, benzofuran [3,2] c] Quinolinyl, naphtho[1,2] b] Benzofuranyl, naphtho[2,3] b] Benzofuranyl and other aromatic composite groups with heteroatoms, but not limited thereto.

[0063] In this invention, the "connected to the single bond" "" indicates a connection or fusion site.

[0064] In this invention, when no linking site is specified in the group, it means that any linkable site in the group is selected as the linking site;

[0065] In this invention, the single bond connecting the substituents extends through the corresponding ring, indicating that the substituent can be connected to any position on the ring, for example... R is attached to any substituted site on the benzene ring.

[0066] According to a first aspect of the embodiments of this application, an aromatic amine organic compound is provided, the aromatic amine organic compound being shown in general formula (1):

[0067] General formula (1);

[0068] in,

[0069] R is selected from methyl or phenyl.

[0070] L1 and L2 may be the same or different each time they appear, and are independently selected from single-bonded, substituted or unsubstituted C. 6~30 Aromatic groups, substituted or unsubstituted C 5~30 At least one of the heteroaromatic groups;

[0071] Ar1 and Ar2 may appear the same or different each time, and are independently selected from hydrogen atoms, substituted or unsubstituted carbon atoms. 6~30 Aromatic groups, substituted or unsubstituted C 5~30 At least one of the heteroaromatic groups;

[0072] In L1, L2, Ar1, and Ar2, the substituted or unsubstituted substituents are selected from deuterium atoms, C atoms, and C atoms. 1~15 alkyl, C 6~30 Aromatic groups or C 5~30 heteroaromatic groups;

[0073] In L1, L2, Ar1, and Ar2, the heteroatom in the heteroaryl group can be selected from one or more of nitrogen, oxygen, or sulfur atoms;

[0074] The way a loop structure is represented by a dash "—" indicates that the connection point is located at any position on the loop structure where bonding can occur.

[0075] In some embodiments of this application, L1 is independently selected from one of single bond, phenyl, biphenyl, and naphthyl.

[0076] In some embodiments of this application, L2 is independently selected from one of single bond, phenyl, naphthyl, biphenyl, benzofuranyl, and dimethylfluorenyl.

[0077] In some embodiments of this application, L1 and L2 may appear the same or different each time, and are independently selected from any one of the following groups: single bond, substituted or unsubstituted:

[0078]

[0079] “ "" indicates a connection point.

[0080] In some embodiments of this application, Ar1 is independently selected from hydrogen atom, phenyl, biphenyl.

[0081] In some embodiments of this application, Ar2 is independently selected from one of phenyl, naphthyl, biphenyl, benzofuranyl, and dimethylfluorenyl.

[0082] In some embodiments of this application, Ar1 and Ar2 may appear the same or different each time, and are independently selected from any one of the following groups: hydrogen atoms, substituted or unsubstituted groups:

[0083]

[0084]

[0085]

[0086]

[0087]

[0088] “ "" indicates a connection point.

[0089] In some embodiments of this application, the substituted or unsubstituted substituents in L1, L2, Ar1, and Ar2 are independently selected from deuterium, methyl, tert-butyl, adamantyl, phenyl, biphenyl, naphthyl, dibenzofuranyl, dibenzothiophene, fluorenyl, or carbazoyl.

[0090] In some embodiments of this application, the organic compound is selected from the following structures, including but not limited to:

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104]

[0105]

[0106]

[0107]

[0108]

[0109]

[0110]

[0111]

[0112]

[0113] .

[0114] The aromatic amine organic compounds according to this application can be used as functional materials in electronic devices, particularly OLED devices. Organic functional materials can be categorized as hole injection materials (HIM), hole transport materials (HTM), luminescence assist materials (Prime), electron transport materials (ETM), electron injection materials (EIM), electron blocking materials (EBM), hole blocking materials (HBM), guest luminescent materials, and host materials. Host materials can be further categorized as phosphorescent host materials, fluorescent host materials, and host materials for TADF luminescent materials. The organic compounds according to this invention can be any of these categories.

[0115] In a preferred embodiment, the organic compound according to the invention can be used as a light-emitting auxiliary material.

[0116] The aromatic amine organic compounds according to the present invention have a glass transition temperature Tg ≥ 100°C. o C, in a preferred embodiment, Tg ≥ 120 oC, In a preferred embodiment, Tg ≥ 140 o C, In a more preferred alternative embodiment, Tg ≥ 160 o C, in a most preferred embodiment, Tg ≥ 180 o C.

[0117] This invention also relates to a mixture comprising at least one of the aforementioned organic compounds and at least one organic functional material, wherein the organic functional material is selected from hole injection materials, hole transport materials, light-emitting auxiliary materials, electron transport materials, electron injection materials, electron blocking materials, hole blocking materials, organic light-emitting guest materials, organic host materials, or inorganic quantum dots. For example, various organic functional materials are described in detail in WO2010135519A1, US20090134784A1, and WO2011110277A1. The entire contents of these three patent documents are hereby incorporated herein by reference. The organic functional material can be a small molecule or a polymer material.

[0118] One object of the present invention is to provide a material solution for vapor-deposited OLEDs.

[0119] In some embodiments, the organic compounds according to the invention have a molecular weight of ≤1100 g / mol, preferably ≤1000 g / mol, very preferably ≤950 g / mol, more preferably ≤900 g / mol, and most preferably ≤800 g / mol.

[0120] Another objective of this invention is to provide a material solution for printed OLEDs.

[0121] In some embodiments, the organic compound according to the invention has a molecular weight ≥500 g / mol, preferably ≥700 g / mol, more preferably ≥900 g / mol, and most preferably ≥1000 g / mol.

[0122] The present invention also relates to a composition comprising at least one of the organic compounds or mixtures as described, and at least one organic solvent.

[0123] The organic solvent may be selected from any one of aromatic or heteroaromatic compounds, esters, aromatic ketones or aromatic ethers, aliphatic ketones or aliphatic ethers, alicyclic or olefinic compounds, or borate esters or phosphate esters, or a mixture of two or more solvents. Preferably, the organic solvent is selected from solvents based on aromatic or heteroaromatic compounds.

[0124] Examples of aromatic or heteroaromatic solvents suitable for this application include, but are not limited to: p-diisopropylbenzene, pentaphenyl, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene, 3-isopropylbiphenyl, p-methylisopropylbenzene, dipentylbenzene, tripentylbenzene, pentylene, 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, 4,4-difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4-isopropylbiphenyl, α,α-dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furanoate, ethyl 2-furanoate, etc.

[0125] Examples of aromatic ketone-based solvents suitable for this application include, but are not limited to: 1-tetrahydronaphthone, 2-tetrahydronaphthone, 2-(phenylepoxy)tetrahydronaphthone, 6-(methoxy)tetrahydronaphthone, acetophenone, phenylacetone, benzophenone, and their derivatives, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylphenylacetone, 3-methylphenylacetone, 2-methylphenylacetone, etc.

[0126] Examples of aromatic ether-based solvents suitable for this application include, but are not limited to: 3-phenoxytoluene, butoxybenzene, p-anisaldehyde dimethyl acetal, tetrahydro-2-phenoxy-2H-pyran, 1,2-dimethoxy-4-(1-propenyl)benzene, 1,4-benzodioxane, 1,3-dipropylbenzene, 2,5-dimethoxytoluene, 4-ethylbenzene, 1,3-dipropoxybenzene, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1,3-dimethoxybenzene, glycidylphenyl ether, dibenzyl ether, 4-tert-butylanisole, trans-p-propenylanisole, 1,2-dimethoxybenzene, 1-methoxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether, etc.

[0127] Examples of aliphatic ketone or aliphatic ether solvents suitable for this application include, but are not limited to: 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 2,5-hexanedione, 2,6,8-trimethyl-4-nonanone, frankinc, phorone, isophorone, di-n-pentyl ketone, pentyl 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, etc.

[0128] Examples of suitable boronic acid ester or phosphate ester-based solvents for this application include, but are not limited to: alkyl octanoate, alkyl sebacate, alkyl stearate, alkyl benzoate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkyl lactone, alkyl oleate, etc. Octyl octanoate, diethyl sebacate, diallyl phthalate, and isononyl isononanoate are particularly preferred.

[0129] In certain preferred embodiments, a composition according to the invention may comprise at least one organic compound or polymer or mixture as described above, at least one organic solvent, and at least one cosolvent. Examples of the cosolvent include (but are not limited to): methanol, ethanol, 2-methoxyethanol, dichloromethane, trichloromethane, 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, naphthane, indene, and / or mixtures thereof.

[0130] In some preferred embodiments, solvents particularly suitable for the present invention are those with Hansen solubility parameters in the following ranges: δd (dispersion force) in the range of 17.0 to 23.2 MPa¹ / ², particularly in the range of 18.5 to 21.0 MPa¹ / ²; δp (polar force) in the range of 0.2 to 12.5 MPa¹ / ², particularly in the range of 2.0 to 6.0 MPa¹ / ²; and δh (hydrogen bonding force) in the range of 0.9 to 14.2 MPa¹ / ², particularly in the range of 2.0 to 6.0 MPa¹ / ².

[0131] According to the compositions of this application, the boiling point of the organic solvent must be considered when selecting it. In this application, the boiling point of the organic solvent is ≥150 °C; preferably ≥180 °C; more preferably ≥200 °C; even more preferably ≥250 °C; and most preferably ≥275 °C or ≥300 °C. Boiling points within these ranges are beneficial for preventing nozzle clogging of the inkjet printhead. The organic solvent can evaporate from the solvent system to form a thin film containing organic functional materials.

[0132] In one embodiment, the composition according to this application is a solution. In another embodiment, the composition according to the invention is a suspension.

[0133] The compositions in the embodiments of this application may include 0.01 to 10 wt% of the organic compound or mixture thereof according to the present invention, preferably 0.1% to 15 wt%, more preferably 0.2% to 5 wt%, and most preferably 0.25% to 3 wt%.

[0134] This application also relates to the use of the composition as a coating or printing ink in the preparation of organic electronic devices, particularly preferably by a preparation method of printing or coating.

[0135] Suitable printing or coating technologies include (but are not limited to) inkjet printing, nozzle printing, letterpress printing, screen printing, dip coating, spin coating, doctor blade coating, roller printing, torsional roller printing, offset printing, flexographic printing, rotary printing, spraying, brushing or pad printing, and slot-fitting coating. Gravure printing, inkjet printing, and gravure printing are preferred. The solution or suspension may additionally include one or more components such as surfactants, lubricants, wetting agents, dispersants, hydrophobic agents, and binders to adjust viscosity, film-forming properties, and improve adhesion. The printing technology and its related requirements for the solution, such as solvent and concentration, viscosity, etc., are also important considerations.

[0136] This application further relates to the use of an aromatic amine organic compound, mixture, or composition as described above in organic electronic devices. In embodiments of the invention, the organic compound is preferably used in the hole transport layer of an OLED device.

[0137] This application further relates to an organic electronic device comprising two electrodes and one or more organic functional layers disposed between the two electrodes, the organic functional layers comprising aromatic amine organic compounds, mixtures thereof, or prepared from the above-described compositions. Further, the organic electronic device comprises a cathode, an anode, and one or more organic functional layers located at the cathode and the anode.

[0138] The anode may comprise a conductive metal or metal oxide, or a conductive polymer. Holes can be readily injected into the hole injection layer (HIL), hole transport layer (HTL), or light-emitting 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 light emitter in the light-emitting layer or the p-type semiconductor material serving as the HIL, HTL, or electron blocking layer (EBL) is less than 0.5 eV, preferably less than 0.3 eV, and 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), etc. Other suitable anode materials are known and can be readily selected by those skilled in the art. The anode material can 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), etc. In some embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to fabricate devices according to this application.

[0139] The cathode may comprise a conductive metal or metal oxide. Electrons can be readily injected 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 luminescent material in the light-emitting layer or the n-type semiconductor material serving as the electron injection layer (EIL), electron transport layer (ETL), or hole blocking layer (HBL) is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. In principle, all materials suitable for use as cathodes in OLEDs may be used as cathode materials for the devices of this 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 can 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), etc.

[0140] In some embodiments, the organic electroluminescent device according to this application includes one or more organic functional layers selected from one or more layers of an electron injection layer, an electron transport layer, a hole blocking layer, a hole injection layer, a hole transport layer, an electron blocking layer, and an emissive layer, wherein at least one emissive layer and one hole transport layer are included. Materials suitable for use in these functional layers are as described above and will not be repeated here.

[0141] For example, refer to Figure 1The organic electronic device includes a substrate 10 and an anode 20, a hole injection layer 30, a hole transport layer 40, a light-emitting auxiliary layer 50, a light-emitting layer 60, an electron transport layer 70, an electron injection layer 80, and a cathode 90, which are sequentially stacked on the substrate 10.

[0142] In some embodiments, in the organic electroluminescent device according to this application, the luminescent material in the luminescent layer is selected from singlet luminescent material, triplet luminescent material, or TADF material.

[0143] In some more alternative embodiments, the organic electroluminescent device according to this application generally has an organic functional layer thickness of 10 nm to 200 nm, preferably 20 nm to 150 nm, more preferably 30 nm to 100 nm, and most preferably 40 nm to 90 nm.

[0144] The organic electronic device may be selected from, but is 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, organic lasers, organic spintronic devices, organic sensors, and organic plasmon emitting diodes, with organic electroluminescent devices such as OLEDs, OLEECs, and organic light-emitting field-effect transistors being particularly preferred.

[0145] The present invention also relates to the application of the electroluminescent device according to this application in various electronic devices, including but not limited to: display devices, lighting devices, light sources, sensors, etc.

[0146] The present invention also relates to electronic devices incorporating organic electronic devices according to the present application, including but not limited to: display devices, lighting devices, light sources, sensors, etc.

[0147] The present application will now be described in conjunction with preferred embodiments, but the present invention is not limited to the following embodiments. It should be understood that the appended claims summarize the scope of the present invention. Under the guidance of the inventive concept, those skilled in the art should realize that any changes made to the various embodiments of the present invention will be covered by the spirit and scope of the claims of the present invention. Specific Implementation

[0149] Examples of the synthesis methods of the compounds described in this application are provided, but this application is not limited to the following examples.

[0150] Synthesis of intermediate A:

[0151]

[0152] Synthesis of intermediate A

[0153] Compound a (10 mmol) was dissolved in a flask containing 200 mL of dry THF. The reaction mixture was cooled to -78 °C. A 2.5 M solution of n-butyllithium (10 mmol) was slowly added dropwise at this temperature. The mixture was stirred at -70 °C for 1 hour. Subsequently, compound b (10 mmol) was dissolved in 100 mL of THF and added dropwise to the above mixture at -70 °C. After the addition was complete, the reaction mixture was slowly heated to room temperature, quenched with NH4Cl, and then concentrated on a rotary evaporator. 36 mL of acetic acid was carefully added to the rotary evaporated solution, followed by 6 mL of fuming hydrochloric acid. The mixture was then heated to 75 °C and stirred for 6 hours. After cooling to room temperature, the mixture was filtered and washed several times with methanol to obtain a solid crude product. The solid crude product was then further purified by column chromatography to obtain intermediate A (yield: 65%), mass spectrometry m / z [H + = 409.

[0154] Synthesis of intermediates B and C:

[0155] ;

[0156] The synthesis of intermediates B and C followed the same steps as intermediate A, with a yield of approximately 60%. Mass spectrometry results were obtained at m / z [H]. + =409.

[0157] The synthetic route for intermediate D is as follows:

[0158] ;

[0159] The synthesis procedure for compound i is as follows:

[0160] Compound g (10 mmol) was dissolved in a flask containing 200 mL of dry THF. The reaction mixture was cooled to -78 °C. A 2.5 M solution of n-butyllithium (10 mmol) was slowly added dropwise at this temperature. The mixture was stirred at -70 °C for 1 h. Subsequently, compound h (10 mmol) was dissolved in 100 mL of THF and added dropwise to the above system at -70 °C. After the addition was complete, the reaction mixture was slowly heated to room temperature and reacted for 6 h. The mixture was extracted with dichloromethane and water, and the organic phase was evaporated to dryness. Further purification was carried out by column chromatography to give compound i in 75% yield, with a mass spectrometry m / z [H+] = 410.

[0161] The synthesis operation of compound j is as follows:

[0162] Compound i (10 mmol) and pyridine (12 mmol) were dissolved in a flask containing 200 mL of dichloromethane. Trifluoromethanesulfonic acid (15 mmol) was then added at 0 °C. After the addition was complete, the reaction mixture was slowly heated to room temperature and reacted for 8 h. The mixture was extracted with dichloromethane and water, and the organic phase was evaporated to dryness. Further purification by column chromatography yielded intermediate j in 85% yield, with a mass spectrometry m / z [H+] = 542.

[0163] The synthesis procedure for compound D is as follows:

[0164] Compound j (10 mmol), compound k (10 mmol), Pd(PPh3)4 (0.1 mmol), and potassium carbonate (30 mmol) were dissolved in a flask containing 1,4-dioxane (150 mL) and water (50 mL). The reaction mixture was then stirred at 100 °C for 8 h. The mixture was extracted with dichloromethane and water, and the organic phase was evaporated to dryness. Further purification by column chromatography yielded intermediate E in 82% yield (m / z [H+] = 471).

[0165] Example 1 Synthesis of Compound M1

[0166]

[0167] Synthesis of compound M1:

[0168] Intermediate A (10 mmol), intermediate 1-1 (10 mmol), dichlorodi-tert-butyl-(4-dimethylaminophenyl)phosphine palladium(II) (0.1 mmol), 2-bicyclohexylphosphine-2',4',6'-triisopropylbiphenyl (0.2 mmol), and sodium tert-butoxide (30 mmol) were dissolved in toluene and stirred at 120 °C for 12 h under nitrogen atmosphere. After cooling the reaction system to room temperature, a portion of the solvent was removed by rotary evaporation. The mixture was then extracted three times with dichloromethane and water. The organic phase was evaporated to dryness to obtain the crude product. Further purification by column chromatography yielded compound M1, with a yield of 83%. Mass spectrometry m / z [H + = 618. The analysis test values ​​are C, 91.39; H, 6.39; N, 2.24.

[0169] The following compounds were prepared using the same method as in Example 1. The structures, starting materials, and relevant synthetic information for these examples are shown in Table 1 below:

[0170] Table 1

[0171]

[0172] Comparative Example

[0173] This application also provides comparative examples 1 to 3, denoted as "Ref-01 to Ref-03", whose chemical structural formulas are shown below:

[0174] .

[0175] Fabrication and characterization of OLED devices

[0176] The following detailed examples illustrate the fabrication method and process of OLED devices using the compounds described in this application. In the following OLED device fabrication method, ITO conductive glass is used as the anode substrate, PD as the hole injection material, HT as the hole transport material, Host-1 and Host-2 as the host materials of the light-emitting layer, Dopant as the dopant material of the light-emitting layer, ET and Liq as electron transport materials, Liq as the electron injection material, and Al as the cathode material. Furthermore, compound M1 from the aforementioned synthesis example is used as the light-emitting auxiliary material to fabricate corresponding OLED devices. The chemical structural formulas of PD, HT, Host-1, Host-2, Dopant, ET, and Liq are shown below:

[0177] .

[0178] The fabrication process of the OLED device using the above-mentioned materials is described in detail below through specific embodiments. In this embodiment, the structure of the fabricated OLED device is as follows: ITO / PD: HT (3:97, 10 nm) / HT (130 nm) / compound M1 of the present invention (45 nm) / Host (Host-1:Host-2=5:5): Dopant (3%, 40 nm) / ET: Liq (5:5, 30 nm) / Liq (1 nm) / Al (100 nm). Taking the fabrication method of compound M1 as the light-emitting auxiliary material for OLED device fabrication as an example, the OLED device obtained is denoted as "OLED-1 device". The fabrication method of OLED-1 device includes the following steps:

[0179] a. Cleaning of conductive glass substrate: Cleaning is performed using chloroform, ketone, and isopropanol, followed by ultraviolet ozone plasma treatment;

[0180] b. Functional layer fabrication: First, the ITO substrate is transferred into a vacuum vapor deposition apparatus and deposited under high vacuum (1×10⁻⁶). -6 At millibars, resistance heating was used for evaporation at 1 Å s. -1 Hole implantation materials PD and HT were deposited on ITO at a deposition rate of 3:97, resulting in a hole implantation layer with a thickness of 10 nm. Then, at a deposition rate of 1.5 Å s⁻¹... -1 Hole transport material HT was deposited on the hole injection layer at a deposition rate of 1 Å s to obtain a hole transport layer with a thickness of 130 nm. Then, at a deposition rate of 1 Å s... -1 The compound M1 provided in the above embodiments was deposited on the hole transport layer at a deposition rate of 1 Å / s to obtain a light-emitting auxiliary layer with a thickness of 45 nm. Next, a dual host (Host-1 and Host-2) and Dopant were co-deposited on the light-emitting auxiliary layer at a deposition rate of 1 Å / s, with a deposition rate ratio of 88:12, to obtain a light-emitting layer with a thickness of 40 nm. Subsequently, in a vacuum chamber, electron transport materials ET and Liq were placed in different evaporation crucibles and subjected to high vacuum (1 × 10⁻⁶) conditions. -6 At a weight ratio of 5:5, ET and Liq were co-deposited at a density of 1 Å / s to form a 30 nm thick electron transport layer on the luminescent layer. Then, at 1 Å / s... -1 Electron injection material Liq was deposited on the electron transport layer at a deposition rate of 1 Å s⁻¹, resulting in an electron injection layer with a thickness of 1 nm. Then, at a deposition rate of 1 Å s⁻¹... -1 The cathode material Al was deposited on the electron injection layer at a certain evaporation rate to obtain a cathode with a thickness of 100 nm.

[0181] c. Encapsulation: The device is encapsulated in a nitrogen glove box using ultraviolet-cured resin to obtain the final OLED device.

[0182] Referring to the fabrication method of OLED-1, compounds synthesized in the examples were selected as luminescent auxiliary materials for OLED devices, and OLED-2 to OLED-34 devices were fabricated accordingly. It is understood that, in the fabrication methods of OLED-2 to OLED-34 devices, all experimental conditions are the same except for the luminescent auxiliary materials.

[0183] In one embodiment, referring to the fabrication method of the device embodiment, comparative compounds Ref-03 and Ref-04 were used as luminescent auxiliary materials to prepare comparative OLED-Ref-01 and OLED-Ref-02 devices, respectively. Compared with the fabrication method of OLED-1 device, the fabrication methods of OLED-Ref-01 and OLED-Ref-02 devices are identical except for the luminescent auxiliary materials.

[0184] In this application, the current-voltage (ND) of OLED-1 to OLED-34 and OLED-Ref-01 to OLED-Ref-03 devices are described. JV The characteristics were characterized, and important parameters such as luminous efficiency and lifetime were recorded, as shown in Table 2. Luminous efficiency is defined as the luminous efficiency at a current density of 50 mA cm⁻¹. -2 The relative value obtained at that time, lifetime (LT95) is the time when the brightness drops to 95% of the initial brightness @1000 nits under constant current.

[0185] Table 2

[0186]

[0187] Table 1 shows that when the organic compounds in Examples 1 to 34 of this invention are used as green light emitting auxiliary materials, the prepared OLED devices (OLED-1 to OLED-34) are significantly superior to the control devices OLED-Ref-01 to OLED-Ref-03 in terms of luminous efficiency and lifetime, and also have lower driving voltages. This indicates that aromatic amine compounds containing monodiphenylpropane-fluorenyl groups can achieve excellent overall performance.

[0188] The foregoing has provided a detailed description of an aromatic amine organic compound, mixture, composition, and organic electronic device provided in the embodiments of this application. Specific examples have been used to illustrate the principles and implementation methods of this application. The descriptions of the above embodiments are only for the purpose of helping to understand the methods and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. An aromatic amine organic compound, characterized in that, As a green light emitting auxiliary material; The aromatic amine organic compounds are shown in general formula (1): General formula (1); in, L1 is independently selected from one of phenyl, biphenyl, and naphthyl; L2 is independently selected from one of phenyl, naphthyl, biphenyl, benzofuranyl, and dimethylfluorenyl; Ar1 is independently selected from phenyl and biphenyl; Ar2 is independently selected from one of phenyl, naphthyl, biphenyl, benzofuranyl, and dimethylfluorenyl.

2. An aromatic amine organic compound, characterized in that, The aromatic amine organic compounds are selected from the following structures: 。 3. A mixture, characterized in that, The mixture includes at least the organic compound as described in claim 1 or 2, and at least one organic functional material, wherein the organic functional material is selected from hole injection materials, hole transport materials, light-emitting auxiliary materials, electron transport materials, electron injection materials, electron blocking materials, hole blocking materials, organic light-emitting guest materials, or organic host materials.

4. A composition, characterized in that, The composition comprises at least one organic solvent and at least one organic compound as claimed in claim 1 or 2, or the composition comprises at least one of the organic solvents and a mixture as claimed in claim 3.

5. An organic electronic device, characterized in that, The organic electronic device comprises at least one organic compound as described in claim 1 or 2, or a mixture as described in claim 3, or is prepared from the composition as described in claim 4.

Images