WO2019114611A1

WO2019114611A1 - Aromatic amine compound, organic electronic device comprising same, and application

Info

Publication number: WO2019114611A1
Application number: PCT/CN2018/119622
Authority: WO
Inventors: 谭甲辉; 张晨; 潘君友
Original assignee: 广州华睿光电材料有限公司
Priority date: 2017-12-14
Filing date: 2018-12-06
Publication date: 2019-06-20
Also published as: CN111278834A; CN111278834B

Abstract

Disclosed in the present invention are an aromatic amine compound and an application of same in an organic electronic device, and in particular, in an organic electroluminescent diode. Also disclosed in the present invention are an organic electronic device comprising the aromatic amine compound according to the present invention, and in particular, an organic electroluminescent diode, and an application of same in display and lighting technology. Also disclosed in the present invention is an organic electronic device comprising the aromatic amine compound according to the present invention.

Description

Aromatic amine compounds, organic electronic devices and applications thereof

This application claims the priority of the Chinese Patent Application entitled "Aromatic Amine Compounds, Organic Electronic Devices and Applications Containing the Same", filed on Dec. 14, 2017, the entire contents of which is hereby incorporated by reference. In this application.

Technical field

The present invention relates to an aromatic amine compound, including mixtures thereof, compositions, and organic electronic devices thereof, particularly in organic light emitting diodes.

Background technique

Organic light-emitting diodes (OLEDs) have great potential for applications in optoelectronic devices such as flat panel displays and illumination due to their versatility in synthesis, relatively low manufacturing costs, and excellent optical and electrical properties.

Organic electroluminescence refers to the phenomenon of converting electrical energy into light energy using organic matter. An organic electroluminescence device utilizing an organic electroluminescence phenomenon generally has a structure in which a positive electrode and a negative electrode and an organic layer are contained therebetween. In order to improve the efficiency and lifetime of the organic electroluminescent element, the organic layer has a multilayer structure, and each layer contains 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 electroluminescence device, 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, and excitons are formed when the injected holes meet the electrons. The excitons emit light when they transition back to the ground state. Such an organic electroluminescence device has characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high responsiveness.

However, the OLED device needs to be further improved in luminous efficiency and service life. Because OLED is used as a current-driven device, it is in a high current density state during operation, and the material is prone to Joule heat, resulting in device degradation, especially between the anode and the hole transport layer. . The commonly used hole transporting materials have a low glass transition temperature, and the accumulation of Joule heat causes a change in the morphology of the film, and at the same time accelerates the decomposition of the material, thereby affecting the life of the device. In addition, the hole mobility of the organic semiconductor material is generally higher than the electron mobility, resulting in a hole-electron transport imbalance that affects the device's luminous efficiency.

Based on this, existing research work is expected to reduce the operating voltage and efficiency of the device (Synthetic Metals, 2009, 159, 69; J. Phys. D: Appl. Phys. 2007, 40, 5553). The use of a 3-position carbazole-substituted arylamine compound as a hole transporting material to improve the luminous efficiency of a device is disclosed in the patent document US Pat. No. 8,021,764 B2; the patent document WO2009148015A1 discloses a class of compounds including carbazole, dibenzofuran and dibenzo The heteroaryl ring of thiophene is directly bonded to the main chain carbon atom of the polycyclic compound which is passed through hydrazine, carbazole, dibenzofuran and dibenzothiophene and includes hydrazine, hydrazine, benzofuran and benzo The heteroaryl group of thiophene is fused; US2015105563 A1 discloses that one or more diarylamine groups are bonded directly or via an aryl group to a snail [芴-9,9'-芴] fused to an aryl or heteroaryl group. A compound of the benzene ring of the main chain.

However, the devices of the above disclosed compounds have to be improved in power efficiency, luminous efficiency and working life, so new OLED materials still need to be proposed to improve the performance of the device.

Summary of the invention

In view of the above deficiencies of the prior art, it is an object of the present invention to provide a novel class of aromatic amine compounds having excellent current efficiency, mixtures and compositions thereof, and their use in organic electronic devices. Through extensive research, it has been found that an aromatic amine group derivative of an anthracene heterocyclic skeleton can be used as an electroluminescent material, particularly as a hole transporting or hole injecting material, to obtain an OLED device having high luminous efficiency and long life. Further studies have found that, based on the compound of the present invention, Ea (electron affinity) is weakened to have an effect of blocking electrons from adjacent layers of the electron transport layer, and has high electrochemical stability, so that the composite efficiency is improved and the luminous efficiency is improved. , device life is extended.

The technical solution of the present invention is as follows:

An aromatic amine compound of the formula (I):

among them:

Each occurrence of R ₀ , R ₁ , and R ₂ is the same or different selected from H, or D, or a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group of 3 to 20 C atoms, or a silyl group, or a ketone group having 1 to 20 C atoms, or 2 to 20 C Alkoxycarbonyl group of an atom, or an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group (-CN), a carbamoyl group (-C(=O)NH ₂ ), a haloformyl group (-C(= O)-X wherein X represents a halogen atom), formyl (-C(=O)-H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF ₃ , Cl , Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryl group having 5 to 40 ring atoms An oxy group, or a combination of these systems, wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded;

L ₁ -L ₃ is a linking group selected from a single bond, an aromatic group or a heteroaromatic group;

Each occurrence of Ar ₁ -Ar ₆ may be independently selected from an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms. Or a combination of these systems, wherein Ar ₁ and Ar ₂ , Ar ₃ and Ar ₄ and Ar ₅ and Ar ₆ may be linked to each other to form a monocyclic or polycyclic aliphatic or aromatic ring system.

o, p, q each independently represent an integer of 0 to 1, and o + p + q ≥ 1;

m and n each independently represent an integer of 0 to 3.

A high polymer characterized by comprising at least one repeating structural unit represented by the general formula (I).

A mixture comprising at least one aromatic amine compound or polymer as described above, and at least one other organic functional material, said another organic functional material being selected from the group consisting of hole injecting materials (HIM), hole transport material (HTM), p-dopant, electron transport material (ETM), electron injecting material (EIM), electron blocking material (EBM), hole blocking material (HBM), luminescent material (Emitter) , host material (Host) and organic dyes.

A composition comprising at least one aromatic amine compound, polymer or mixture as described above, and at least one organic solvent.

An application of an aromatic amine compound, polymer, mixture or composition according to the above in an organic electronic device.

An organic electronic device comprising at least one aromatic amine compound, polymer or mixture as described above.

An electroluminescent device according to the above, characterized in that the luminescent layer comprises at least one aromatic amine compound, polymer, or mixture according to the above.

Advantageous Effects: The aromatic amine compound of the present invention contains an anthracene heterocyclic skeleton, and when used as a hole transporting or hole injecting material, an OLED device having high luminous efficiency and long life can be obtained. At the same time, based on the compound of the present invention, EA (electron affinity) is weakened to have an effect of blocking electrons from adjacent layers of the electron transport layer, and has high electrochemical stability, so compounding efficiency is improved, luminous efficiency is improved, and device life is prolonged. .

Detailed ways

The present invention provides an aromatic amine compound, an organic electronic device comprising the same, and an application thereof. In order to make the objects, technical solutions and effects of the present invention more clear and clear, the present invention will be further described in detail below. It is understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

In the embodiment of the present invention, the host material, the matrix material, the Host material, and the Matrix material have the same meaning and are interchangeable.

In the embodiment of the present invention, the singlet states and the singlet states have the same meaning and are interchangeable.

In the embodiment of the present invention, the triplet state and the triplet state have the same meaning and are interchangeable.

In the present invention, the composition and the printing ink, or ink, have the same meaning and are interchangeable.

In the present invention, the complex excited state, exciplex, and Exciplex have the same meaning and are interchangeable.

The term "small molecule" as defined herein refers to a molecule that is not a polymer, oligomer, dendrimer, or blend. In particular, there are no repeating structures in small molecules. The molecular weight of the small molecule is ≤ 3000 g/mol, preferably ≤ 2000 g/mol, preferably ≤ 1500 g/mol.

The present invention relates to an aromatic amine compound of the formula (I):

among them:

Each occurrence of Ar ₁ -Ar ₆ may be independently selected from an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms. Or a combination of these systems, wherein between Ar ₁ and Ar _{2 ,} between Ar ₃ and Ar ₄ , and between Ar ₅ and Ar ₆ may be linked to form a monocyclic or polycyclic aliphatic or aromatic ring system.

o, p, q each independently represent an integer of 0 to 1, and o + p + q ≥ 1;

m and n each independently represent an integer of 0 to 3.

In a preferred embodiment, each occurrence of R ₀ , R ₁ , R ₂ is the same or different selected from H, or D, or a linear alkyl, alkoxy group having from 1 to 10 C atoms or a thioalkoxy group, or a branched or cyclic alkyl, alkoxy or thioalkoxy group having 3 to 10 C atoms, or a silyl group, or a keto group having 1 to 10 C atoms Or an alkoxycarbonyl group having 2 to 10 C atoms, or an aryloxycarbonyl group having 7 to 10 C atoms, a cyano group (-CN), a carbamoyl group (-C(=O)NH ₂ ), Haloformyl (-C(=O)-X wherein X represents a halogen atom), formyl (-C(=O)-H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxyl , nitro, CF ₃ , Cl, Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 20 ring atoms, or having 5 to 20 rings An aryloxy or heteroaryloxy group of an atom, or a combination of these, wherein one or more groups may form a monocyclic or polycyclic aliphatic or a ring bonded to each other and/or to the group Aromatic ring system;

In a more preferred embodiment, R _{0 is} selected from H, or D, or a substituted or unsubstituted aromatic or heteroaromatic ring system having from 5 to 20 ring atoms. In a most preferred embodiment, R _{0 is} selected from H, or D.

In a preferred embodiment, an aromatic amine compound according to the present invention is characterized in that the aromatic amine compound has a structure represented by the general formula (II-1)-(II-8):

Wherein Ar ₁ -Ar ₆ , o, p, q, m, n, R ₀ , R ₁ , R _{2 ,} L ₁ -L ₃ have the same meaning as in claim 1.

In a preferred embodiment, according to the aromatic amine compound of the present invention, each of Ar ₁ -Ar ₆ may be independently selected from an aromatic or heteroaromatic ring system having 5 to 30 ring atoms. Or an aryloxy or heteroaryloxy group having 5 to 30 ring atoms, or a combination of these systems, wherein one or more groups may form a single ring to each other and/or to the ring to which the group is bonded Or a polycyclic aliphatic or aromatic ring system;

In a more preferred embodiment, according to the aromatic amine compound of the present invention, each of Ar ₁ -Ar ₆ may be independently selected from an aromatic or heteroaromatic ring system having 5 to 20 ring atoms. Or an aryloxy or heteroaryloxy group having 5 to 20 ring atoms, or a combination of these systems, wherein between Ar ₁ and Ar _{2 ,} between Ar ₃ and Ar ₄ , and between Ar ₅ and Ar ₆ It may be linked to form a monocyclic or polycyclic aliphatic or aromatic ring system.

Specifically, the Ar ₁ -Ar ₆ may be independently selected from the following structures:

Wherein each occurrence of Z may be independently selected from N or CR ₅ , and two adjacent Zs may not be N at the same time; when Z is connected to N in the general formula (I), Z is C;

R ₃ , R ₄ and R ₅ have the same meanings as R ₁ ;

P represents a saturated cycloalkane or heterocycloalkane having 3 to 10 ring atoms; preferably represents a saturated cycloalkane or heterocycloalkane having 3 to 8 ring atoms; more preferably represents a saturation having 3 to 5 ring atoms a cycloalkane or a heterocycloalkane;

The dotted line indicates a single bond in which the group is bonded to the N atom of the aromatic amine.

In a more preferred embodiment, wherein Ar ₁ to Ar ₆ are independently selected from the following structures:

In a preferred embodiment, L ₁ -L ₃ is a linking group selected from a single bond, an aromatic group or a heteroaromatic group;

An aromatic group refers to a hydrocarbon group containing at least one aromatic ring, including a monocyclic group and a polycyclic ring system. Heteroaromatic groups refer to hydrocarbyl groups (containing heteroatoms) comprising at least one heteroaromatic ring, including monocyclic groups and polycyclic ring systems. These polycyclic rings may have two or more rings in which two carbon atoms are shared by two adjacent rings, a fused ring. At least one of these heterocyclic rings is an aromatic or heteroaromatic group. For the purposes of the present invention, an aromatic group or a heteroaromatic group includes not only a system of an aromatic group or a heteroaryl group, but also a plurality of aryl or heteroaryl groups may also be interrupted by short non-aromatic units (for example, <10). % of non-H atoms, 5% of non-H atoms, such as C, N or O atoms). Thus, systems such as 9,9'-spirobifluorene, 9,9-diarylfluorene, triarylamine, diaryl ether and the like are also considered to be aromatic groups for the purposes of the present invention.

Specifically, preferred examples of the aromatic group are: benzene, naphthalene, anthracene, phenanthrene, perylene, tetracene, anthracene, benzopyrene, triphenylene, anthracene, anthracene, and derivatives thereof.

Specifically, preferred examples of heteroaromatic groups are: furan, benzofuran, thiophene, benzothiophene, pyrrole, pyrazole, triazole, imidazole, oxazole, oxadiazole, thiazole, tetrazole, hydrazine, hydrazine Oxazole, pyrroloimidazole, pyrrolopyrrole, thienopyrrole, thienothiophene, furopyrrol, furanfuran, thienofuran, benzisoxazole, benzisothiazole, benzimidazole, pyridine, pyrazine, Pyridazine, pyrimidine, triazine, quinoline, isoquinoline, o-diazine, quinoxaline, phenanthridine, carbaidine, quinazoline, quinazolinone, and derivatives thereof.

In one embodiment, the L ₁ -L _{3 of the} present invention is selected from an aromatic group having 6 to 40 carbon atoms or a heteroaromatic group having 3 to 40 carbon atoms. Further, L ₁ -L _{3 is} selected from an aromatic group having 6 to 30 carbon atoms or a heteroaromatic group having 3 to 30 carbon atoms. Further, L ₁ -L _{3 is} selected from an aromatic group having 6 to 20 carbon atoms or a heteroaromatic group having 3 to 20 carbon atoms.

Examples of suitable aromatic or heteroaromatic groups which may be L ₁ -L ₃ are, but not limited to, benzene, naphthalene, anthracene, phenanthrene, anthracene, pyridine, pyrimidine, triazine, anthracene, sulfonium, silicon germanium. , carbazole, thiophene, furan, thiazole, triphenylamine, triphenylphosphine oxide, tetraphenyl silicon, snail, spirosilicone and the like.

Specifically, the linking group L ₁ -L _{3 of the} present invention may comprise one or more combinations of the following structural formulas:

Wherein each occurrence of X may be independently selected from N or CR ₆ ; each occurrence of Y may be independently selected from CR ₇ R ₈ , SiR ₉ R ₁₀ , NR ₁₁ or C(=O), S, Or O; R _{6 -} R ₁₁ has the same meaning as R ₁ ;

Further, the linking group L ₁ -L _{3 of the} present invention may be selected from the following structural units, which may be further substituted:

In the embodiment of the present invention, the energy level structure of the organic compound, the triplet energy level E _T , the highest occupied orbital energy level HOMO, and the lowest occupied orbital energy level LUMO play an important role. The following is an introduction to the determination of these energy levels.

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

The triplet energy level E _{T of} organic materials can be measured by low temperature time-resolved luminescence spectroscopy, or by quantum simulation calculations (eg by Time-dependent DFT), as by commercial software Gaussian 03W (Gaussian Inc.), specific simulation methods. See WO2011141110 or as described below in the examples.

It should be noted that the absolute values of HOMO, LUMO, E _T depend on the measurement method or calculation method used. Even for the same method, different evaluation methods, such as starting point and peak point on the CV curve, can give different HOMO/ LUMO value. Therefore, reasonable and meaningful comparisons should be made using the same measurement method and the same evaluation method. In the description of the embodiments of the present invention, the values of HOMO, LUMO, and E _T are simulations based on Time-dependent DFT, but do not affect the application of other measurement or calculation methods. The energy level values determined by different methods should be calibrated against each other.

In the invention, (HOMO-1) is defined as the second highest occupied orbital level, (HOMO-2) is 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.

In a preferred embodiment, the compound according to the invention is at least partially deuterated, preferably 10% of H is deuterated, more preferably 20% of H is deuterated, very preferably 30% H It is best to be replaced by 40% of H.

The compounds according to the invention can be used in various functional layers of organic electronic devices. In a preferred embodiment, the compound according to the invention is used as a hole transporting material, a hole injecting material, and a host material.

In certain preferred embodiments, the compound according to the invention has a HOMO ≥ -5.5 eV, preferably ≥ - 5.2 eV, more preferably ≥ - 5.1 eV, most preferably ≥ - 5.0 eV.

In certain preferred embodiments, the compound according to the invention, ((HOMO-(HOMO-1)) ≥ 0.15 eV, preferably ≥ 0.25 eV, more preferably ≥ 0.3 eV, more preferably ≥ 0.35 eV, very good is ≥0.4eV, preferably ≥0.5eV.

In certain embodiments, the compound according to the invention has a LUMO ≥ -3.0 eV, preferably ≥ -2.3 eV, more preferably ≥ -2.2 eV, most preferably ≥ - 2.0 eV.

In other preferred embodiments, the compound according to the invention has a triplet energy level E _T ≥ 2.4 eV, preferably ≥ 2.6 eV, more preferably ≥ 2.7 eV, most preferably ≥ 2.8 eV.

As a hole transporting material, a hole injecting material, and a host material, hole mobility is sometimes a very important parameter.

In some preferred embodiments, the compounds according to the present invention has a high hole mobility, typically ≥10 ^-5 cm ² / Vs, Jiaoyou ≥10 ^-4 cm ² / Vs, and most ≥10 ^-3 cm ² /Vs.

In other preferred embodiments, the compound according to the invention has a glass transition temperature of ≥ 100 ° C, preferably ≥ 110 ° C, more preferably ≥ 120 ° C, most preferably ≥ 140 ° C.

In a preferred embodiment, a compound according to the invention is preferably, but not limited to, the following structure:

In certain embodiments, the aromatic amine compound according to the present invention also has luminescent properties with an emission wavelength of between 300 and 1000 nm, preferably between 350 and 900 nm, more preferably between 400 and 800 nm. The luminescence referred to herein means photoluminescence or electroluminescence.

In certain preferred embodiments, the aromatic amine compound according to the present invention has a photo or electroluminescence efficiency of ≥ 30%, preferably ≥ 40%, more preferably ≥ 50%, most preferably ≥ 60%.

In certain embodiments, the aromatic amine compound according to the present invention may also be a hole transport material or an electron injecting material.

The invention still further relates to a high polymer comprising at least one repeating unit comprising a structural unit represented by the general formula (I).

In a preferred embodiment, the method for synthesizing the high polymer is selected from the group consisting of SUZUKI-, YAMAMOTO-, STILLE-, NIGESHI-, KUMADA-, HECK-, SONOGASHIRA-, HIYAMA-, FUKUYAMA-, HARTWIG-BUCHWALD- and ULLMAN.

In a preferred embodiment, the polymer according to the invention has a glass transition temperature (Tg) ≥ 100 ° C, preferably ≥ 120 ° C, more preferably ≥ 140 ° C, more preferably ≥ 160 ° C, optimal. It is ≥180 °C.

In a preferred embodiment, the polymer according to the present invention preferably has a molecular weight distribution (PDI) in the range of from 1 to 5; more preferably from 1 to 4; more preferably from 1 to 3, still more preferably 1 ～2 is most preferably 1 to 1.5.

In a preferred embodiment, the weight average molecular weight (Mw) of the high polymer according to the present invention preferably ranges from 10,000 to 1,000,000; more preferably from 50,000 to 500,000; more preferably from 100,000 to 40. More preferably, it is 150,000 to 300,000, and most preferably 200,000 to 250,000.

The present invention also provides a mixture comprising at least one of the above-described aromatic amine compounds or polymers, and at least one other organic functional material, said at least one other organic functional material being selectable In hole injection material (HIM), hole transport material (HTM), p-dopant, electron transport material (ETM), electron injecting material (EIM), electron blocking material (EBM), hole blocking material (HBM), Emitter, host material and organic dye. Various organic functional materials are described in detail in, for example, WO2010135519A1, US20090134784A1, and WO 2011110277A1, the entire disclosure of which is hereby incorporated by reference.

In a more preferred embodiment, the mixture of the ones comprises at least one aromatic amine compound or polymer according to the invention and a p-dopant, wherein the p-dopant weight percentage is ≤ 10 wt%, preferably ≤ 9 wt%, more preferably ≤ 7 wt%, particularly preferably ≤ 6 wt%, most preferably ≤ 5 wt%.

In certain embodiments, the mixture comprises at least one aromatic amine compound or polymer according to the present invention, and a fluorescent host material. Such a mixture may be used as a fluorescent host material, and may further comprise a fluorescent illuminant, wherein the fluorescent illuminant has a weight percentage of ≤10% by weight, preferably ≤9wt%, more preferably ≤8wt%, particularly preferably ≤7wt% Preferably, it is ≤ 5 wt%.

In another preferred embodiment, the mixture of said one comprises at least one aromatic amine compound or polymer according to the invention and a phosphorescent host material. Such a mixture may be used as a phosphorescent host material, and may further comprise a phosphorescent emitter, wherein the phosphorescent emitter has a weight percentage of ≤ 25 wt%, preferably ≤ 20 wt%, more preferably ≤ 15 wt%.

The fluorescent host material, singlet illuminant, phosphorescent host material, triplet illuminant and p-dopant material are described in detail below (but are not limited to):

1. Singlet emitter (Singlet Emitter)

Singlet emitters tend to have longer conjugated pi-electron systems. Heretofore, there have been many examples, such as styrylamine and its derivatives disclosed in JP 2913116 B and WO 2001021729 A1, indenoindoles and derivatives thereof disclosed in WO 2008/006449 and WO 2007/140847, and disclosed in US Pat. No. 7,233,019, KR2006-0006760 A quinone triarylamine derivative.

In a preferred embodiment, the singlet emitter can be selected from the group consisting of monostyrylamine, dibasic styrylamine, ternary styrylamine, quaternary styrylamine, styrene phosphine, styrene ether and aromatic amine.

A monostyrylamine refers to a compound comprising an unsubstituted or substituted styryl group and at least one amine, preferably an aromatic amine. A dibasic styrylamine refers to a compound comprising two unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A ternary styrylamine refers to a compound comprising three unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A quaternary styrylamine refers to a compound comprising four unsubstituted or substituted styryl groups and at least one amine, preferably an aromatic amine. A preferred styrene is stilbene, which may be further substituted. The corresponding phosphines and ethers are defined similarly to amines. An arylamine or an aromatic amine refers to a compound comprising three unsubstituted or substituted aromatic ring or heterocyclic systems directly bonded to a nitrogen. At least one of these aromatic or heterocyclic ring systems is preferably selected from the fused ring system and preferably has at least 14 aromatic ring atoms. Preferred examples thereof are aromatic decylamine, aromatic quinone diamine, aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine. An aromatic amide refers to a compound in which a diaryl arylamine group is attached directly to the oxime, preferably at the position of 9. An aromatic quinone diamine refers to a compound in which two diaryl arylamine groups are attached directly to the oxime, preferably at the 9,10 position. The definitions of aromatic decylamine, aromatic quinone diamine, aromatic thiamine and aromatic quinone diamine are similar, wherein the diaryl aryl group is preferably bonded to the 1 or 1,6 position of hydrazine.

Examples of singlet emitters based on vinylamines and arylamines are also preferred examples and can be found in the following patent documents: WO 2006/000388, WO 2006/058737, WO 2006/000389, WO 2007/065549, WO 2007 /115610, US 7250532 B2, DE 102005058557 A1, CN 1583691 A, JP 08053397 A, US 6251531 B1, US 2006/210830 A, EP 1957606 A1 and US 2008/0113101 A1 are hereby incorporated by reference in their entirety. This article is incorporated herein by reference.

An example of a singlet emitter based on a stilbene extreme derivative is US 5121029.

Further preferred singlet emitters can be selected from indenoindole-amines and indenofluorene-diamines, as disclosed in WO 2006/122630, benzoindoloindole-amines and benzoindenoindole-diamines , as disclosed in WO 2008/006449, dibenzoindolo-amine and dibenzoindeno-diamine, as disclosed in WO 2007/140847.

Further preferred singlet emitters are selected from the group consisting of ruthenium-based fused ring systems as disclosed in US2015333277A1, US2016099411A1, US2016204355A1.

More preferred singlet emitters may be selected from the derivatives of hydrazine, such as those disclosed in US2013175509A1; triarylamine derivatives of hydrazine, such as triarylamine derivatives of hydrazine containing dibenzofuran units disclosed in CN102232068B; A triarylamine derivative of hydrazine having a specific structure, as disclosed in CN105085334A, CN105037173A. Other materials which can be used as singlet emitters are polycyclic aromatic hydrocarbon compounds, in particular derivatives of the following compounds: for example, 9,10-bis(2-naphthoquinone), naphthalene, tetraphenyl, xanthene, phenanthrene , 芘 (such as 2,5,8,11-tetra-t-butyl fluorene), anthracene, phenylene such as (4,4'-bis(9-ethyl-3-carbazolevinyl)-1 , 1 '-biphenyl), indenyl hydrazine, decacycloolefin, hexacene benzene, anthracene, spirobifluorene, aryl hydrazine (such as US20060222886), arylene vinyl (such as US5121029, US5130603), cyclopentane Alkene such as tetraphenylcyclopentadiene, rubrene, coumarin, rhodamine, quinacridone, pyran such as 4 (dicyanomethylidene)-6-(4-p-dimethylaminobenzene Vinyl-2-methyl)-4H-pyran (DCM), thiopyran, bis(pyridazinyl)imine boron compound (US 2007/0092753 A1), bis(pyridazinyl)methylene compound, carbostyryl Compounds, oxazinone, benzoxazole, benzothiazole, benzimidazole and pyrrolopyrroledione. Materials for some singlet illuminants can be found in the following patent documents: US 20070252517 A1, US 4769292, US 6020078, US 2007/0252517 A1, US 2007/0252517 A1. The entire contents of the above-listed patent documents are hereby incorporated by reference.

Some examples of suitable singlet emitters are listed in the table below:

2. Triplet emitter (Triplet Emitter)

Triplet emitters are also known as phosphorescent emitters. In a preferred embodiment, the triplet emitter is a metal complex of the formula M(L)n, wherein M is a metal atom, and each occurrence of L may be the same or different and is an organic ligand. It is bonded to the metal atom M by one or more positional bonding or coordination, and n is an integer greater than 1, preferably 1, 2, 3, 4, 5 or 6. Alternatively, these metal complexes are coupled to a polymer by one or more positions, preferably by an organic ligand.

In a preferred embodiment, the metal atom M is selected from a transition metal element or a lanthanide or a lanthanide element, preferably Ir, Pt, Pd, Au, Rh, Ru, Os, Sm, Eu, Gd, Tb, Dy Re, Cu or Ag, with Os, Ir, Ru, Rh, Re, Pd, Au or Pt being particularly preferred.

Preferentially, the triplet emitter comprises a chelating ligand, ie a ligand, coordinated to the metal by at least two bonding sites, with particular preference being given to the triplet emitter comprising two or three identical or different pairs Tooth or multidentate ligand. Chelating ligands are beneficial for increasing the stability of metal complexes.

Examples of the organic ligand may be selected from a phenylpyridine derivative, a 7,8-benzoquinoline derivative, a 2(2-thienyl)pyridine derivative, a 2(1-naphthyl)pyridine derivative, or a 2 benzene. A quinolinol derivative. All of these organic ligands may be substituted, for example by fluorine or trifluoromethyl. The ancillary ligand may preferably be selected from the group consisting of acetone acetate or picric acid.

In a preferred embodiment, the metal complex that can be used as the triplet emitter has the following form:

Wherein M is a metal selected from a transition metal element or a lanthanide or actinide element, particularly preferably Ir, Pt, Au;

Ar ₁ may be the same or different at each occurrence, and is a cyclic group containing at least one donor atom, that is, an atom having a lone pair of electrons, such as nitrogen or phosphorus, through which a cyclic group is coordinated to a metal. Connection; Ar ₂ may be the same or different each time it appears, is a cyclic group containing at least one C atom through which a cyclic group is attached to the metal; Ar ₁ and Ar ₂ are bonded by a covalent bond Together, each may carry one or more substituent groups, which may also be joined together by a substituent group; L' may be the same or different at each occurrence, and is a bidentate chelate auxiliary ligand, preferably Is a monoanionic bidentate chelate ligand; q1 can be 0, 1, 2 or 3, preferably 2 or 3; q2 can be 0, 1, 2 or 3, preferably 1 or 0.

Examples of the application of materials for some triplet emitters can be found in the following patent documents and documents: WO 200070655, WO 200141512, WO 200202714, WO 200215645, EP 1191613, EP 1191612, EP 1191614, WO 2005033244, WO 2005019373, US 2005 /0258742, WO 2009146770, WO 2010015307, WO 2010031485, WO 2010054731, WO 2010054728, WO 2010086089, WO 2010099852, WO 2010102709, US 20070087219 A1, US 20090061681 A1, US 20010053462 A1, Baldo, Thompson et al. Nature 403, (2000) ), 750-753, US 20090061681 A1, US 20090061681 A1, Adachi et al. Appl. Phys. Lett. 78 (2001), 1622-1624, J. Kido et al. Appl. Phys. Lett. 65 (1994), 2124, Kido et al. Chem. Lett. 657, 1990, US 2007/0252517 A1, Johnson et al., JACS 105, 1983, 1795, Wrighton, JACS 96, 1974, 998, Ma et al., Synth. Metals 94 , 1998, 245, US 6824895, US 7029766, US 6835469, US 6830828, US 20010053462 A1, WO 2007095118 A1, US 2012004407A1, WO 2012007088A1, WO2012007087A1, WO 2012007086A1, US 2008027220A1, WO 2011157339A1, CN 102282150A, WO 2009118087A1, WO 2013107487A1 , WO 201309 4620A1, WO 2013174471A1, WO 2014031977A1, WO 2014112450A1, WO 2014007565A1, WO 2014038456A1, WO 2014024131A1, WO 2014008982A1, WO2014023377A1. The entire contents of the above-listed patent documents and documents are hereby incorporated by reference.

Some examples of suitable triplet emitters are listed in the table below:

3. Fluorescent host material

The fluorescent host material is also referred to as a singlet host material, and the example of the fluorescent host material is not particularly limited, and any organic compound may be used as a host as long as it has a singlet energy ratio illuminant, particularly a singlet illuminant. Or the fluorescent illuminant is higher.

Examples of the organic compound used as the fluorescent host material may be selected from the group consisting of a cyclic aromatic hydrocarbon compound such as benzene, biphenyl, triphenyl, benzo, naphthalene, anthracene, anthracene, phenanthrene, anthracene, anthracene, fluorene, fluorene, fluorene; Aromatic heterocyclic compounds such as dibenzothiophene, dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, carbazole, carbazole, pyridinium , pyrrole dipyridine, pyrazole, imidazole, triazole, isoxazole, thiazole, oxadiazole, triazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, evil Pyrazine, oxazine, oxadiazine, hydrazine, benzimidazole, oxazole, pyridazine, benzoxazole, benzoisoxazole, benzothiazole, quinoline, isoquinoline, porphyrin, quinazoline Porphyrin, quinoxaline, naphthalene, anthracene, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furan dipyridine, benzothienopyridine, thiophene dipyridine, benzene And selenophene pyridine and selenophene dipyridine; groups containing a 2 to 10 ring structure, which may be the same or different types of cyclic aromatic hydrocarbon groups or Hong heterocyclic group, and at least one of the following groups coupled together directly or through another, such as an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, chain structural unit and the aliphatic cyclic group.

In a preferred embodiment, the fluorescent host material can be selected from compounds comprising at least one of the following groups:

Wherein R ¹ may be independently of one another selected from the group consisting of hydrogen, deuterium, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl; n is a An integer from 0 to 20; X ¹ -X ^{8 is} selected from CH or N; X ⁹ and X ^{10 are} selected from CR ¹ R ² or NR ¹ . R ² has the same meaning as R ¹ .

In some preferred embodiments, the fluorescent host is selected from the group consisting of hydrazine derivatives, such as those disclosed in the patent documents CN102224614 B, CN 100471827 C, CN 1914293 B, WO2015033559A1, US2014246657A1, WO2016117848A1, WO2016117861A1, WO2016171429A2, CN102369256B, CN102428158B.

Some examples of fluorenyl-based fluorescent host materials are listed in the table below:

In some more preferred embodiments, the fluorenyl-based fluorescent host material is deuterated, that is, the host material molecule contains at least one ruthenium atom, such as disclosed in the patent documents CN102369256B, CN102428158B, CN102639671B, US2015021586A1, and the like. Specific examples are:

4. Phosphorescent host material

The phosphorescent host material is also referred to as a triplet host material, and the example of the triplet host material is not particularly limited, and any metal complex or organic compound may be used as a host as long as its triplet level is higher than that of the illuminant, especially The triplet emitter or phosphorescent emitter is higher, and examples of metal complexes that can be used as a triplet host include, but are not limited to, the following general structure:

M is a metal; (Y ³ -Y ⁴ ) is a bidentate ligand, Y ³ and Y ^{4 are} independently selected from C, N, O, P, and S; L is an ancillary ligand; m is an integer The value is from 1 to the maximum coordination number of the metal; in a preferred embodiment, the metal complex that can be used as the triplet host has the following form:

(O-N) is a two-tooth ligand in which a metal is coordinated to an O and N atom. m is an integer whose value ranges from 1 to the maximum coordination number of the metal;

In one embodiment, M is optional for Ir and Pt.

Examples of the organic compound which can be used as the host of the triplet state are selected from compounds containing a cyclic aromatic hydrocarbon group such as benzene, biphenyl, triphenylbenzene, benzindene; compounds containing an aromatic heterocyclic group such as dibenzothiophene, Dibenzofuran, dibenzoselenophene, furan, thiophene, benzofuran, benzothiophene, benzoselenophene, oxazole, dibenzoxazole, carbazole, pyridinium, pyrrole dipyridine, Pyrazole, imidazole, triazole, oxazole, thiazole, oxadiazole, oxatriazole, dioxazole, thiadiazole, pyridine, pyridazine, pyrimidine, pyrazine, triazine, oxazine, oxazine , oxadiazine, anthraquinone, benzimidazole, oxazole, oxazole, dibenzoxazole, benzoisoxazole, benzothiazole, quinoline, isoquinoline, o-naphthyridine, quinazoline, Quinoxaline, naphthalene, anthracene, pteridine, xanthene, acridine, phenazine, phenothiazine, phenoxazine, benzofuranpyridine, furopypyridine, benzothienopyridine, thienopyridine, benzoselenophene Pyridine and selenophene benzopyridine; groups containing a 2 to 10 ring structure, which may be the same or different types of cyclic aromatic hydrocarbon groups or Hong heterocyclic group, and at least one of the following groups coupled together directly or through another, such as an oxygen atom, a nitrogen atom, a sulfur atom, a silicon atom, a phosphorus atom, a boron atom, chain structural unit and the aliphatic cyclic group. Wherein, each Ar may be further substituted, and the substituent may be hydrogen, hydrazine, cyano, halogen, alkyl, alkoxy, amino, alkene, alkyne, aralkyl, heteroalkyl, aryl and heteroaryl. base.

In a preferred embodiment, the triplet host material can be selected from compounds comprising at least one of the following groups:

R ² -R ⁷ have the same meaning as R ¹ , X ^{9 is} selected from CR ¹ R ² or NR ¹ , and Y is selected from CR ¹ R ² or NR ¹ or O or S. R ¹ , n, X ¹ -X ⁸ , and Ar ¹ to Ar ³ have the same meanings as described above.

Examples of suitable triplet host materials are listed in the table below but are not limited to:

5.p-dopant

In recent years, many published organic semiconductors have introduced the concept of molecular doping in their conductivity control methods. Such an organic semiconductor material may be composed of a compound having good electron donating properties or good electron withdrawing properties. For P-type dopants used in doping hole transport materials, strong electron acceptors such as tetracyanoquinone dimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4- Benzoyl dimethane (F4TCNQ) is well known. See article M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, App. Phys. Lett., 73 (22), 3202-3204 (1998) and J. Blochwitz, M. Pfeiffer, T. Fritz, K. Leo, App. Phys. Lett., 73 (6), 729-731 (1998).

Due to defects in TCNQ and F4TCNQ in specific applications (molecular weight is too small, too volatile), a series of hydroquinone derivatives can be used as P-type dopants, the structure of which includes but is not limited to the following structure (patent TW200629362A):

Wherein R ⁸ to R ^{19 are} independently F, Cl, CN, NO ₂ , CF ₃ , perfluoroalkyl, SO ₃ R ²⁰ , aryl or heteroaryl, wherein the aryl and heteroaryl are from one to the other F, Cl, CN, NO ₂ , CF ₃ , perfluoroalkyl, SO ₃ R;

R ²⁰ at each occurrence, the same or different, H, D, a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or having 3 to 20 C a branched or cyclic alkyl, alkoxy or thioalkoxy group of an atom or a silyl group, or a substituted keto group having 1 to 20 C atoms, or having 2 to 20 C atom alkoxycarbonyl groups, or an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group (-CN), a carbamoyl group (-C(=O)NH ₂ ), haloformyl group (-C(=O)-X wherein X represents a halogen atom), formyl group (-C(=O)-H), isocyanato group, isocyanate group, sulfur Cyanate group or isothiocyanate group, hydroxyl group, nitro group, CF ₃ group, Cl, Br, F, crosslinkable group or substitution with 5 to 40 ring atoms Or an unsubstituted aromatic or heteroaromatic ring system, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms, or a combination of these systems, wherein one or more of the groups R ₂ may And/or a ring bonded to the group to form a monocyclic or polycyclic aliphatic or aromatic Family ring system;

Wherein A, B, C, and D are independently selected from C(CN) ₂ , (CF ₃ )C(CN), (NO ₂ )C(CN), C(halogen) ₂ , C(CF ₃ ) ₂ , NCN , O, S, NR ²⁰ and the following structure:

There is another class of compounds having an axis as a core, which is characterized by having the following structure

Wherein n2 is selected from a natural number from 1 to 4; each of X ₁ , X ₂ , and X _{3 is} independently selected from the group consisting of C(CN) ₂ , (CF ₃ )C(CN), (NO ₂ )C(CN), C ( Halogen) ₂ , C(CF ₃ ) ₂ , NCN, O, S, NR1 and the following structures:

R ⁸ to R ¹⁵ have the same meanings as defined above, wherein X ₁ to X _{3 are} independently selected from C(CN) ₂ , (CF ₃ )C(CN), (NO ₂ )C(CN), C(halogen) ₂ , C ( CF ₃ ) ₂ , NCN, O, S, NR ₁ , wherein Y=CN, NO ₂ , COR ₁ or all halogen-substituted alkyl; aryl is substituted or unsubstituted arene or biaryl; heteroaryl Is a substituted or unsubstituted aromatic heterocyclic compound or a diheteroaryl group;

It is an object of the present invention to provide a material solution for an evaporated OLED.

In certain embodiments, the 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 kg/mol, most preferably ≤800 g/mol.

Another object of the invention is to provide a material solution for printing OLEDs.

In certain embodiments, the compounds according to the invention have a molecular weight of ≥ 700 g/mol, preferably ≥ 800 g/mol, very preferably ≥ 900 g/mol, more preferably ≥ 1000 g/mol, most preferably ≥ 1100 g/mol.

In other embodiments, the compound according to the invention has a solubility in toluene of > 2 mg/ml, preferably > 3 mg/ml, more preferably > 4 mg/ml, most preferably > 5 mg/ml at 25 °C.

Another object of the invention is a solution for providing materials for printing OLEDs.

The invention further relates to a composition or ink comprising the aromatic amine compound, polymer or mixture of any of the above, and at least one organic solvent.

According to a composition of the invention, the at least one organic solvent is selected from the group consisting of aromatic or heteroaromatic, ester, aromatic ketone or aromatic ether, aliphatic ketone or aliphatic ether, alicyclic or olefinic a compound, or a borate or phosphate 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 selected from solvents based on aromatic or heteroaromatic.

Examples of aromatic or heteroaromatic solvents suitable for the present invention are, but are not limited to, p-diisopropylbenzene, pentylbenzene, tetrahydronaphthalene, cyclohexylbenzene, chloronaphthalene, 1,4-dimethylnaphthalene. , 3-isopropylbiphenyl, p-methyl cumene, dipentylbenzene, triphenylbenzene, 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, 4,4 -difluorodiphenylmethane, 1,2-dimethoxy-4-(1-propenyl)benzene, diphenylmethane, 2-phenylpyridine, 3-phenylpyridine, N-methyldiphenylamine, 4 -isopropylbiphenyl, -dichlorodiphenylmethane, 4-(3-phenylpropyl)pyridine, benzyl benzoate, 1,1-bis(3,4-dimethylphenyl)ethane, 2-isopropylnaphthalene, quinoline, isoquinoline, methyl 2-furancarboxylate, ethyl 2-furancarboxylate, etc.;

Examples of aromatic ketone solvents suitable for the present invention are, but are not limited to, 1-tetralone, 2-tetralone, 2-(phenyl epoxy) tetralone, 6-(methoxy Tetrendanone, acetophenone, propiophenone, benzophenone, and derivatives thereof, such as 4-methylacetophenone, 3-methylacetophenone, 2-methylacetophenone, 4-methylpropiophenone, 3-methylpropiophenone, 2-methylpropiophenone, etc.;

Examples of aromatic ether-based solvents suitable for the present invention are, 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-dimethoxy Toluene, 4-ethyl ether, 1,3-dipropoxybenzene, 1,2,4-trimethoxybenzene, 4-(1-propenyl)-1,2-dimethoxybenzene, 1, 3-dimethoxybenzene, glycidyl phenyl ether, dibenzyl ether, 4-tert-butyl anisole, trans-p-propenyl anisole, 1,2-dimethoxybenzene, 1-methyl Oxynaphthalene, diphenyl ether, 2-phenoxymethyl ether, 2-phenoxytetrahydrofuran, ethyl-2-naphthyl ether;

In some preferred embodiments, according to the composition of the present invention, the at least one organic solvent may be selected from the group consisting of: an aliphatic ketone, for example, 2-fluorenone, 3-fluorenone, 5-fluorenone, 2 - anthrone, 2,5-hexanedione, 2,6,8-trimethyl-4-indanone, anthrone, phorone, isophorone, di-n-pentyl ketone, etc.; or an aliphatic ether For example, 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, and the like.

In still other preferred embodiments, according to the composition of the present invention, the at least one organic solvent may be selected from ester-based solvents: alkyl octanoate, alkyl sebacate, alkyl stearate, benzene. Alkyl formate, alkyl phenylacetate, alkyl cinnamate, alkyl oxalate, alkyl maleate, alkanolide, alkyl oleate, and the like. Particularly preferred are octyl octanoate, diethyl sebacate, diallyl phthalate, isodecyl isononanoate.

The solvent may be used singly or as a mixture of two or more organic solvents.

In certain preferred embodiments, a composition according to the present invention, comprising the organic compound or composition of any one of the above, and at least one organic solvent, may further comprise another organic solvent, An example of an organic solvent, including but not limited to: methanol, ethanol, 2-methoxyethanol, dichloromethane, 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, hydrazine and/or mixtures thereof.

The invention further relates to the use of a composition as a printing ink for the preparation of organic electronic devices, particular preference being given to a preparation process by printing or coating.

Among them, suitable printing or coating techniques include, but are not limited to, inkjet printing, typography, screen printing, dip coating, spin coating, blade coating, roller printing, twist roll printing, lithography, flexography Printing, rotary printing, spraying, brushing or pad printing, slit-type extrusion coating, etc. Preferred are gravure, screen printing and inkjet printing. Gravure printing, ink jet printing will be applied in embodiments of the invention. The solution or suspension may additionally comprise one or more components such as surface active compounds, lubricants, wetting agents, dispersing agents, hydrophobic agents, binders and the like for adjusting viscosity, film forming properties, adhesion, and the like. For information on printing techniques and their requirements for solutions, such as solvents and concentrations, viscosity, etc., please refer to Helmut Kipphan's "Printing Media Handbook: Techniques and Production Methods" (Handbook of Print Media: Technologies and Production Methods). ), ISBN 3-540-67326-1.

The preparation method as described above, characterized in that the formed functional layer has a thickness of from 5 nm to 1000 nm.

The invention further relates to the use of an aromatic amine compound, polymer, mixture or composition according to any of the preceding claims in an organic electronic device.

An organic electronic device characterized by comprising an aromatic amine compound, a polymer, or a mixture thereof according to any one of the above.

The organic electronic device may be selected from, but not limited to, an organic light emitting diode (OLED), an organic photovoltaic cell (OPV), an organic light emitting cell (OLEEC), an organic field effect transistor (OFET), an organic light emitting field effect transistor, and an organic Lasers, organic spintronic devices, organic sensors and organic plasmon emitting diodes (Organic Plasmon Emitting Diode), etc., particularly preferred are organic electroluminescent devices such as OLED, OLEEC, organic light-emitting field effect transistors.

In some particularly preferred embodiments, the organic electronic device is an electroluminescent device comprising a hole injection layer or a hole transport layer, the hole injection layer or the hole transport layer comprising at least An aromatic amine compound, polymer, or mixture as described above.

In the above light-emitting device, particularly an OLED, a substrate, an anode, at least one light-emitting layer, and a cathode are included.

The substrate can be opaque or transparent. A transparent substrate can be used to make a transparent light-emitting component. See, for example, Bulovic et al. Nature 1996, 380, p29, and Gu et al, Appl. Phys. Lett. 1996, 68, p2606. The substrate can be rigid or elastic. The substrate can be plastic, metal, semiconductor wafer or glass. Preferably, the substrate has a smooth surface. Substrates without surface defects are a particularly desirable choice. In a preferred embodiment, the substrate is flexible, optionally in the form of a polymer film or plastic, having a glass transition temperature Tg of 150 ° C or higher, preferably more than 200 ° C, more preferably more than 250 ° C, preferably More than 300 ° C. Examples of suitable flexible substrates are poly(ethylene terephthalate) (PET) and polyethylene glycol (2,6-naphthalene) (PEN).

The anode can 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 a light-emitting layer. In one embodiment, the absolute value of the difference between the work function of the anode and the HOMO level or the valence band level of the illuminant in the luminescent layer or the p-type semiconductor material as the HIL or 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 the anode material 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 can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like. In certain embodiments, the anode is patterned. Patterned ITO conductive substrates are commercially available and can be used to prepare devices in accordance with the present invention.

The cathode can include a conductive metal or metal oxide. The cathode can easily inject electrons into the EIL or ETL or directly into the luminescent layer. In one embodiment, the work function of the cathode and the LUMO level of the illuminant or the n-type semiconductor material as an electron injection layer (EIL) or electron transport layer (ETL) or hole blocking layer (HBL) in the luminescent layer or The absolute value of the difference in conduction band energy levels is less than 0.5 eV, preferably less than 0.3 eV, and most preferably less than 0.2 eV. In principle, all materials which can be used as cathodes for OLEDs are possible as cathode materials for the devices of the invention. Examples of the cathode material include, but are not limited to, Al, Au, Ag, Ca, Ba, Mg, LiF/Al, MgAg alloy, BaF ₂ /Al, Cu, Fe, Co, Ni, Mn, Pd, Pt, ITO, and the like. The cathode material can be deposited using any suitable technique, such as a suitable physical vapor deposition process, including radio frequency magnetron sputtering, vacuum thermal evaporation, electron beam (e-beam), and the like.

The OLED may further include other 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), and a hole blocking layer. (HBL). Materials suitable for use in these functional layers are described in detail above and in WO2010135519A1, US20090134784A1, and WO2011110277A1, the entire contents of each of which are hereby incorporated by reference.

The light-emitting device according to the present invention has an emission wavelength of between 300 and 1000 nm, preferably between 350 and 900 nm, more preferably between 400 and 800 nm.

The invention further relates to the use of an electroluminescent device according to the invention in various electronic devices, including, but not limited to, display devices, illumination devices, light sources, sensors and the like.

The present invention will be described with reference to the preferred embodiments thereof, but the present invention is not limited to the embodiments described below. It is to be understood that the scope of the invention is intended to be It is to be understood that the modifications of the various embodiments of the invention are intended to be

Specific embodiment

1. Synthesis of compounds

Example 1: Synthesis of Compound 1

Synthesis of Intermediate 1:

15.0 g of 1-fluoro-2-nitrobenzene was dissolved in 300 ml of DMF, and 4.0 g of NaH was added under a nitrogen atmosphere. After stirring at 80 ° C for 30 minutes, after cooling, 11.4 g of hydrazine was added. After stirring at 120 ° C for 12 h. After cooling, DMF was distilled off under reduced pressure, and dichloromethane was added to extract, and washed with water to neutral. The organic phase was spin-dried and recrystallized to give the intermediate 1.

Synthesis of Intermediate 2:

20.0 g of Intermediate 1 was dissolved in 400 ml of triethyl phosphite and stirred at 150 ° C for 12 h. The excess triethyl phosphite was distilled off under reduced pressure, and column chromatography gave intermediate 2.

Synthesis of Compound 1:

10.0 g of Intermediate 2, 28.5 g of Intermediate 3, 560 mg of palladium acetate, 10 ml of 10% strength tris-tert-butylphosphine, 5.8 g of sodium t-butoxide were dissolved in 300 ml of toluene, and refluxed for 12 hours under a nitrogen atmosphere to obtain Compound 1.

Example 2: Synthesis of Compound 2

Synthesis of Compound 2:

10.0 g of Intermediate 2, 28.5 g of Intermediate 3, 560 mg of palladium acetate, 10 ml of 10% strength tri-tert-butylphosphine, 5.8 g of sodium t-butoxide were dissolved in 300 ml of toluene, and refluxed for 12 hours under a nitrogen atmosphere to obtain HT-2. .

Example 3: Synthesis of Compound 3

Synthesis of intermediate 6:

20.0 g of Intermediate 5, 11.4 g of dibenzothiophene-4-boronic acid, 2.8 g of Pd(PPh ₃ ) _{4 were} dissolved in a mixed solvent of 300 ml of THF and 30 ml of water, and refluxed under nitrogen for 12 h. The solvent was removed by rotary distillation, extracted with dichloromethane, washed with water and then evaporated.

Synthesis of intermediate 7:

20.2 g of Intermediate 6, 12.6 g of diboronic acid pinacol ester, 1.5 g of Pd(dppf)Cl ₂ and 4.5 g of potassium acetate were dissolved in 300 ml of 1,4-dioxane, and refluxed for 12 h under a nitrogen atmosphere. The solvent was dried and the column chromatography gave the intermediate 7.

Synthesis of Intermediate 8:

19.4 g of Intermediate 7, 11.3 g of 1-bromo-4-iodobenzene, 2.2 g of Pd(PPh ₃ ) ₄ and 4.0 g of potassium carbonate were placed in a mixed solution of 300 ml of toluene, 50 ml of ethanol and 30 ml of water, and refluxed under a nitrogen atmosphere. 12h. The solvent was evaporated to dryness, extracted with dichloromethane, and washed with water.

Synthesis of Compound 3:

10.0 g of Intermediate 2, 29.5 g of Intermediate 8, 560 mg of palladium acetate, 10 ml of 10% strength tri-tert-butylphosphine, 5.8 g of sodium t-butoxide were dissolved in 300 ml of toluene, and refluxed under a nitrogen atmosphere for 12 h. The solvent was evaporated to dryness, and the mixture was evaporated to dichloromethane.

Example 4: Synthesis of Compound 4

Synthesis of Intermediate 9:

13.0 g of 1-fluoro-2-nitrobenzene was dissolved in 300 ml of DMF, and 4.0 g of NaH was added under a nitrogen atmosphere. After stirring at 80 ° C for 30 minutes, after cooling, 11.6 g of 5-bromoindole was added. After stirring at 120 ° C for 12 h. After cooling, DMF was distilled off under reduced pressure, and dichloromethane was added to extract, and washed with water to neutral. The organic phase was spun dry and recrystallized to give Intermediate 9.

Synthesis of intermediate 10:

26.0 g of Intermediate 9 was dissolved in 400 ml of triethyl phosphite and stirred at 150 ° C for 12 h. The excess triethyl phosphite was distilled off under reduced pressure, and the residue was purified by column chromatography.

Synthesis of intermediate 11:

7.8 g of 1-fluorobenzene was dissolved in 200 ml of DMF, and 3.0 g of NaH was added under a nitrogen atmosphere. After stirring at 80 ° C for 30 minutes, after cooling, 20.0 g of the intermediate 10 was added. The mixture was stirred at 120 ° C for 12 hours. After cooling, DMF was evaporated under reduced pressure, and dichloromethane was added to extract, and washed with water to neutral. The organic phase was spun dry and recrystallized to give the intermediate 11.

Synthesis of Compound 4:

10.0 g of Intermediate 11, 6.6 g of Intermediate 8, 360 mg of palladium acetate, 6.5 ml of 10% strength tri-tert-butylphosphine, 4.0 g of sodium t-butoxide were dissolved in 150 ml of toluene, and refluxed under a nitrogen atmosphere for 12 h. The solvent was evaporated to dryness, and the mixture was partitioned with dichloromethane.

Example 5: Synthesis of Compound 5

Synthesis of intermediate 13:

15.0 g of 1-fluoro-2-nitrobenzene was dissolved in 300 ml of DMF, and 4.0 g of NaH was added under a nitrogen atmosphere. After stirring at 80 ° C for 30 minutes, after cooling, 19.6 g of 5-bromoindole was added. After stirring at 120 ° C for 12 h. After cooling, DMF was distilled off under reduced pressure, and dichloromethane was added to extract, and washed with water to neutral. The organic phase was spun dry and recrystallized to give intermediate 13.

Synthesis of intermediate 14:

26.0 g of the intermediate 13 was dissolved in 400 ml of triethyl phosphite, and stirred at 150 ° C for 12 h. Excess triethyl phosphite was distilled off under reduced pressure, and column chromatography gave Intermediate 14.

Synthesis of intermediate 15:

7.8 g of 1-fluorobenzene was dissolved in 200 ml of DMF, and 3.0 g of NaH was added under a nitrogen atmosphere. After stirring at 80 ° C for 30 minutes, after cooling, 20.0 g of Intermediate 14 was added. The mixture was stirred at 120 ° C for 12 hours. After cooling, DMF was evaporated under reduced pressure, and dichloromethane was added to extract and partitioned and washed to neutral. The organic phase was spun dry and recrystallized to give intermediate 15.

Synthesis of Compound 5:

10.0 g of Intermediate 11, 6.6 g of Intermediate 15, 360 mg of palladium acetate, 6.5 ml of 10% strength tri-tert-butylphosphine, 4.0 g of sodium t-butoxide were dissolved in 150 ml of toluene, and refluxed under a nitrogen atmosphere for 12 h. The solvent was evaporated to dryness, and the mixture was partitioned with dichloromethane.

2.2. Compound energy level structure

The energy structure of the organic repeating structural unit can be obtained by quantum calculation, for example, by TD-DFT (time-dependent density functional theory) by Gaussian 03W (Gaussian Inc.), and the specific simulation method can be found in WO2011141110. First, the semi-empirical method "Ground State/Semi-empirical/Default Spin/AM1" (Charge 0/Spin Singlet) is used to optimize the molecular geometry, and then the energy structure of the organic molecule is determined by TD-DFT (time-dependent density functional theory) method. Calculated "TD-SCF/DFT/Default Spin/B3PW91" and the base group "6-31G(d)" (Charge 0/Spin Singlet). The HOMO and LUMO levels are calculated according to the following calibration formula, and S1 and T1 are used directly.

HOMO(eV)=((HOMO(G)×27.212)-0.9899)/1.1206

LUMO(eV)=((LUMO(G)×27.212)-2.0041)/1.385

Among them, HOMO(G) and LUMO(G) are direct calculation results of Gaussian 09W, and the unit is eV. The results are shown in Table 1, where ΔHOMO=HOMO-(HOMO-1):

Table 1

3. Preparation and characterization of OLED devices

In this embodiment, Compound 1, Compound 4, Compound 5, Ref-1, NPB are used as hole transport materials, DNTPD is used as hole injection material, and B3PYMPM is used as electron transport material, and the device structure is ITO/HATCN/empty. Hole transport material / BH: BD (95: 5) / B3PYMPM / LiF / Al electroluminescent device. The preparation process using the above OLED device will be described in detail below through specific embodiments:

a, ITO (indium tin oxide) conductive glass substrate cleaning: using a variety of solvents (such as one or several of chloroform, acetone or isopropanol) cleaning, and then UV ozone treatment;

b, DNTPD (60 nm), hole transport material (20 nm), BH: BD (95:5; 20 nm), B3PYMPM (30 nm), LiF (1 nm), Al (100 nm) in high vacuum (1 × 10 ^-6 m Ba) is made by heat evaporation;

c. Package: The device is encapsulated in a nitrogen glove box with an ultraviolet curable resin.

The current and voltage (IVL) characteristics of each OLED device are characterized by characterization equipment, as described in Table 2.

Table 2

The above-described embodiments are merely illustrative of several embodiments of the present invention, and the description thereof is more specific and detailed, but is not to be construed as limiting the scope of the invention. It should be noted that a number of variations and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, the scope of the invention should be determined by the appended claims.

Claims

An aromatic amine compound of the formula (I):

among them:

Each occurrence of R 0 , R 1 , and R 2 is the same or different selected from H, or D, or a linear alkyl, alkoxy or thioalkoxy group having 1 to 20 C atoms, or a branched or cyclic alkyl, alkoxy or thioalkoxy group of 3 to 20 C atoms, or a silyl group, or a ketone group having 1 to 20 C atoms, or 2 to 20 C Alkoxycarbonyl group of an atom, or an aryloxycarbonyl group having 7 to 20 C atoms, a cyano group (-CN), a carbamoyl group (-C(=O)NH 2 ), a haloformyl group (-C(= O)-X wherein X represents a halogen atom), formyl (-C(=O)-H), isocyano, isocyanate, thiocyanate or isothiocyanate, hydroxy, nitro, CF 3 , Cl , Br, F, a crosslinkable group, or a substituted or unsubstituted aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryl group having 5 to 40 ring atoms An oxy group, or a combination of these systems, wherein one or more groups may form a monocyclic or polycyclic aliphatic or aromatic ring system with each other and/or with a ring to which the group is bonded;

L 1 -L 3 is a linking group selected from a single bond, an aromatic group or a heteroaromatic group;

Each occurrence of Ar 1 -Ar 6 is independently selected from an aromatic or heteroaromatic ring system having 5 to 40 ring atoms, or an aryloxy or heteroaryloxy group having 5 to 40 ring atoms. Or a combination of these systems, wherein between Ar 1 and Ar 2 , between Ar 3 and Ar 4 , and between Ar 5 and Ar 6 are linked to form a monocyclic or polycyclic aliphatic or aromatic ring system,

o, p, q independently of each other represent an integer from 0 to 1, and o + p + q ≥ 1;

m and n represent an integer of 0 to 3 independently of each other.
The aromatic amine compound according to claim 1, wherein the compound has a structure represented by the formulae (II-1) to (II-8):
The aromatic amine compound according to any one of claims 1 to 2, wherein each occurrence of the Ar 1 -Ar 6 is independently selected from the following structures:

Wherein each occurrence of Z is independently selected from N or CR 5 , and two adjacent Z cannot be N at the same time; when Z is linked to N in the general formula (I), Z is C;

R 3 , R 4 and R 5 have the same meanings as R 1 ;

P represents a saturated cycloalkane or heterocycloalkane having 3 to 10 ring atoms;

The dotted line indicates a single bond in which the group is bonded to the N atom of the aromatic amine.
The aromatic amine compound according to any one of claims 1 to 3, wherein the linking group L 1 -L 3 comprises one or more combinations of the following structural formulas:

Wherein each occurrence of X is independently selected from N or CR 6 ; each occurrence of Y, independently selected from CR 7 R 8 , SiR 9 R 10 , NR 11 or C(=O), S, or O ; R 6 -R 11 have the same meaning as R 1 .
The aromatic amine compound according to any one of claims 1 to 4, wherein HOMO ≥ -5.5 eV, HOMO represents the highest occupied orbital energy level of the aromatic amine compound.
A polymer comprising at least one repeating structural unit represented by the formula (I).
A mixture comprising at least one aromatic amine compound according to any one of claims 1 to 5 or a polymer according to claim 6, and at least one organic functional material, said organic The functional material may be selected from the group consisting of a hole injecting material, a hole transporting material, a p-dopant, an electron 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.
A composition comprising at least one aromatic amine compound according to any one of claims 1 to 5 or a polymer according to claim 6 or a mixture according to claim 7, and At least one organic solvent.
An aromatic amine compound according to any one of claims 1 to 5 or a polymer according to claim 6 or a mixture according to claim 7 or a composition according to claim 8 in an organic electronic device Application in .
An organic electronic device characterized by comprising at least one aromatic amine compound according to any one of claims 1 to 5 or the polymer according to claim 6 or the mixture according to claim 7.
The organic electronic device according to claim 10, wherein the organic electronic device is an organic light emitting diode, an organic photovoltaic cell, an organic light emitting battery, an organic field effect transistor, an organic light emitting field effect transistor, an organic laser, and an organic spin. Electronic devices, organic sensors and organic plasmon emitting diodes.
The organic electronic device according to claim 10 is an electroluminescent device comprising a hole injecting layer or a hole transporting layer, the hole injecting layer or hole transporting layer comprising the method according to claim 1 The aromatic amine compound according to any one of the above claims 5 or the polymer according to claim 6 or the mixture according to claim 7.