CN113248462B - Organic electroluminescent device - Google Patents

Organic electroluminescent device Download PDF

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CN113248462B
CN113248462B CN202110519303.4A CN202110519303A CN113248462B CN 113248462 B CN113248462 B CN 113248462B CN 202110519303 A CN202110519303 A CN 202110519303A CN 113248462 B CN113248462 B CN 113248462B
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CN113248462A (en
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杜明珠
鲁秋
王英雪
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Changchun Hyperions Technology Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/50—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/80—Constructional details
    • H10K50/85—Arrangements for extracting light from the devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
    • H10K85/626—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene containing more than one polycyclic condensed aromatic rings, e.g. bis-anthracene
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/633—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom
    • H—ELECTRICITY
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/631—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine
    • H10K85/636—Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine comprising heteroaromatic hydrocarbons as substituents on the nitrogen atom
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6574—Polycyclic condensed heteroaromatic hydrocarbons comprising only oxygen in the heteroaromatic polycondensed ring system, e.g. cumarine dyes
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6576—Polycyclic condensed heteroaromatic hydrocarbons comprising only sulfur in the heteroaromatic polycondensed ring system, e.g. benzothiophene
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    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
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Abstract

The invention provides an organic electroluminescent device, and relates to the technical field of organic electroluminescence. The organic electroluminescent device comprises an anode, an organic layer, a cathode, a first covering layer and a second covering layer in sequence, wherein the refractive index of the second covering layer is less than 1.7, and the first covering layer contains triarylamine derivatives. The organic electroluminescent device has the advantages that due to the existence of the double covering layers and the synergistic effect between the first covering layer and the second covering layer, the device not only has higher luminous efficiency, but also has longer service life. In addition, the organic electroluminescent device also has weak angle dependence, and after the visual angle is changed from 0 degrees to 60 degrees, the color coordinate of the device is less changed, and the change of the luminous color of the device along with the change of the angle is less.

Description

Organic electroluminescent device
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to an organic electroluminescent device.
Background
An Organic Light Emitting Diode (OLED) is a display device utilizing self-luminescence phenomenon, and compared with the traditional display technology, the OLED has the advantages of active luminescence, large visual angle, high response speed, wide temperature adaptation range, low driving voltage, low power consumption, large brightness, simple production process, lightness and thinness, flexible display and the like, and has huge application prospect in the fields of OLED display and illumination.
Generally, OLEDs have a layered or laminated structure, and organic light emitting devices generally include a substrate, a first electrode, an organic layer, a second electrode, and a first electrode. The light emitting principle of the OLED is as follows: electrons and holes are injected from the cathode and the anode respectively, the injected electrons and holes are transmitted through the organic layer and are recombined in the light-emitting layer to form excitons, and the excitons are radiatively transited back to the ground state, thereby emitting light. The organic layer is mainly used for improving the efficiency and stability of the organic light-emitting device, and generally comprises: a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), an emission layer (EML), an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and the like.
The OLED device may be classified into three types, a bottom light emitting device, a top light emitting device, and a both-side light emitting device, according to a light emitting direction. In recent years, top emission devices have been receiving attention from research and development workers because of their advantages such as being not limited by pixel circuits and having a large light emission area. Although the top emission device does not consider the influence of the pixel circuit on the light emitting area, a large portion of light is lost by light emitted from the light emitting layer of the light emitting element during external conversion, resulting in low light extraction efficiency of the OLED device.
Currently, methods for improving the light extraction efficiency of an OLED basically include the following categories: and forming structures such as folds, photonic crystals, Micro Lens Arrays (MLA) and added surface covering layers on the light emergent surface of the substrate. The first two ways affect the angular distribution of the radiation spectrum of the OLED, and the third way is a more complex fabrication process, so adding a cover layer on the surface of the OLED device is the most effective way at present. However, most of the conventional devices have a single thin film as a cover layer, and thus, the light emitting efficiency is low and the angle dependence is large.
Disclosure of Invention
The invention provides an organic electroluminescent device aiming at the problems in the prior art.
The invention provides an organic electroluminescent device, which sequentially comprises an anode, an organic layer, a cathode, a first covering layer and a second covering layer, wherein the refractive index of the second covering layer is less than 1.7, the first covering layer contains triarylamine derivatives shown in a structural formula 1,
Figure BDA0003063302580000011
x is selected from O or S;
the ring P and the ring Q are independently selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring or a substituted or unsubstituted phenanthrene ring, and the ring P and the ring Q are not simultaneously the substituted or unsubstituted benzene ring;
ar is1、Ar2Independently selected from substituted or unsubstituted aryl of C6-C60 and substituted or unsubstituted heteroaryl of C3-C60, and Ar1、Ar2At least one of the aryl groups is a substituted or unsubstituted condensed ring aryl group of C10-C60;
said L1、L2Independently selected from a single bond, substituted or unsubstituted arylene of C6-C60 and substituted or unsubstituted heteroarylene of C3-C60;
the ring P, ring Q, Ar1、Ar2、L1、L2Contains deuterium.
Has the advantages that: the organic electroluminescent device of the present invention has a double capping layer, in which the triarylamine compound of formula 1 in the first capping layer has a higher refractive index than the metal halide (such as LiF, KBr, MgF) in the second capping layer2、NaF、KF、RbF、CaF2) Is used as a refractive index of (1). The organic electroluminescent device of the present invention has high luminous efficiency and long service life due to the synergy between the specific first and second capping layers of the present invention. In addition, the organic electroluminescent device also has weak angle dependence, and after the visual angle is changed from 0 degrees to 60 degrees, the color coordinate of the device is less changed, and the change of the luminous color of the device along with the change of the angle is less.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be purely exemplary and are not intended to limit the scope of the invention, as various equivalent modifications of the invention will fall within the scope of the claims of this application after reading the present invention.
"C6 to C60" in the "substituted or unsubstituted aryl group having C6 to C60" in the present invention represent the number of carbon atoms in the unsubstituted "aryl group" and do not include the number of carbon atoms in the substituent. "C3 to C60" in the "substituted or unsubstituted heteroaryl group having C3 to C60" represents the number of carbon atoms in the unsubstituted "heteroaryl group" and does not include the number of carbon atoms in the substituent. And so on.
The alkyl group having more than three carbon atoms in the present invention includes isomers thereof, for example, propyl group includes n-propyl group and isopropyl group, butyl group includes n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, and the like.
The total number of aromatic rings in a certain substituent group or certain substituent groups in the invention refers to the sum of the number of single aromatic rings and fused aromatic rings independently existing in the substituent group. For example, the following substituent groups,
Figure BDA0003063302580000021
the total number of aromatic rings in the group is 2, and the following substituent groups,
Figure BDA0003063302580000022
the total number of aromatic rings in (1) is 3, and so on.
The "-" on the substituent groups described herein represents the attachment site.
The alkyl refers to a univalent group formed by subtracting one hydrogen atom from alkane molecules. The alkyl group has a carbon number of from C1 to C30, preferably from C1 to C20, and more preferably from C1 to C10. Examples of the alkyl group include, but are not limited to, the groups described below, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, and the like.
The cycloalkyl refers to a monovalent group formed by omitting one hydrogen atom from a cycloalkane molecule. The cycloalkyl group has carbon atoms of C3 to C30, preferably C3 to C20, and more preferably C3 to C10. Examples of the cycloalkyl group include, but are not limited to, the groups described below, cyclohexyl, adamantyl, bornyl, norbornyl and the like.
The aryl refers to a univalent group formed by subtracting one hydrogen atom from an aromatic nucleus carbon of an aromatic hydrocarbon molecule. The aryl group includes monocyclic aryl group, polycyclic aryl group, and condensed ring aryl group. The monocyclic aryl group refers to a group having only one benzene ring in the structure, the polycyclic aryl group refers to a group having two or more independent benzene rings in the structure, and the fused ring aryl group refers to a group in the structure in which two or more benzene rings are fused together by sharing two adjacent carbon atoms. The aryl group has a carbon number of C6 to C60, preferably C6 to C30, more preferably C6 to C20, and most preferably C6 to C14. Examples of the aryl group include, but are not limited to, the groups described below, phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, anthracyl, triphenylene, pyrenyl, perylenyl, fluorenyl and the like. Phenyl, biphenyl, terphenyl, quaterphenyl, naphthyl, phenanthryl, anthracenyl are preferred.
The heteroaryl group in the present invention refers to a monovalent group in which at least one of the aromatic nuclear carbon atoms in the aryl group is substituted with a heteroatom. Such heteroatoms include, but are not limited to, the atoms depicted below, O, S, N, Si, B, P, and the like. The heteroaryl includes monocyclic heteroaryl and fused ring heteroaryl. The monocyclic heteroaryl refers to a group having only one heteroaromatic ring in the structure, and the fused-ring heteroaryl refers to a group formed by fusing a benzene ring and a monocyclic heterocycle or by fusing two or more monocyclic heterocycles. The heteroaryl group has a carbon number of from C3 to C60, preferably from C3 to C30, more preferably from C3 to C20, and most preferably from C3 to C10. Examples of such heteroaryl groups include, but are not limited to, dibenzofuranyl, dibenzothiophenyl, pyridyl, pyrazinyl, pyridazinyl, pyrimidinyl, triazinyl, quinolinyl, isoquinolinyl, quinoxalinyl, quinazolinyl, and the like, as described below. Dibenzofuranyl, dibenzothienyl, pyridyl, pyrimidyl, triazinyl are preferred.
The arylene group in the invention is a divalent group formed by omitting two hydrogen atoms from an aromatic nucleus carbon in an aromatic hydrocarbon molecule. The arylene group includes monocyclic arylene, polycyclic arylene, fused ring arylene, or combinations thereof. The arylene group has carbon atoms of C6 to C60, preferably C6 to C30, more preferably C6 to C20, and most preferably C6 to C14. Examples of the arylene group include, but are not limited to, the groups described below, phenylene, biphenylene, terphenylene, quaterphenylene, naphthylene, phenanthrylene, anthracenylene, triphenylene, pyrenylene, peryleneene, and the like. Preferred are phenylene, biphenylene, terphenylene, quaterphenylene, naphthylene, phenanthrylene, anthracenylene.
The heteroarylene group means a divalent group in which at least one carbon atom in the arylene group is substituted with a heteroatom. The heteroatoms include, but are not limited to, the atoms shown below, O, S, N, Si, B, P, and the like. The heteroarylene group includes a monocyclic heteroarylene group, a polycyclic heteroarylene group, a fused ring heteroarylene group, or a combination thereof. The polycyclic heteroarylene group may have only one benzene ring substituted with a heteroatom or may have a plurality of benzene rings substituted with a heteroatom. The heteroarylene group has carbon atoms of from C3 to C60, preferably from C3 to C30, more preferably from C3 to C20, and most preferably from C3 to C10. Examples of the heteroarylene group include, but are not limited to, a pyridylene group, a pyrimidylene group, a triazinylene group, a quinolylene group, an isoquinolylene group, a quinoxalylene group, a quinazolinylene group, a dibenzofuranylene group, a dibenzothiophenylene group and the like. Preferred are pyridinylene and pyrimidinylene.
The term "unsubstituted" in "substituted or unsubstituted" as used herein means that a hydrogen atom on the group is not replaced with any substituent.
The term "substituted" in the "substituted or unsubstituted" as used herein means that at least one hydrogen atom on the group is replaced by a substituent. When a plurality of hydrogens is replaced with a plurality of substituents, the plurality of substituents may be the same or different. The position of the hydrogen substituted by the substituent may be any position.
The substituent represented by the "substituted" in the "substituted or unsubstituted" is selected from one of deuterium, cyano, methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclohexyl, adamantyl, bornyl, norbornyl, phenyl, biphenyl, terphenyl, naphthyl, deuterated phenyl, deuterated biphenyl, deuterated terphenyl, deuterated naphthyl, and deuterated naphthyl.
The invention provides an organic electroluminescent device, which sequentially comprises an anode, an organic layer, a cathode, a first covering layer and a second covering layer, wherein the refractive index of the second covering layer is less than 1.7, the first covering layer contains triarylamine derivatives shown in a structural formula 1,
Figure BDA0003063302580000041
x is selected from O or S;
the ring P and the ring Q are independently selected from a substituted or unsubstituted benzene ring, a substituted or unsubstituted naphthalene ring or a substituted or unsubstituted phenanthrene ring, and the ring P and the ring Q are not simultaneously the substituted or unsubstituted benzene ring;
ar is1、Ar2Independently selected from substituted or unsubstituted aryl of C6-C60 and substituted or unsubstituted heteroaryl of C3-C60, and Ar1、Ar2At least one of the aryl groups is a substituted or unsubstituted condensed ring aryl group of C10-C60;
said L1、L2Independently selected from a single bond, substituted or unsubstituted arylene of C6-C60 and substituted or unsubstituted heteroarylene of C3-C60;
the ring P, ring Q, Ar1、Ar2、L1、L2Contains deuterium.
Preferably, the refractive index of the second covering layer is 1.0-1.7.
Preferably, the refractive index of the second covering layer is 1.1-1.65, preferably 1.2-1.65 or 1.3-1.6 or 1.3-1.5.
Preferably, the second coating layer contains one or more of the compounds LiF, KBr, MgF2、NaF、KF、RbF、CaF2. Wherein the refractive index of LiF is 1.39, the refractive index of KBr is 1.56, MgF2Has a refractive index of 1.38, a refractive index of NaF of 1.34, a refractive index of KF of 1.36, a refractive index of RbF of 1.40, CaF2Has a refractive index of 1.43.
Preferably, the second coating layer contains one or more of the compounds LiF, KBr, MgF2。
Preferably, the second coating layer contains one or more of the compounds LiF, KBr as described below.
Preferably, the second capping layer comprises LiF.
Preferably, the first cover layer has a film thickness of 1 to 150nm, preferably 5 to 100nm, more preferably 10 to 80nm, and most preferably 20 to 35 nm.
Preferably, the second cover layer has a film thickness of 1 to 150nm, preferably 5 to 100nm, more preferably 10 to 80nm, and most preferably 20 to 35 nm.
Preferably, the ring P and the ring Q are independently selected from one of the following groups,
Figure BDA0003063302580000051
m1 is selected from 0, 1, 2, 3 or 4; m2 is selected from 0, 1, 2, 3, 4, 5 or 6; m3 is selected from 0, 1, 2, 3, 4 or 5; the m4 is selected from 0, 1, 2 or 3.
Preferably, Ar is1、Ar2Independently selected from one of substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, substituted or unsubstituted naphthyl, substituted or unsubstituted phenanthryl, substituted or unsubstituted anthryl and substituted or unsubstituted triphenylene, and Ar1、Ar2At least one of which is selected from a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted anthryl group, or a substituted or unsubstituted triphenylene group.
Preferably, Ar is1、Ar2、L1、L2The total number of aromatic rings in (a) is 2, 3, 4, 5, 6, 7, 8, 9 or 10.
Preferably, Ar is1、L1The total number of aromatic rings in the group is 1, 2, 3, 4 or 5; ar is2、L2The total number of aromatic rings in (a) is 1, 2, 3, 4 or 5.
Preferably, Ar is1、Ar2At least one of which is selected from substituted or unsubstituted naphthyl.
Preferably, theAr1、Ar2Independently selected from one of the groups shown in formula I and formula II, and Ar1、Ar2At least one of which is selected from the group represented by formula II,
Figure BDA0003063302580000052
the R is1The same or different one selected from the group consisting of hydrogen, deuterium, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted bornyl, substituted or unsubstituted norbornanyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, and substituted or unsubstituted naphthyl;
n1 is selected from 0, 1, 2, 3, 4 or 5; the n2 is selected from 0, 1, 2, 3, 4, 5, 6 or 7.
Preferably, Ar is1、Ar2Independently selected from one of the groups shown in formulas I-1 to I-9 or formulas II-1 to II-6, and Ar1、Ar2At least one of them is selected from the group represented by the formulae II-1 to II-6,
Figure BDA0003063302580000053
Figure BDA0003063302580000061
n1 is selected from 0, 1, 2, 3 or 4; n2 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; n3 is selected from 0, 1, 2, 3, 4, 5 or 6; n4 is selected from 0, 1, 2, 3, 4 or 5; the n5 is selected from 0, 1, 2 or 3.
Preferably, Ar is1、Ar2Independently selected from one of the groups shown in the following,
Figure BDA0003063302580000062
preferably, said L1、L2Independently selected from a single bond or one of the groups shown below,
Figure BDA0003063302580000063
the R is2The same or different one selected from the group consisting of hydrogen, deuterium, cyano, substituted or unsubstituted methyl, substituted or unsubstituted ethyl, substituted or unsubstituted propyl, substituted or unsubstituted butyl, substituted or unsubstituted pentyl, substituted or unsubstituted cyclohexyl, substituted or unsubstituted adamantyl, substituted or unsubstituted bornyl, substituted or unsubstituted norbornanyl, substituted or unsubstituted phenyl, substituted or unsubstituted biphenyl, substituted or unsubstituted terphenyl, and substituted or unsubstituted naphthyl;
r1 is selected from 0, 1, 2, 3 or 4; r2 is selected from 0, 1, 2, 3, 4, 5 or 6.
Preferably, said L1、L2Independently selected from a single bond or one of the groups shown below,
Figure BDA0003063302580000071
r1 is selected from 0, 1, 2, 3 or 4; r2 is selected from 0, 1, 2, 3, 4, 5 or 6; r3 is selected from 0, 1, 2, 3, 4 or 5; r4 is selected from 0, 1, 2 or 3.
Preferably, said L1、L2Independently selected from a single bond or one of the groups shown below,
Figure BDA0003063302580000072
it is preferable thatAr is said1、Ar2、L1、L2The total number of the benzene rings and the naphthalene rings in the ring system is 2, 3, 4, 5, 6, 7, 8, 9 or 10.
Preferably, Ar is1、L1The total number of the benzene rings and the naphthalene rings is 1, 2, 3, 4 or 5; ar is2、L2The total number of the benzene rings and the naphthalene rings in the compound is 1, 2, 3, 4 or 5.
Preferably, the triarylamine derivative is selected from one of the structures shown below,
Figure BDA0003063302580000073
Figure BDA0003063302580000081
Figure BDA0003063302580000091
Figure BDA0003063302580000101
Figure BDA0003063302580000111
Figure BDA0003063302580000121
Figure BDA0003063302580000131
Figure BDA0003063302580000141
Figure BDA0003063302580000151
Figure BDA0003063302580000161
some specific chemical structures of the triarylamine derivative shown in formula 1 of the present invention are listed above, but the present invention is not limited to these listed chemical structures, and all the groups with substituents as defined above are included based on the structure shown in formula 1.
For the triarylamine derivative of formula 1, see, for example, applicant's prior application CN202110164825.7, which is hereby incorporated by reference in its entirety.
The device structure of the organic electroluminescent device of the present invention is preferably as follows:
anode/hole transport layer/light emitting layer/electron transport layer/cathode/first cladding layer/second cladding layer;
anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode/first cladding layer/second cladding layer;
anode/hole transport layer/luminescent layer/electron transport layer/electron injection layer/cathode/first cover layer/second cover layer;
anode/hole transport layer/light-emitting auxiliary layer/light-emitting layer/electron transport layer/cathode/first cover layer/second cover layer;
anode/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/cathode/first cladding layer/second cladding layer;
anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode/first cover layer/second cover layer;
an anode/a hole injection layer/a hole transport layer/a light emitting layer/a hole blocking layer/an electron transport layer/a cathode/a first clad layer/a second clad layer;
anode/hole injection layer/hole transport layer/light-emitting auxiliary layer/light-emitting layer/electron transport layer/cathode/first cover layer/second cover layer;
anode/hole transport layer/light-emitting auxiliary layer/light-emitting layer/hole blocking layer/electron transport layer/cathode/first cover layer/second cover layer;
an anode/a hole transport layer/a light emitting layer/a hole blocking layer/an electron transport layer/an electron injection layer/a cathode/a first clad layer/a second clad layer;
an anode/a hole injection layer/a hole transport layer/a light emitting layer/a hole blocking layer/an electron transport layer/an electron injection layer/a cathode/a first cover layer/a second cover layer;
anode/hole transport layer/light-emitting auxiliary layer/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/first cover layer/second cover layer;
anode/hole injection layer/hole transport layer/light-emitting auxiliary layer/light-emitting layer/hole blocking layer/electron transport layer/cathode/first cover layer/second cover layer;
anode/hole injection layer/hole transport layer/light-emitting auxiliary layer/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/first cladding layer/second cladding layer.
The first covering layer of the device of the present invention may be a single-layer film or a multi-layer film, and each layer of the film may contain one material or a plurality of materials. The second cover layer may be a single-layer film or a multi-layer film, and each layer of film may contain one material or a plurality of materials. The organic layer of the organic electroluminescent device of the present invention may be a single functional layer or a plurality of functional layers, each functional layer may be formed of a single-layer film or a multilayer film, and each layer of the film may contain one material or a plurality of materials. The organic layer of the organic electroluminescent device of the present invention may include one or more of a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, a functional layer having hole injection and/or transport properties, and a functional layer having electron injection and/or transport properties.
The material of each layer of the thin film in the organic electroluminescent device of the present invention is not particularly limited, and those known in the art can be used. The organic functional layers of the above-mentioned organic electroluminescent device and the electrodes on both sides of the device are described below:
as the anode material of the present invention, a material having a high work function and capable of promoting hole injection into the organic layer is preferably used. The thickness of the anode is generally 50nm to 250 nm. Specific examples of the anode material usable in the present invention may include: metals such as aluminum (Al), copper (Cu), gold (Au), etc., or alloys thereof; metal oxides such as Indium Tin Oxide (ITO), Aluminum Zinc Oxide (AZO), Indium Zinc Oxide (IZO), and the like; indium tin oxide/silver/indium tin oxide (ITO/Ag/ITO), silver/indium tin oxide/silver (Ag/ITO/Ag), aluminum/silver (Al/Ag), and the like. But is not limited thereto.
As the cathode material of the present invention, a material having a low work function and capable of promoting electron injection into the organic layer is preferably used. The thickness of the cathode film is generally 1nm to 100 nm. Specific examples of the cathode material that can be used in the present invention may include: metals such as silver (Ag), aluminum (Al), magnesium (Mg), calcium (Ca), and the like; alloys such as lithium calcium magnesium alloy (Li: Ca: Mg), magnesium silver alloy (Mg: Al), lithium aluminum alloy (Li: Al), etc.; laminate materials such as ytterbium/silver (Yb/Ag), calcium/magnesium (Ca/Mg), etc., but are not limited thereto.
The hole injection layer of the present invention has the effect of reducing the hole injection barrier between the anode and the organic layer, and allowing holes to be efficiently injected into the organic layer. The thickness of the hole injection layer is generally 1nm to 150 nm. Specific examples of the hole injection material that can be used in the present invention may include metal oxides, phthalocyanine-based compounds, arylamine-based compounds, and the like, such as vanadium pentoxide (V)2O5) Molybdenum trioxide (MoO)3) Copper phthalocyanine (CuPc), 4',4 ″ -tris (N-3-methylphenyl-N-phenylamino) triphenylamine (m-MTDATA), and the like, but is not limited thereto.
The hole transport layer of the present invention has the effects of lowering the energy level barrier between the functional layers and injecting holes and balancing carriers. The thickness of the hole transport layer is generally 5nm to 200 nm. Specific examples of the hole transport material that can be used in the present invention may include: aromatic amine derivatives, fluorene derivatives, and carbazole derivatives, such as N, N ' -diphenyl-N, N ' - (1-naphthyl) -1,1' -biphenyl-4, 4' -diamine (NPB), 4',4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), 2,7, 7-tetrakis (diphenylamino) -9, 9-spirobifluorene (Spiro-TAD), and the like, but are not limited thereto.
The light-emitting layer of the present invention may be a blue light-emitting layer, a green light-emitting layer, a red light-emitting layer, a white light-emitting layer, or a light-emitting layer of another color. The thickness of the light-emitting layer is generally 5nm to 150 nm. Specific examples of the light emitting material may include styrylamine derivatives, metal complexes, pyrene derivatives, fluorene derivatives, coumarin dyes, DCM derivatives, and the like, such as 4,4' - [1, 4-phenylenebis- (1E) -2, 1-vinyldiyl]Bis [ N, N-diphenylaniline](DSA-Ph), bis (4, 6-difluorophenylpyridine-C2, N) picolinoylium (FIrpic), tris (2-phenylpyridine) iridium (Ir (ppy)3) N1, N6-bis ([ [1,1' -biphenyl ]]-4-yl]-N1, N6-bis (dibenzo [ b, d ]]Furan-4-yl) pyrene-1, 6-diamine, 9- (9-phenylcarbazol-3-yl) -10-naphthalen-1-yl) anthracene (PCAN), 9- [4- (2- (7- (N, N-diphenylamino) -9, 9-diethylfluoren-2-yl) vinyl) phenyl]-9-phenyl-fluorene (DPAFVF), coumarin 545T, 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM), and the like. But is not limited thereto.
The light-emitting layer of the present invention may contain only the light-emitting material described above, or may be doped as a guest material into a host material. Specific examples of the host material may include anthracene derivatives, metal complexes, fluorene derivatives, carbazole derivatives, and the like, such as 2- (tert-butyl) -9, 10-di (2-naphthyl) anthracene (TBADN), 8-hydroxyquinoline zinc (Znq)2)2, 7-bis [9, 9-bis (4-methylphenyl) -fluoren-2-yl]9, 9-bis (4-methylphenyl) fluorene (TDAF), 1,3, 5-tris (9-carbazolyl) benzene (TCP), and the like. But is not limited thereto.
The hole-blocking layer of the present invention has a function of blocking holes in the light-emitting layer. The thickness of the hole-blocking layer is generally 1nm to 80 nm. Specific examples of the electron transport material that can be used in the present invention may include imidazole derivatives, phenanthroline derivatives, and the like, for example, 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), and the like. But is not limited thereto.
The electron transport layer of the present invention has the effects of lowering energy level barriers between the functional layers and injecting electrons and balancing carriers. The thickness of the electron transporting layer is generally 5nm to 200 nm. Specific examples of the electron transport material usable in the present invention may include metal complexes, imidazole derivatives, phenanthroline derivatives, quinolines, triazines, pyridine derivatives and the like, for example, tris (8-hydroxyquinoline) aluminum (III) (Alq)3) Bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BAlq), 1,3, 5-tris (1-phenyl-1H-benzimidazol-2-yl) benzene (TPBi), 4, 7-diphenyl-1, 10-phenanthroline (Bphen), 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), 2,4, 6-tris (3- (3-pyridyl) - (1,1' -biphenyl) -3-yl) -1,3, 5-triazine (tmppytz), 3' - [5' - [3- (3-pyridyl) phenyl ] methyl (TPBi), and a pharmaceutically acceptable salt thereof](TmPyPB) and the like. But is not limited thereto.
The electron injection layer of the present invention has the effect of reducing the electron injection barrier between the cathode and the organic layer, and allowing electrons to be efficiently injected into the organic layer. The thickness of the electron injection layer is generally 0.1nm to 50 nm. Examples of the electron injecting material usable in the present invention include alkali metals, alkaline earth metals, compounds containing alkali metals and alkaline earth metals, and the like, for example, lithium (Li), sodium (Na), 8-hydroxyquinoline Lithium (LiQ), rubidium fluoride (RbF), lithium oxide (LiO), lithium boron oxide (LiBO)2) Silicon potassium oxide (K)2SiO3) Cesium carbonate (Cs)2CO3) And the like. But is not limited thereto.
The coating layer of the present invention may be located on both the outside of the anode and the outside of the cathode, or may be located on the outside of the anode or the outside of the cathode. The coating layer of the present invention is preferably located outside the cathode, and the coating layer of the present invention preferably has at least two different coating layer films, and when the coating layer has two coating layers, the first coating layer contains the triarylamine derivative represented by formula 1 of the present invention, and the second coating layer contains the compound having a refractive index of 1.7 or less in this order from the cathode. The thickness of the covering layer is 10nm to 160nm, preferably 20nm to 150nm, and more preferably 30nm to 70 nm; the first cover layer has a film thickness of 1nm to 150nm, and the second cover layer has a film thickness of 1nm to 150 nm.
The method for preparing each layer of the thin film in the organic electroluminescent device of the present invention is not particularly limited, and vacuum evaporation, sputtering, spin coating, spray coating, screen printing, laser transfer printing, and the like can be used, but is not limited thereto.
The organic electroluminescent device is mainly applied to the technical field of information display, and is widely applied to various information displays in the aspect of information display, such as tablet computers, flat televisions, mobile phones, smart watches, digital cameras, VR, vehicle-mounted systems, wearable equipment and the like.
Synthetic examples
The method for preparing the triarylamine derivative of formula 1 of the present invention is not particularly limited, and conventional methods well known to those skilled in the art may be used. For example, carbon-carbon coupling reaction, carbon-nitrogen coupling reaction, etc., the triarylamine derivative of formula 1 of the present invention can be prepared by the following synthetic route.
Figure BDA0003063302580000201
The Xn is selected from halogens such as Cl, Br, I.
Raw materials and reagents: the starting materials and reagents used in the following synthetic examples are not particularly limited, and may be commercially available products or prepared by methods known to those skilled in the art. The raw materials and reagents used in the invention are all pure reagents.
The instrument comprises the following steps: G2-Si quadrupole tandem time-of-flight high resolution mass spectrometer (waters, uk); a Vario EL cube type organic element analyzer (Elementar corporation, germany); model Bruker-510 nuclear magnetic resonance spectrometer (Bruker, germany).
Synthesis example 1 Synthesis of Compound 11
Figure BDA0003063302580000202
Preparation of intermediate c-1:
16.3g (74.46mmol) of a-1, 15.2g (70.92mmol) of b-1, 8.17g (85.10mmol) of sodium tert-butoxide (t-BuONa), 0.641g (0.70mmol) of dibenzylideneacetone dipalladium (Pd) were added to the reaction flask in this order2(dba)3) 0.203g (0.70mmol) of tri-tert-butylphosphine tetrafluoroborate (P (t-Bu)3HBF4) Reacting for 4 hours under the condition of heating at 90 ℃ under the protection of argon and 300mL of toluene, after the reaction is finished, pouring the reaction solution into 700mL of water, adding 600mL of dichloromethane, layering, extracting a water layer for 2 times by using 250mL of dichloromethane, combining organic phases, recovering a solvent under reduced pressure, and purifying by column chromatography to obtain an intermediate c-1(21.3g, yield 85%); the HPLC purity is more than or equal to 99.54 percent.
Preparation of compound 11:
20.0g (56.73mmol) of c-1, 16.1g (54.03mmol) of d-1, 6.23g (64.83mmol) of sodium tert-butoxide (t-BuONa), 0.494g (0.54mmol) of tris-dibenzylideneacetone dipalladium (Pd) were added to the reaction flask in this order2(dba)3) 0.257g (0.54mmol) of 2-dicyclohexyl phosphorus-2, 4, 6-triisopropyl biphenyl (XPhos) and 260mL of toluene are reacted under the condition of heating at 115 ℃ for 3.5 hours under the protection of argon, after the reaction is finished, the reaction solution is poured into 600mL of water, 500mL of dichloromethane is added, layers are separated, a water layer is extracted for 2 times by 250mL of dichloromethane, organic phases are combined, the solvent is recovered under reduced pressure, and the toluene is recrystallized to obtain a compound 11(25.79g, the yield is 84%); the HPLC purity is more than or equal to 99.59 percent.
Mass spectrum m/z: 568.2512 (theoretical value: 568.2532). Theoretical element content (%) C42H20D7NO: c, 88.70; h, 6.02; and N, 2.46. Measured elemental content (%): c, 88.59; h, 6.17; and N, 2.40. The above results confirmed that the obtained product was the objective product.
Synthesis example 2 Synthesis of Compound 29
Figure BDA0003063302580000211
Preparation of intermediate b-2:
13.2g (63.53mmol) of e-2 and 16.2g (69.8 mmol) were added to the reaction flask in this order8mmol) f-2, 1.46g (1.27mmol) Tetratriphenylphosphine palladium (Pd [ PPh ]3]4) 9.35g (95.29mmol) of potassium acetate (KOAc) and 100mL of toluene, 50mL of ethanol, 50mL of water under argon protection, stirring the mixture, and heating and refluxing the mixed solution of the above reactants at 85 ℃ for 5 hours; after the reaction, the mixture was extracted with toluene, the organic phase was washed with saturated brine, and after the organic phase was dried, it was purified by column chromatography to obtain intermediate b-2(16.6g, yield 83%); the HPLC purity is more than or equal to 99.64 percent.
Preparation of intermediate c-2:
to a reaction flask were added 7.52g (50.03mmol) of a-2, 14.8g (47.0mmol) of b-2, 5.49g (57.18mmol) of sodium tert-butoxide (t-BuONa), 0.430g (0.47mmol) of dibenzylideneacetone dipalladium (Pd) in that order2(dba)3) 0.136g (0.47mmol) of tri-tert-butylphosphine tetrafluoroborate (P (t-Bu)3HBF4) 200mL of toluene and argon protection, reacting for 4 hours under the condition of heating at 90 ℃, after the reaction is finished, pouring the reaction solution into 550mL of water, adding 500mL of dichloromethane, layering, extracting a water layer with 250mL of dichloromethane for 2 times, combining organic phases, recovering a solvent under reduced pressure, and purifying by column chromatography to obtain an intermediate c-2(16.9g, yield 84%); the HPLC purity is more than or equal to 99.46 percent.
Preparation of compound 29:
16.0g (37.32mmol) of c-2, 10.6g (35.55mmol) of d-1, 4.10g (42.66mmol) of sodium tert-butoxide (t-BuONa), 0.330g (0.36mmol) of palladium (Pd) tris-dibenzylideneacetone were added to the reaction flask in this order2(dba)3) 0.172g (0.36mmol) of 2-dicyclohexyl phosphorus-2, 4, 6-triisopropyl biphenyl (XPhos) and 150mL of toluene under the protection of argon, the reaction is carried out for 3.5 hours under the condition of heating at 115 ℃, after the reaction is finished, the reaction solution is poured into 400mL of water, 400mL of dichloromethane is added, the layers are separated, a water layer is extracted for 2 times by 250mL of dichloromethane, organic phases are combined, the solvent is recovered under reduced pressure, and the toluene is recrystallized to obtain a compound 29(19.46g, the yield is 85%); the HPLC purity is more than or equal to 99.62 percent.
Mass spectrum m/z: 644.2860 (theoretical value: 644.2845). Theoretical element content (%) C48H24 D7NO: c, 89.41; h, 5.94; and N, 2.17. Measured elemental content (%): c, 89.48; h, 5.81; and N, 2.23. As described aboveAs a result, it was confirmed that the obtained product was the objective product.
Synthesis example 3 Synthesis of Compound 37
Figure BDA0003063302580000221
Preparation of compound 37:
compound 37(28.54g) was obtained in the same manner as in Synthesis example 1 except for replacing a-1 and b-1 in Synthesis example 1 with equimolar a-3 and b-3; the HPLC purity is more than or equal to 99.61 percent.
Mass spectrum m/z: 644.2823 (theoretical value: 644.2845). Theoretical element content (%) C48H24 D7NO: c, 89.41; h, 5.94; and N, 2.17. Measured elemental content (%): c, 89.48; h, 5.76; and N, 2.23.
Synthesis example 4 Synthesis of Compound 48
Figure BDA0003063302580000222
Preparation of compound 48:
compound 48(27.84g) was obtained by the same preparation method as in Synthesis example 1 except for replacing b-1 in Synthesis example 1 with equimolar b-4; the HPLC purity is more than or equal to 99.68 percent.
Mass spectrum m/z: 644.2818 (theoretical value: 644.2845). Theoretical element content (%) C48H24D7NO: c, 89.41; h, 5.94; and N, 2.17. Measured elemental content (%): c, 89.36; h, 5.90; and N, 2.29.
Synthesis example 5 Synthesis of Compound 81
Figure BDA0003063302580000223
Preparation of compound 81:
compound 81(19.17g) was obtained in the same manner as in Synthesis example 2 except that e-2, f-2, a-2 and b-2 in Synthesis example 2 were replaced with equimolar amounts of e-5, f-5, a-5 and b-5; the HPLC purity is more than or equal to 99.55 percent.
Mass spectrum m/z: 642.2703 (theoretical value: 642.2719). Theoretical element content (%) C48H26D5NO: c, 89.69; h, 5.64; and N, 2.18. Measured elemental content (%): c, 89.56; h, 5.69; and N, 2.27.
Synthesis example 6 Synthesis of Compound 85
Figure BDA0003063302580000231
Preparation of compound 85:
compound 85(28.10g) was obtained in the same manner as in Synthesis example 1 except for replacing a-1 and b-1 in Synthesis example 1 with equimolar a-6 and b-6; the HPLC purity is more than or equal to 99.52 percent.
Mass spectrum m/z: 642.2732 (theoretical value: 642.2719). Theoretical element content (%) C48H26D5NO: c, 89.69; h, 5.64; and N, 2.18. Measured elemental content (%): c, 89.63; h, 5.69; and N, 2.13.
Synthesis example 7 Synthesis of Compound 89
Figure BDA0003063302580000232
Preparation of compound 89:
compound 89(28.80g) was obtained in the same manner as in Synthesis example 2 except that f-2, a-2 and b-2 in Synthesis example 2 were replaced with equimolar amounts of f-7, a-7 and b-7; the HPLC purity is more than or equal to 99.45 percent.
Mass spectrum m/z: 642.2736 (theoretical value: 642.2719). Theoretical element content (%) C48H26D5NO: c, 89.69; h, 5.64; and N, 2.18. Measured elemental content (%): c, 89.73; h, 5.51; and N, 2.26.
Synthesis example 8 Synthesis of Compound 92
Figure BDA0003063302580000233
Preparation of compound 92:
compound 92(22.60g) was obtained by the same preparation method as in Synthesis example 1 except for replacing a-1 and d-1 in Synthesis example 1 with equimolar a-5 and d-8; the HPLC purity is more than or equal to 99.61 percent.
Mass spectrum m/z: 492.2236 (theoretical value: 492.2219). Theoretical element content (%) C36H16D7NO: c, 87.77; h, 6.14; n, 2.84. Measured elemental content (%): c, 87.86; h, 6.19; n, 2.67.
Synthesis example 9 Synthesis of Compound 100
Figure BDA0003063302580000241
Preparation of compound 100:
compound 100(24.25g) was obtained in the same manner as in Synthesis example 1 except for replacing a-1, b-1 and d-1 in Synthesis example 1 with equimolar a-3, b-9 and d-8; the HPLC purity is more than or equal to 99.60 percent.
Mass spectrum m/z: 568.2547 (theoretical value: 568.2532). Theoretical element content (%) C42H20D7NO: c, 88.70; h, 6.02; and N, 2.46. Measured elemental content (%): c, 88.56; h, 6.11; n, 2.53.
Synthesis example 10 Synthesis of Compound 123
Figure BDA0003063302580000242
Preparation of compound 123:
compound 123(27.15g) was obtained in the same manner as in Synthesis example 1 except for replacing a-1, b-1 and d-1 in Synthesis example 1 with equimolar a-2, b-10 and d-10; the HPLC purity is more than or equal to 99.53 percent.
Mass spectrum m/z: 644.2826 (theoretical value: 644.2845). Theoretical element content (%) C48H24D7NO: c, 89.41; h, 5.94; and N, 2.17. Measured in factElement content (%): c, 89.47; h, 5.80; n, 2.21.
Synthesis example 11 Synthesis of Compound 134
Figure BDA0003063302580000243
Preparation of compound 134:
compound 134(25.34g) was obtained in the same manner as in Synthesis example 1 except that a-1, b-1 and d-1 in Synthesis example 1 were replaced with equimolar amounts of a-11, b-11 and d-11; HPLC purity is more than or equal to 99.67%.
Mass spectrum m/z: 565.2332 (theoretical value: 565.2344). Theoretical element content (%) C42H23D4NO: c, 89.17; h, 5.52; and N, 2.48. Measured elemental content (%): c, 89.13; h, 5.41; and N, 2.56.
Synthesis example 12 Synthesis of Compound 138
Figure BDA0003063302580000251
Preparation of compound 138:
compound 138(18.52g) was obtained in the same manner as in Synthesis example 2 except that e-1, f-1, b-1 and d-1 in Synthesis example 2 were replaced with equimolar amounts of e-12, f-12, b-12 and d-11; the HPLC purity is more than or equal to 99.58 percent.
Mass spectrum m/z: 651.3296 (theoretical value: 651.3284). Theoretical element content (%) C48H17D14NO: c, 88.44; h, 6.95; and N, 2.15. Measured elemental content (%): c, 88.48; h, 6.79; and N, 2.27.
Synthesis example 13 Synthesis of Compound 170
Figure BDA0003063302580000252
Preparation of compound 170:
compound 170(24.16g) was obtained in the same manner as in Synthesis example 1 except for replacing a-1, b-1 and d-1 in Synthesis example 1 with equimolar a-11, b-13 and d-13; the HPLC purity is more than or equal to 99.51 percent.
Mass spectrum m/z: 566.2423 (theoretical value: 566.2406). Theoretical element content (%) C42H22D5NO: c, 89.02; h, 5.69; and N, 2.47. Measured elemental content (%): c, 89.23; h, 5.52; n, 2.51.
Synthesis example 14 Synthesis of Compound 174
Figure BDA0003063302580000253
Preparation of compound 174:
compound 174(24.86g) was obtained in the same manner as in Synthesis example 1 except for using a-1, b-1 and d-1 in Synthesis example 1 in place of equimolar amounts of a-3, b-14 and d-14; the HPLC purity is more than or equal to 99.66 percent.
Mass spectrum m/z: 568.2518 (theoretical value: 568.2532). Theoretical element content (%) C42H20D7NO: c, 88.70; h, 6.02; and N, 2.46. Measured elemental content (%): c, 88.61; h, 6.09; and N, 2.54.
Synthesis example 15 Synthesis of Compound 183
Figure BDA0003063302580000261
Preparation of compound 183:
compound 183(18.95g) was obtained in the same manner as in Synthesis example 1 except that e-1, f-1, a-1, b-1 and d-1 in Synthesis example 2 were replaced with equimolar amounts of e-15, f-15, a-15, b-15 and d-16; the HPLC purity is more than or equal to 99.47 percent.
Mass spectrum m/z: 642.2702 (theoretical value: 642.2719). Theoretical element content (%) C48H26D5NO: c, 89.69; h, 5.64; and N, 2.18. Measured elemental content (%): c, 89.73; h, 5.69; and N, 2.04.
Synthesis example 16 Synthesis of Compound 184
Figure BDA0003063302580000262
Preparation of compound 184:
compound 184(27.27g) was obtained in the same manner as in Synthesis example 1 except for replacing a-1, b-1 and d-1 in Synthesis example 1 with equimolar amounts of a-7, b-6 and d-16; the HPLC purity is more than or equal to 99.39 percent.
Mass spectrum m/z: 647.3047 (theoretical value: 647.3033). Theoretical element content (%) C48H21D10NO: c, 88.99; h, 6.38; and N, 2.16. Measured elemental content (%): c, 88.73; h, 6.34; and N, 2.41.
Synthesis example 17 Synthesis of Compound 212
Figure BDA0003063302580000263
Preparation of compound 212:
compound 212(28.37g) was obtained in the same manner as in Synthesis example 1 except that b-1 and d-1 in Synthesis example 1 were replaced with equimolar amounts of b-17 and d-17; the HPLC purity is more than or equal to 99.43 percent.
Mass spectrum m/z: 648.3087 (theoretical value: 648.3096). Theoretical element content (%) C48H20D11NO: c, 88.85; h, 6.52; and N, 2.16. Measured elemental content (%): c, 88.77; h, 6.31; and N, 2.12.
Synthesis example 18 Synthesis of Compound 293
Figure BDA0003063302580000271
Preparation of compound 293:
compound 293(22.87g) was obtained in the same manner as in Synthesis example 1 except for replacing a-1 and b-1 in Synthesis example 1 with equimolar a-18 and b-7; the HPLC purity is more than or equal to 99.53 percent.
Mass spectrum m/z: 516.2238 (theoretical value: 516.2250). Theory of thingsArgument content (%) C38H20D5NO: c, 88.34; h, 5.85; n, 2.71. Measured elemental content (%): c, 88.43; h, 5.70; and N, 2.76.
Synthesis example 19 Synthesis of Compound 344
Figure BDA0003063302580000272
Preparation of compound 344:
compound 344(29.60g) was obtained in the same manner as in Synthesis example 1 except that c-1 and d-1 in Synthesis example 1 were replaced with equimolar amounts of c-3 and d-19; the HPLC purity is more than or equal to 99.46 percent.
Mass spectrum m/z: 660.2602 (theoretical value: 660.2617). Theoretical element content (%) C48H24D7NS: c, 87.24; h, 5.79; and N, 2.12. Measured elemental content (%): c, 87.32; h, 5.61; and N, 2.16.
Synthesis example 20 Synthesis of Compound 365
Figure BDA0003063302580000273
Preparation of compound 365:
compound 365(27.82g) was obtained in the same manner as in Synthesis example 1 except that c-1 and d-1 in Synthesis example 1 were replaced with equimolar amounts of c-4 and d-20; the HPLC purity is more than or equal to 99.57 percent.
Mass spectrum m/z: 660.2636 (theoretical value: 660.2617). Theoretical element content (%) C48H24D7And NS: c, 87.24; h, 5.79; and N, 2.12. Measured elemental content (%): c, 87.30; h, 5.66; and N, 2.18.
Other compounds of the invention, such as compounds 1, 24, 50, 66, 110, 156, and the like, are synthesized similarly.
Measurement of refractive index
The refractive index of the triarylamine derivative shown in the structural formula 1 of the invention is measured by adopting the following instrument: the measuring instrument is an M-2000 spectroscopic ellipsometer of J.A.Woollam, USA; the scanning range of the instrument is 245-1000 nm; the size of the glass substrate is 200 multiplied by 200mm, and the thickness of the material film is 20-60 nm. The measured refractive index (n) at 450nm is shown in Table 1.
Refractive index (n) of the Compounds of Table 1
Compound of refractive index Compound of refractive index Compound of refractive index Compound of refractive index Compound of refractive index
Compound 11, 2.330 Compound 29, 2.347 Compound 37, 2.358 Compound 48, 2.351 Compound 81, 2.338
Compound 85, 2.333 Compound 89, 2.355 Compound 92, 2.325 Compound 100, 2.328 Compound 123, 2.342
Compound 134, 2.318 Compound 138, 2.344 Compound 170, 2.323 Compounds 174, 2.316 Compound 183, 2.335
Compound 184, 2.326 Compound 212, 2.321 Compound 293, 2.201 Compound 344, 2.314 Compound 365, 2.312
Device embodiments
In the invention, the ITO glass substrate is ultrasonically cleaned for 2 times and 20 minutes each time by 5% glass cleaning liquid, and then ultrasonically cleaned for 2 times and 10 minutes each time by deionized water. Ultrasonic cleaning with acetone and isopropanol for 20 min, and oven drying at 120 deg.C. The organic materials are sublimated, and the purity of the organic materials is over 99.99 percent.
The driving voltage, the luminous efficiency and the CIE color coordinate of the organic electroluminescent device are tested by combining test software, a computer, a K2400 digital source meter manufactured by Keithley of the United states and a PR788 spectral scanning luminance meter manufactured by Photo Research of the United states into a combined IVL test system. The lifetime was measured using the M6000 OLED lifetime test system from McScience. The environment of the test is atmospheric environment, and the temperature is room temperature.
The device is prepared by adopting a vacuum evaporation system and continuously evaporating under a vacuum uninterrupted condition. The materials are respectively arranged in different evaporation source quartz crucibles, and the temperatures of the evaporation sources can be independently controlled. The thermal evaporation rate of the organic material or the doped parent organic material is generally set at 0.1nm/s, and the evaporation rate of the doped material is adjusted according to the doping ratio; the evaporation rate of the electrode metal is 0.4-0.6 nm/s. Placing the processed glass substrate into an OLED vacuum coating machine, wherein the vacuum degree of the system should be maintained at 5 x 10 in the film manufacturing process-5And (3) evaporating an organic layer and a metal electrode respectively by replacing a mask plate under Pa, detecting the evaporation speed by using an SQM160 quartz crystal film thickness detector of Inficon, and detecting the film thickness by using a quartz crystal oscillator.
Example 1: preparation of organic electroluminescent device 1
ITO/Ag/ITO is used as an anode on the glass substrate; performing vacuum evaporation on the anode to form m-MTDATA as a hole injection layer, wherein the evaporation thickness is 35 nm; carrying out vacuum evaporation on the NPB on the hole injection layer to form a hole transport layer, wherein the evaporation thickness is 40 nm; evaporating TBADN-DSA-Ph-1 ═ 97:3 on the hole transport layer in vacuum to form a light-emitting layer, wherein the evaporation thickness is 30 nm; vacuum evaporating TPBi on the luminous layer to be used as a hole blocking layer, wherein the evaporation thickness is 15 nm; evaporating Bphen on the hole blocking layer in vacuum to be used as an electron transport layer, wherein the evaporation thickness is 40 nm; vacuum evaporation plating LiQ on the electron transport layer to be used as an electron injection layer, wherein the evaporation plating thickness is 0.5 nm; vacuum evaporating Mg, Ag (9:1) as a cathode on the electron injection layer, wherein the evaporation thickness is 15 nm; vacuum evaporating the compound 1 of the invention on a cathode to be used as a first covering layer, wherein the evaporation thickness is 35 nm; and evaporating LiF on the first covering layer in vacuum to form the first covering layer, wherein the evaporation thickness is 35 nm.
The device structure of the organic electroluminescent device 1 is as follows:
ITO/Ag/ITO/m-MTDATA (35nm)/NPB (40nm)/TBADN-DSA-Ph-1 ═ 97:3(30nm)/TPBi (15nm)/Bphen (40nm)/LiQ (0.5nm)/Mg: Ag (9:1) (15 nm)/Compound 1(35nm)/LiF (35 nm).
Examples 2 to 26: preparation of organic electroluminescent devices 2-26
Compound 1 in the first capping layer in synthesis example 1 was replaced with compound 11, compound 24, compound 29, compound 37, compound 48, compound 50, compound 66, compound 81, compound 85, compound 89, compound 92, compound 100, compound 110, compound 123, compound 134, compound 138, compound 156, compound 170, compound 174, compound 183, compound 184, compound 212, compound 293, compound 344, compound 365, respectively; LiF in the second covering layer is respectively changed into LiF, KBr, LiF and MgF2、LiF、LiF、KBr、LiF、MgF2、KBr、KBr、LiF、NaF、LiF、LiF、MgF2、NaF、LiF、KBr、MgF2、CaF2And KF and RbF, and obtaining the organic electroluminescent devices 2-26 by the same steps.
Comparative example 1: preparation of comparative organic electroluminescent device 1
ITO/Ag/ITO is used as an anode on the glass substrate; performing vacuum evaporation on the anode to form m-MTDATA as a hole injection layer, wherein the evaporation thickness is 35 nm; carrying out vacuum evaporation on the NPB on the hole injection layer to form a hole transport layer, wherein the evaporation thickness is 40 nm; evaporating TBADN-DSA-Ph-1 ═ 97:3 on the hole transport layer in vacuum to form a light-emitting layer, wherein the evaporation thickness is 30 nm; vacuum evaporating TPBi on the luminous layer to be used as a hole blocking layer, wherein the evaporation thickness is 15 nm; evaporating Bphen on the hole blocking layer in vacuum to be used as an electron transport layer, wherein the evaporation thickness is 40 nm; vacuum evaporation plating LiQ on the electron transport layer to be used as an electron injection layer, wherein the evaporation plating thickness is 0.5 nm; vacuum evaporating Mg, Ag (9:1) as a cathode on the electron injection layer, wherein the evaporation thickness is 15 nm; the compound 11 was vacuum-deposited on the cathode as a coating layer to a thickness of 70 nm.
Comparative examples 2 to 3: preparation of comparative organic electroluminescent devices 2 to 3
And respectively replacing the compound 11 in the covering layer in the comparative example 1 with a compound 29 and LiF, and obtaining comparative organic electroluminescent devices 2-3 by the same steps.
Comparative examples 4 to 5: preparation of comparative organic electroluminescent devices 4 to 5
The compound 1 in the first capping layer in example 1 was replaced with R-1 and R-2, respectively, and the other steps were the same, to obtain comparative organic electroluminescent devices 4 to 5.
Figure BDA0003063302580000301
The results of the test of the light emitting characteristics of the organic electroluminescent devices prepared in examples 1 to 26 of the present invention and comparative examples 1 to 5 are shown in table 2.
Table 2 light emitting characteristic test data of organic electroluminescent device
Figure BDA0003063302580000302
Figure BDA0003063302580000311
As can be seen from Table 2, compared with the comparison devices 1 to 5, the organic electroluminescent devices 1 to 26 of the present invention have smaller color coordinate changes after the viewing angle changes from 0 ° to 60 °, which indicates that the change of the luminescent color of the device of the present invention with the change of the angle is smaller, indicating that the organic electroluminescent device of the present invention has weaker angle-dependent characteristics.
In addition, the device of the present invention also has higher luminous efficiency and longer life span than the comparative device. This shows that the organic electroluminescent device of the present invention has effectively improved luminous efficiency due to the synergistic effect of the specific high refractive index of the triarylamine compound of formula 1 in the first cover layer and the specific low refractive index of the metal halide in the second cover layer due to the presence of the specific double cover layer. In addition, the metal halide serving as the second covering layer is not easily influenced by the external environment and plays a role in protecting the organic layer, the first covering layer has better stability and is not easily deformed due to the influence of temperature, and the first covering layer cooperate to enable each layer of thin film of the organic light-emitting device to be in a stable state for a longer time, so that the service life of the device is effectively prolonged.
It should be understood that the present invention has been particularly described with reference to particular embodiments thereof, but that various changes in form and details may be made therein by those skilled in the art without departing from the principles of the invention and, therefore, within the scope of the invention.

Claims (5)

1. An organic electroluminescent device is characterized by sequentially comprising an anode, an organic layer, a cathode, a first covering layer and a second covering layer, wherein the refractive index of the second covering layer is below 1.7, the first covering layer contains triarylamine derivatives shown in a structural formula 1,
Figure FDA0003492603090000011
x is selected from O or S;
the ring P and the ring Q are independently selected from one of the following groups,
Figure FDA0003492603090000012
wherein, when ring P is selected from
Figure FDA0003492603090000013
When ring Q is selected from
Figure FDA0003492603090000014
M1 is selected from 0, 1, 2, 3 or 4; m2 is selected from 0, 1, 2, 3, 4, 5 or 6; m3 is selected from 0, 1, 2, 3, 4 or 5; m4 is selected from 0, 1, 2 or 3;
ar is1、Ar2Independently selected from one of the groups shown in formulas I-1 to I-9 or formulas II-1 to II-6, and Ar1、Ar2At least one of them is selected from the group represented by the formulae II-1 to II-6,
Figure FDA0003492603090000015
n1 is selected from 0, 1, 2, 3 or 4; n2 is selected from 0, 1, 2, 3, 4, 5, 6 or 7; n3 is selected from 0, 1, 2, 3, 4, 5 or 6; n4 is selected from 0, 1, 2, 3, 4 or 5; n5 is selected from 0, 1, 2 or 3;
said L1、L2Independently selected from a single bond or one of the groups shown below,
Figure FDA0003492603090000016
r1 is selected from 0, 1, 2, 3 or 4; r2 is selected from 0, 1, 2, 3, 4, 5 or 6; r3 is selected from 0, 1, 2, 3, 4 or 5; r4 is selected from 0, 1, 2 or 3;
the ring P, ring Q, Ar1、Ar2、L1、L2At least one of which contains deuterium;
the second coating layer contains one or more of LiF, KBr and MgF2、NaF、KF、RbF、CaF2。
2. The organic electroluminescent device as claimed in claim 1, wherein the refractive index of the second capping layer is 1.0 to 1.7.
3. The organic electroluminescent device as claimed in claim 1, wherein the first capping layer has a film thickness of 1 to 150nm, and the second capping layer has a film thickness of 1 to 150 nm.
4. The organic electroluminescent device as claimed in claim 1, wherein Ar is Ar1、Ar2Independently selected from one of the groups shown in the following,
Figure FDA0003492603090000021
5. the organic electroluminescent device according to claim 1, wherein the triarylamine derivative represented by formula 1 is selected from one of the following structures,
Figure FDA0003492603090000022
Figure FDA0003492603090000031
Figure FDA0003492603090000041
Figure FDA0003492603090000051
Figure FDA0003492603090000061
Figure FDA0003492603090000071
Figure FDA0003492603090000081
Figure FDA0003492603090000091
Figure FDA0003492603090000101
Figure FDA0003492603090000111
Figure FDA0003492603090000121
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