CN110845394B - Aromatic amine compound and organic electroluminescent device thereof - Google Patents

Aromatic amine compound and organic electroluminescent device thereof Download PDF

Info

Publication number
CN110845394B
CN110845394B CN201911161661.1A CN201911161661A CN110845394B CN 110845394 B CN110845394 B CN 110845394B CN 201911161661 A CN201911161661 A CN 201911161661A CN 110845394 B CN110845394 B CN 110845394B
Authority
CN
China
Prior art keywords
compound
layer
aromatic amine
group
amine compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201911161661.1A
Other languages
Chinese (zh)
Other versions
CN110845394A (en
Inventor
董秀芹
王英雪
鲁秋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changchun Hyperions Technology Co Ltd
Original Assignee
Changchun Hyperions Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changchun Hyperions Technology Co Ltd filed Critical Changchun Hyperions Technology Co Ltd
Priority to CN201911161661.1A priority Critical patent/CN110845394B/en
Publication of CN110845394A publication Critical patent/CN110845394A/en
Application granted granted Critical
Publication of CN110845394B publication Critical patent/CN110845394B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C07D209/82—Carbazoles; Hydrogenated carbazoles
    • C07D209/88—Carbazoles; Hydrogenated carbazoles with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D209/00—Heterocyclic compounds containing five-membered rings, condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D209/56—Ring systems containing three or more rings
    • C07D209/80—[b, c]- or [b, d]-condensed
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D219/00—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems
    • C07D219/04—Heterocyclic compounds containing acridine or hydrogenated acridine ring systems with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to carbon atoms of the ring system
    • C07D219/08—Nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D265/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one oxygen atom as the only ring hetero atoms
    • C07D265/28—1,4-Oxazines; Hydrogenated 1,4-oxazines
    • C07D265/34—1,4-Oxazines; Hydrogenated 1,4-oxazines condensed with carbocyclic rings
    • C07D265/38—[b, e]-condensed with two six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D279/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom and one sulfur atom as the only ring hetero atoms
    • C07D279/10—1,4-Thiazines; Hydrogenated 1,4-thiazines
    • C07D279/14—1,4-Thiazines; Hydrogenated 1,4-thiazines condensed with carbocyclic rings or ring systems
    • C07D279/18—[b, e]-condensed with two six-membered rings
    • C07D279/22—[b, e]-condensed with two six-membered rings with carbon atoms directly attached to the ring nitrogen atom
    • 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
    • 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
    • C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D311/78—Ring systems having three or more relevant rings
    • C07D311/80—Dibenzopyrans; Hydrogenated dibenzopyrans
    • C07D311/82—Xanthenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
    • C07D311/96—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings spiro-condensed with carbocyclic rings or ring systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D327/00—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D327/02—Heterocyclic compounds containing rings having oxygen and sulfur atoms as the only ring hetero atoms one oxygen atom and one sulfur atom
    • C07D327/06—Six-membered rings
    • C07D327/08—[b,e]-condensed with two six-membered carbocyclic rings
    • 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
    • C07D333/76—Dibenzothiophenes
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D407/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00
    • C07D407/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings
    • C07D407/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen atoms as the only ring hetero atoms, not provided for by group C07D405/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D411/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D411/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D411/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
    • C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/06—Peri-condensed 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
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/14—Carrier transporting layers
    • H10K50/15—Hole transporting layers
    • 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
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
    • 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
    • H10K85/649—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
    • 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
    • H10K85/649—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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Optics & Photonics (AREA)
  • Electroluminescent Light Sources (AREA)

Abstract

The invention provides an aromatic amine compound and an organic electroluminescent device thereof, and relates to the technical field of organic photoelectric materials. The aromatic amine compound is obtained by introducing a specific heteroaryl group and a bicycloheptane group into a triarylamine structure, has good hole transport capacity, high glass transition temperature, good thermal stability, good film forming property, high refractive index and simple synthesis, can be applied to an organic electroluminescent device as a hole transport layer and/or a covering layer, can effectively solve the problems of poor thermal stability, low luminous efficiency and short service life of the organic electroluminescent device, and has the advantages of high luminous efficiency and long service life.

Description

Aromatic amine compound and organic electroluminescent device thereof
Technical Field
The invention relates to the technical field of organic electroluminescence, in particular to an aromatic amine compound and an organic electroluminescent device thereof.
Background
With the advent of the information age, the research on new displays on human-computer interfaces has attracted more and more attention, especially, various flat panel display device technologies, wherein organic electroluminescent devices have advantages of being thinner and lighter, actively emitting light, wide in viewing angle, high in definition, stable in image, rich in color, fast in response, low in energy consumption, low in temperature, excellent in anti-seismic performance, flexible and low in manufacturing cost, and are increasingly applied to the fields of mobile phones, personal electronic assistants (PDAs), digital cameras, vehicle-mounted displays, notebook computers, televisions and military, are considered as a new flat panel display device capable of replacing liquid crystal displays, are known as a flat panel display technology with illusion display characteristics, and become a hot spot for research and development of new materials and display technology fields in recent years.
The initial organic electroluminescent device is realized by spin coating, dip coating or vacuum evaporation of a luminescent material (luminescent layer) on a conductive glass substrate (anode), then evaporation of a cathode material and connection of a power supply. The hole injection layer, the hole transport layer, the electron injection layer and the electron transport layer are mainly used for reducing an injection barrier between an electrode and a light-emitting layer and improving the injection rate and the mobility of holes and electrons, so that the power consumption of the device is reduced and the light-emitting efficiency of the device is improved; the luminescent layer can be formed by a single substance or a doped host material and an object material, wherein the host and object doping mode is adopted, so that the recombination probability of electrons and holes is improved, the concentration quenching of excitons is avoided, the utilization rate of light is improved, the accumulation of non-radiative energy is avoided, and the service life of the device is prolonged; the covering layer is mainly applied to the outer side of the cathode of the device, is generally applied to a top-emitting organic electroluminescent device, generally adopts an organic luminescent material with larger refractive index and stable property, and utilizes the microcavity effect to effectively refract light in the device out of one side of the cathode, so that the light extraction efficiency of the device is improved, the total reflection effect of the light in the device is reduced, and the final luminous efficiency of the device is effectively improved.
The material and structure of the organic electroluminescent device directly determine the efficiency and service life of the device.
The organic electroluminescent device still has many problems due to the limitation of the types of organic luminescent materials at present, the change of the physical form of an organic layer is one of the factors of the aging of the organic electroluminescent device, and the heat generated during the operation of the device causes the melting and recrystallization of the organic layer, which not only damages the uniformity of the thin film, but also damages the good interface contact between the electrode and each organic layer, thereby causing the reduction of the efficiency and the service life of the device. Wherein, the hole transport layer mostly adopts triarylamine and benzidine compounds, NPB and TAPC are the most commonly used hole transport layer materials, and the hole mobility of TAPC can reach 1.0 multiplied by 10- 2cm2V-1S-1The material has a high triplet state energy level, but the glass transition temperature is only 89 ℃, so that the material is easy to crystallize in the using process, and the stability of a device is seriously influenced; NPB hole mobility of 8.8X 10-4cm2V-1S-1The glass transition temperature is raised to 99 ℃, but the triplet state energy level is only 2.29eV, so that the loss of excitons to the hole transport layer can not be effectively avoided, and the efficiency and the stability of the device are reduced.
In addition, for the selection of the structure of the organic electroluminescent device, the structure of the organic electroluminescent device can be divided into a bottom emitting device and a top emitting device according to a light emitting path, the light emitting efficiency of the bottom emitting device is only 20%, so that the serious waste of the device efficiency is caused, heat is accumulated in the device, and cannot be dissipated, so that the service life of the device is shortened. The theoretical light extraction efficiency of the top emission device can reach 100%, but because the cathode and the outermost covering layer have plasma element effect, waveguide effect and the like, the matching of the material type, thickness and refractive index is difficult to achieve, at present, the covering layer mostly adopts organic luminescent materials with the refractive index within the range of 1.7-1.9, but the conventional covering layer material adopted at present has certain absorption in a blue light wave band, so that the luminescent efficiency and color purity of a blue light device and the loss of a blue light part in a white light device can be reduced, the deviation of the color temperature and the display of the device can be caused, the blue light material can be further wasted, and the cost of the device can be increased.
With the increasing market demand and the continuous progress of industrial technology, an organic electroluminescent device is required to have higher luminous efficiency and longer service life in the future, how to ensure that a hole transport material has higher hole mobility, high glass transition temperature and high triplet state energy level and how to ensure that a covering layer has higher refractive index so as to improve the thermal stability and the light-emitting efficiency of the device, and finally, the improvement of the luminous efficiency and the service life of the device become problems to be solved urgently.
Disclosure of Invention
In order to solve the problems of poor thermal stability caused by low glass transition temperature of a hole transport material at the present stage, low luminous efficiency caused by the fact that excitons cannot be effectively prevented from dissipating to the anode side, low light extraction efficiency caused by low refractive index of a covering layer and the like, the invention provides an aromatic amine compound and an organic electroluminescent device thereof.
The invention provides an aromatic amine compound, wherein the molecular structural general formula of the aromatic amine compound is shown as a chemical formula I:
Figure BDA0002286295280000021
wherein R is1The following structure is shown:
Figure BDA0002286295280000022
"+" indicates the position of the connection, R3Selected from any one of alkyl groups of H, C1-C10, b is selected from an integer from 1 to 6, and when the value of b is more than 1, each R is3The same or different;
R2selected from substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6-C24 aryl, substituted or unsubstituted C6-C30 aralkyl, substituted or unsubstituted C6-C30 aralkenyl, substituted or unsubstituted C6-C24 arylamine, substituted or unsubstituted C6-C24 aryloxy, substituted or unsubstituted C6-C24 arylthio, substituted or unsubstituted C3-C24 heteroaryl, a is selected from an integer from 0 to 4, and when a is more than 1, each R is not less than 12Identical or different, or adjacent R2Can be connected into a ring;
L1any one selected from substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene;
L2selected from single bonds, substituted or notAny one of substituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene;
ar is any one of substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl;
X1selected from NR4O, S; x2Selected from single bonds, NR5、CR6R7O, S;
R4、R5、R6、R7independently selected from any one of C1-C10 alkyl, substituted or unsubstituted C6-C31 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or R6、R7Are connected into a ring.
The invention also provides an organic electroluminescent device which comprises an anode, a cathode and an organic layer, wherein the organic layer contains the aromatic amine compound.
Advantageous effects
The invention provides an aromatic amine compound and an organic electroluminescent device thereof, wherein the aromatic amine compound is obtained by introducing heteroaryl (containing N, O, S heteroatom) and substituted or unsubstituted bicycloheptane into a triarylamine structure.
Specific heteroaryl containing N, O, S and bicycloheptane groups are introduced into a triarylamine structure, bicycloheptane is a non-conjugated structure, specific heteroaryl containing N, O, S is a small conjugated structure, and finally formed aromatic amine compound has higher triplet state energy level, glass transition temperature, refractive index and hole mobility, and shows good hole transport capacity, thermal stability and easy film forming characteristics; the aromatic amine compound has higher glass transition temperature, can effectively improve the stability of a device and prolong the service life of the device; in addition, the aromatic amine compound has a high refractive index of 1.85-2.0, and can be applied to an organic electroluminescent device as a covering layer, so that the light extraction efficiency of the device can be effectively improved, the light loss of a visible light wave band can be reduced, the heat accumulation in the device can be avoided due to the increase of the light extraction efficiency, and the service life of the device can be effectively prolonged.
Drawings
FIG. 1 shows the preparation of Compound 21H NMR chart; FIG. 2 shows preparation of compound 261H NMR chart;
FIG. 3 shows Compound 1471H NMR chart; FIG. 4 shows a compound 2591H NMR chart;
FIG. 5 shows the preparation of compound 3151H NMR chart.
Detailed Description
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of protection of the present invention.
The aryl group in the present invention refers to a general term of monovalent group remaining after one hydrogen atom is removed from an aromatic nucleus carbon of an aromatic hydrocarbon molecule, and may be monocyclic aryl group, polycyclic aryl group or condensed ring aryl group, and examples may include phenyl group, biphenyl group, terphenyl group, naphthyl group, binaphthyl group, anthracenyl group, phenanthrenyl group, triphenylenyl group, pyrenyl group, fluorenyl group, spirofluorenyl group, chrysenyl group, anthryl group, benzofluorenyl group, benzofluoranthryl group and the like, but are not limited thereto.
The heteroaryl group of the present invention is a general term for a monovalent group obtained by removing a hydrogen atom from a nuclear carbon of an aromatic heterocyclic ring composed of carbon and a hetero atom, examples of the hetero atom include, but are not limited to, oxygen, sulfur, nitrogen atoms, the heteroaryl group may be a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a fused heteroaryl group, and examples may include carbazolyl, furyl, thienyl, pyrrolyl, imidazolyl, oxazolyl, thiazolyl, pyridyl, pyrimidinyl, triazinyl, acridinyl, benzothienyl, benzofuryl, dibenzofuryl, dibenzothienyl, benzocarbazolyl, phenoxazinyl, phenothiazinyl, phenoxathiyl, quinazolinyl, quinoxalinyl, quinolyl, indolyl, azacarbazolyl, azafluorenyl, azaspirobifluorenyl, oxaanthracyl, thiaanthracenyl, and the like, but are not limited thereto.
The arylene group in the present invention refers to a general term of divalent groups remaining after two hydrogen atoms are removed from an aromatic core carbon of an aromatic hydrocarbon molecule, and may be monocyclic arylene group, polycyclic arylene group or condensed ring aryl group, and examples may include phenylene group, biphenylene group, terphenylene group, naphthylene group, binaphthylene group, anthracenylene group, phenanthrenylene group, triphenylene group, pyrenylene group, fluorenylene group, spirofluorenylene group, chrysenylene group, fluoranthenylene group, benzofluorenylene group, benzofluoranthenylene group and the like, but are not limited thereto.
The heteroarylene group of the present invention is a general term in which two hydrogen atoms are removed from a nuclear carbon of an aromatic heterocyclic ring composed of carbon and hetero atoms including, but not limited to, oxygen, sulfur and nitrogen atoms, and the heteroarylene group may be a monocyclic heteroarylene group, a polycyclic heteroarylene group or a condensed ring heteroarylene group, and examples may include a furanylene group, a thiophenylene group, a pyrrolylene group, an imidazolyl group, an oxazolylene group, a thiazolyl group, a pyridylene group, a pyrimidylene group, a carbazolyl group, an acridinylene group, a benzothiophenylene group, a benzofuranylene group, a dibenzofuranylene group, a dibenzothiophenylene group, a phenoxazylene group, a quinazolinylene group, a quinoxalylene group, an indoliylene group, an azacarbazylene group, an azafluorenyl group, an azaspirobifluorylene group, an azaspirofluorene group, a naphthoylene group, a fused ring group, a, Xanthylene, thioxylene, and the like, but are not limited thereto.
The invention provides an aromatic amine compound, wherein the molecular structural general formula of the aromatic amine compound is shown as a chemical formula I:
Figure BDA0002286295280000041
wherein R is1The following structure is shown:
Figure BDA0002286295280000042
"+" indicates the position of the connection, R3Selected from any one of alkyl groups of H, C1-C10, b is selected from an integer from 1 to 6, and when the value of b is more than 1, each R is3The same or different;
R2selected from substituted or unsubstituted C1-C10 alkyl, substituted or unsubstituted C6-C24 aryl, substituted or unsubstituted C6-C30 aralkyl, substituted or unsubstituted C6-C30 aralkenyl, substituted or unsubstituted C6-C24 arylamine, substituted or unsubstituted C6-C24 aryloxy, substituted or unsubstituted C6-C24 arylthio, substituted or unsubstituted C3-C24 heteroaryl, a is selected from an integer from 0 to 4, and when a is more than 1, each R is not less than 12Identical or different, or adjacent R2Can be connected into a ring;
L1any one selected from substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene;
L2any one selected from single bond, substituted or unsubstituted C6-C30 arylene, substituted or unsubstituted C3-C30 heteroarylene;
ar is any one of substituted or unsubstituted C6-C60 aryl and substituted or unsubstituted C3-C60 heteroaryl;
X1selected from NR4O, S; x2Selected from single bonds, NR5、CR6R7O, S;
R4、R5、R6、R7independently selected from any one of C1-C10 alkyl, substituted or unsubstituted C6-C31 aralkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C3-C30 heteroaryl, or R6、R7Are connected into a ring.
In the present invention, the substituted alkyl, substituted aryl, substituted aralkyl, substituted aralkenyl, substituted arylamine, substituted aryloxy, substituted arylthio, substituted heteroaryl, substituted arylene, substituted heteroarylene, wherein the substituents are independently selected from deuterium, alkyl of C1-C10, aryl of C6-C24, heteroaryl of C3-C24, preferably deuterium, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, phenyl, naphthyl, biphenyl, terphenyl, phenanthryl, anthryl, fluoranthenyl, benzofluoranthenyl, triphenylenyl, chrysyl, carbazolyl, furyl, thienyl, benzofuranyl, benzothienyl, dibenzofuranyl, dibenzothienyl, pyridizinyl, phenoxazinyl, phenothiazinyl, 9-dimethyl acridinyl, 9-dimethyl fluorenyl, thiophene, furan, thiophene, and benzene thiophene, and benzene, thiophene, and benzene, thiophene, 9-dimethyl, 9-, Any one of 9, 9-diphenylfluorenyl group and spirofluorenyl group.
Preferably, R is1Any one selected from the following groups:
Figure BDA0002286295280000043
"+" indicates the connection position.
Preferably, the aromatic amine compound is selected from any one of the following formulas:
Figure BDA0002286295280000051
wherein R is2Is selected from any one of C1-C10 alkyl, C6-C24 aryl and C3-C24 heteroaryl, a is selected from an integer from 0 to 4, and when a is more than 1, each R2The same or different; r4Any one selected from aryl of C6-C18 and heteroaryl of C3-C18;
a is selected from any one of the following structures:
Figure BDA0002286295280000052
wherein "+" represents a bonding site.
More preferably, said L1、L2Independently selected from any one of the following groups:
Figure BDA0002286295280000053
wherein R is8、R9、R10Independently selected from any one of methyl, ethyl, propyl, isopropyl, tert-butyl, hexyl, phenyl, biphenyl, terphenyl and naphthyl; m is an integer from 0 to 4, n is an integer from 0 to 4, and when n is greater than 1, each R8Identical or different, L1Is composed of
Figure BDA0002286295280000054
When m is not 0; p is selected from 1 or 2.
Preferably, Ar is selected from any one of the following groups:
Figure BDA0002286295280000055
Figure BDA0002286295280000061
wherein R is11Selected from any one of H, methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, pyrenyl, carbazolyl, phenylcarbazolyl, dibenzofuranyl, dibenzothienyl, 9-methyl-9-phenylfluorenyl, 9-dimethylfluorenyl, spirobifluorenyl, 9-diphenylfluorenyl, furyl, thienyl, benzofuranyl, benzothienyl, azacarbazolyl, azaspirobifluorenyl, phenoxazinyl, phenoxathiinyl, phenothiazinyl, acridinyl, c is selected from an integer of 1 to 5, d is selected from an integer of 1 to 6, e is selected from an integer of 1 to 8, f is selected from an integer of 1 to 4, and when c, d, e or f takes a value greater than 1, each R is selected from an integer of 1 to 511The same or different;
R12、R13independently selected from any one of methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, pyrenyl, carbazolyl, phenylcarbazolyl, dibenzofuranyl, dibenzothienyl, 9-methyl-9-phenylfluorenyl, 9-dimethylfluorenyl, spirobifluorenyl, 9-diphenylfluorenyl, furyl, thienyl, benzofuranyl, benzothienyl, azacarbazolyl, azaspirobifluorenyl, phenoxazinyl, phenoxathiinyl, phenothiazinyl, acridinyl;
b is selected from one of phenyl or naphthyl.
More preferably, said L1、L2Independently selected from any one of the following groups:
Figure BDA0002286295280000062
or L is2Selected from single bonds;
ar is selected from any one of the following groups:
Figure BDA0002286295280000063
Figure BDA0002286295280000071
said R2Any one selected from the group consisting of methyl, ethyl, propyl, isopropyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, triphenylene, pyrenyl, carbazolyl, phenylcarbazolyl, dibenzofuranyl, dibenzothienyl, 9-methyl-9-phenylfluorenyl, 9-dimethylfluorenyl, spirobifluorenyl, 9-diphenylfluorenyl, furanyl, thienyl, benzofuranyl, benzothienyl, azacarbazolyl, azaspirobifluorenyl, phenoxazinyl, phenoxathiinyl, phenothiazinyl, and acridinyl.
Most preferably, the aromatic amine compound is selected from any one of the following chemical structures:
Figure BDA0002286295280000081
Figure BDA0002286295280000091
Figure BDA0002286295280000101
Figure BDA0002286295280000111
Figure BDA0002286295280000121
Figure BDA0002286295280000131
Figure BDA0002286295280000141
Figure BDA0002286295280000151
Figure BDA0002286295280000161
the synthetic route of the aromatic amine compound of the invention is as follows:
Figure BDA0002286295280000162
Figure BDA0002286295280000171
when Ar-and R1-L1-not simultaneously:
1. the raw materials a-1-1, a-2-1 are Pd (pph)3)4Is a catalyst, K2CO3Is alkali, and reacts to obtain an intermediate b-1-1; intermediate b-1-1, starting material a-3-1, with P (t-Bu)3、Pd(OAC)2Is used as a catalyst, NaOBu-t is used as alkali, and an intermediate b-2 is obtained after the reaction when L2When the intermediate is a bond, the intermediate b-1-1 can be directly used as a starting material for reaction;
2. the raw materials a-1-2, a-2-2 are Pd (pph)3)4Is a catalyst, K2CO3Is alkali, and reacts to obtain an intermediate b-1-2; intermediate b-1-2, starting material a-3-2, with P (t-Bu)3、Pd(OAC)2Is used as a catalyst, NaOBu-t is used as alkali, and an intermediate b-2 is obtained after the reaction; when L is2When the intermediate b-1-2 is a bond, the intermediate b-1-2 can be directly used as a starting material for reaction;
3. reacting a raw material a-4 and triisopropyl borate by taking n-BuLi as alkali to obtain an intermediate b-3;
4. intermediate b-3, starting material a-5, in Pd (pph)3)4Is a catalyst, K2CO3Is alkali, and reacts to obtain an intermediate b-4;
5. intermediates b-4, b-2, with P (t-Bu)3、Pd(OAC)2Is used as a catalyst and NaOBu-t is used as alkali, and the aromatic amine compound I is obtained by reaction.
When Ar-and R1-L1-when the same:
1. intermediates b-4, b-1-2, with P (t-Bu)3、Pd(OAC)2Is used as a catalyst and NaOBu-t is used as alkali, and the aromatic amine compound I is obtained by reaction.
The present invention has no particular limitation on the above reaction, and conventional reactions well known to those skilled in the art can be adopted, and the synthesis method is easy to operate, simple and feasible.
The invention also provides an organic electroluminescent device which comprises an anode, a cathode and an organic layer, wherein the organic layer contains the aromatic amine compound.
An organic electroluminescent device according to the present invention may be manufactured using materials and methods known in the art, except that one or more organic layers in the organic electroluminescent device may include the aromatic amine compound according to the present invention.
Preferably, the organic layer is located between the anode and the cathode, and the device structure includes two cases:
(1) the bottom emission device comprises an anode, an organic layer and a cathode in sequence, wherein the organic layer comprises at least one of a hole injection layer, a hole transport layer, a hole auxiliary layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer, preferably, at least one of the organic layers contains the aromatic amine compound, and more preferably, the hole transport layer contains the aromatic amine compound.
(2) The top emission device comprises an anode, a first organic layer, a cathode and a second organic layer in sequence, wherein the first organic layer comprises at least one of a hole injection layer, a hole transport layer, a hole auxiliary layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer, the second organic layer comprises a covering layer, preferably, at least one of the first organic layer contains the aromatic amine compound provided by the invention, and more preferably, the hole transport layer contains the aromatic amine compound provided by the invention.
Further, the hole transport layer according to the present invention may be any one selected from a single layer structure composed of a single compound, a single layer structure composed of two or more compounds, and a multi-layer structure composed of two or more compounds, wherein the hole transport layer contains at least one aromatic amine compound according to the present invention, or contains a conventional hole transport material known to those skilled in the art.
Preferably, the organic layer is located on the side of the cathode facing away from the anode, and the device structure includes one of:
(1) the top emission device comprises an anode, a first organic layer, a cathode and a second organic layer in sequence, wherein the first organic layer comprises at least one of a hole injection layer, a hole transport layer, a hole auxiliary layer, an electron blocking layer, a light emitting layer, a hole blocking layer, an electron transport layer and an electron injection layer, the second organic layer comprises a covering layer, preferably, at least one of the second organic layers contains the aromatic amine compound provided by the invention, and preferably, the covering layer contains the aromatic amine compound provided by the invention; further preferably, the aromatic amine compound according to the present invention is contained in both the first organic material layer and the second organic material layer, and most preferably, the aromatic amine compound according to the present invention is contained in both the hole transport layer and the cover layer.
Further, the cover layer according to the present invention is selected from any one of a single layer structure composed of a single compound, a single layer structure composed of two or more compounds, and a multi-layer structure composed of two or more compounds, wherein the cover layer contains at least one aromatic amine compound according to the present invention, or contains a conventional cover layer material well known to those skilled in the art.
Further, the hole transport layer according to the present invention may be any one selected from a single layer structure composed of a single compound, a single layer structure composed of two or more compounds, and a multi-layer structure composed of two or more compounds, wherein the hole transport layer may contain at least one aromatic amine compound according to the present invention, or a conventional hole transport material known to those skilled in the art.
More preferably, the organic electroluminescent device structure of the present invention is preferably:
(1) bottom emission device: substrate/anode/hole injection layer/hole transport layer (aromatic amine compound according to the present invention)/light emitting layer/electron transport layer/electron injection layer/cathode;
(2) bottom emission device: substrate/anode/hole injection layer/hole transport layer (the aromatic amine compound of the present invention)/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode;
(3) bottom emission device: substrate/anode/hole injection layer/hole transport layer (the aromatic amine compound of the present invention)/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;
(4) top emission device: substrate/anode/hole injection layer/hole transport layer (aromatic amine compound according to the present invention)/light-emitting layer/electron transport layer/electron injection layer/cathode/cover layer;
(5) top emission device: substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode/cover layer (aromatic amine compound according to the present invention);
(6) top emission device: substrate/anode/hole injection layer/hole transport layer (the aromatic amine compound described in the present invention)/light-emitting layer/electron transport layer/electron injection layer/cathode/cover layer (the aromatic amine compound described in the present invention);
(7) top emission device: substrate/anode/hole injection layer/hole transport layer/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/cover layer (aromatic amine compound according to the present invention);
(8) top emission device: substrate/anode/hole injection layer/hole transport layer (aromatic amine compound described in the present invention)/light-emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/cover layer (aromatic amine compound described in the present invention).
However, the structure of the organic electroluminescent device is not limited thereto. The organic electroluminescent device can be selected and combined according to the parameter requirements of the device and the characteristics of materials, and part of organic layers can be added or omitted.
The organic electroluminescent device can be used in the application fields of flat panel displays, lighting sources, signboards, signal lamps and the like
The invention is explained in more detail by the following examples, without wishing to restrict the invention accordingly. Based on this description, one of ordinary skill in the art will be able to practice the invention and prepare other compounds and devices according to the invention within the full scope of the disclosure without undue inventive effort.
The raw materials used in the following examples are not particularly limited, and may be commercially available products or prepared by methods known to those skilled in the art.
The aromatic amine compounds synthesized in the examples of the present invention were characterized by the following test instruments:
nuclear magnetic hydrogen spectrum (1H NMR): model Bruker-510 NMR spectrometer (Bruker, Germany), 500MHz, CDCl3TMS is an internal standard, and chloroform is a solvent;
mass spectrometry: AXIMA-CFR plus matrix assisted laser desorption ionization flight mass spectrometer (Kratos Analytical, Inc. of Shimadzu corporation);
elemental analysis: a Vario EL cube type organic element analyzer (Elementar, Germany).
EXAMPLE 1 Synthesis of Compound 2
Figure BDA0002286295280000191
Adding toluene solvent into a reaction bottle, sequentially adding 3-bromo-N-phenylcarbazole (33.85g, 200mmol), 4-aminobiphenyl (70.89g, 220mmol) and sodium tert-butoxide (57.66g, 600mmol), vacuumizing, introducing nitrogen for three times, and adding Pd (OAc)2(0.9g, 4.0mmol), vacuum-pumping and nitrogen-filling three times, then adding P (t-Bu)3(6.4mL of a 1.0M toluene solution, 6.4mmol), performing nitrogen replacement three times, performing reflux reaction on the mixture for 2 hours in a nitrogen environment, after the reaction is stopped, cooling the mixture to room temperature, filtering the mixture through diatomite to obtain a filtrate, concentrating the filtrate, adding 20mL of methanol, standing for recrystallization, and filtering to obtain the compound 2-1(68.97g, 84%), wherein the solid purity is not less than 99.9% through HPLC (high performance liquid chromatography).
Adding 500mL of THF, raw material a-1(35.01g, 200mmol) into a reaction bottle, vacuumizing, filling nitrogen for three times, cooling to-78 ℃, slowly dropwise adding 200mmol of n-butyllithium, and dropwise adding at-78 DEG CAdding triisopropyl borate (56.42g, 300mmol), stirring for reaction after dropwise addition, naturally heating to normal temperature, adding 2mol/L diluted hydrochloric acid to adjust the reaction solution to be neutral, adding 100mL ethyl acetate into the reaction solution to extract an organic phase, repeating the steps for three times, and passing the organic phase through anhydrous MgSO4Drying and concentrating, filtering, washing a filter cake, mixing and concentrating the obtained filtrate to 100mL, adding 20mL of n-hexane, standing and recrystallizing, standing for a period of time to separate out a solid, and filtering to obtain an intermediate 2-2(20.16g, 72%), wherein the purity of the solid is not less than 99.1% by HPLC (high performance liquid chromatography).
400mL of toluene was added to a reaction flask, followed by sequential addition of intermediate 2-2(19.6g, 140mmol), 4-bromo-4-iodobiphenyl (55.29g, 154mmol), 160mL of ethanol, and an aqueous solution of potassium carbonate (58.05g, 420mmol), vacuum evacuation and nitrogen purging were carried out three times, and Pd (pph) was placed under nitrogen protection3)4(1.62g and 1.4mmol), vacuumizing and filling nitrogen for three times, refluxing and stirring at 80 ℃ for 4 hours for reaction, stopping heating, adding 240mL of water, stirring for 0.5 hour, cooling to 40 ℃, filtering under reduced pressure, washing a filter cake with water (160mL) and acetone (200mL) in sequence to ensure that a filtrate is neutral, drying the filter cake at 100 ℃, dissolving the filter cake with chloroform, filtering through an active silica gel funnel, concentrating the solution to 500mL, adding 50mL of methanol for recrystallization while stirring while the solution is hot, filtering under reduced pressure to obtain an intermediate 2-3(36.65g and 80%), and detecting the solid purity by HPLC (high performance liquid chromatography) to be not less than 99.1%.
The toluene solvent was charged into a reaction flask, followed by the sequential addition of intermediate 2-3(26.18g, 80mmol), intermediate 2-1(36.13g, 88mmol) and sodium tert-butoxide (23.06g, 240mmol), vacuum-pumping and nitrogen-purging three times, followed by the addition of Pd (OAc)2(0.36g, 1.6mmol), vacuum-pumping and nitrogen-filled three times, then adding P (t-Bu)3(6.4mL of a 1.0M toluene solution, 6.4mmol), performing nitrogen replacement three times, performing reflux reaction on the mixture for 2 hours in a nitrogen environment, after the reaction is stopped, cooling the mixture to room temperature, filtering the mixture through diatomite to obtain a filtrate, concentrating the filtrate, adding 20mL of ethanol, standing the filtrate for recrystallization, and filtering the filtrate to obtain the compound 2(42.57g, 81%) with the solid purity being equal to or greater than 99.9% through HPLC (high performance liquid chromatography).
Mass spectrum m/z: 656.41 (calculated value: 656.32). Theoretical element content (%) C49H40N2: c, 89.60; h, 6.14; and N, 4.26. Measured elemental content (%): c, 89.62; h, 6.14; and N, 4.24.1H-NMR(500MHz，CDCl3) (, ppm): 8.39(dd, J ═ 7.4,1.5Hz,1H),8.09(dd, J ═ 7.5,1.4Hz,1H),7.92(dd, J ═ 7.5,2.0Hz,2H),7.85(d, J ═ 1.4Hz,1H),7.70(d, J ═ 7.5Hz,1H), 7.62-7.57 (m, J ═ 7.5,2.4Hz,6H),7.48(d, J ═ 7.5Hz,2H),7.44(t, J ═ 7.6Hz,4H), 7.42-7.38 (m,5H),7.36(d, J ═ 7.6Hz,2H),7.33(dd, J ═ 5.4,2.1, 3.1H, 19, 19.6H), 1.50(m, 1.6H), 1.6H, 1.68 (d, 1.6H), 1.6H, 6H), 1.68 (d, 1.6H), 2H, 6H, 1.68 (1H), 1H, 6H, 1H, 6H, 1H, 6H. The above results confirmed that the obtained product was the objective product.
EXAMPLE 2 Synthesis of Compound 26
By replacing 4-aminobiphenyl, which was the starting material in example 1, with an equimolar amount of 2-amino-9, 9-spirobifluorene, compound 26(51.76g, 79%) was obtained according to the method for synthesizing compound 2, and the solid purity was 99.9% or more by HPLC.
Mass spectrum m/z: 818.43 (calculated value: 818.37). Theoretical element content (%) C62H46N2: c, 90.92; h, 5.66; and N, 3.42. Measured elemental content (%): c, 90.95; h, 5.65; and N, 3.40.1H-NMR(500MHz,CDCl3) (, ppm): 8.39(dd, J ═ 7.4,1.5Hz,1H),8.08(dd, J ═ 7.4,1.5Hz,1H), 7.95-7.86 (m,3H),7.82(dd, J ═ 6.9,5.1Hz,3H),7.78(d, J ═ 1.5Hz,1H), 7.69-7.64 (m,2H), 7.64-7.55 (m, J ═ 7.3,5.7Hz,7H), 7.55-7.51 (m,2H),7.49(d, J ═ 1.6Hz,2H), 7.46-7.41 (m,4H), 7.41-7.35 (m,6H), 7.35-7.31 (m, J ═ 7.5,1.5, 7.5H), 7.46-7.41 (m,4H), 7.35-7.35 (m,6H), 7.35-7.31 (m, J ═ 7.5,1.5, 1.7.7.7.65, 7.7.7.1H), 7.7.6H, 7.1, 7.1.9 (d, 1.6Hz, 7.6H), 7.7.7.6H), 7.7.6H), 7.7.7.6H, 7.1.6H), 7.6H, 7.31 (d, 7.7.7.7.7.7.9, 7.6H), 7.1.7.7.6H, 7.6H), 7.6H, 7.1.6H, 2H) in that respect The above results confirmed that the obtained product was the objective product.
EXAMPLE 3 Synthesis of Compound 67
By replacing 4-aminobiphenyl, which was the starting material in example 1, with an equimolar amount of 3-aminodibenzofuran, compound 67(42.94g, 80%) was obtained according to the method for synthesizing compound 2, and the solid purity by HPLC ≧ 99.9%.
Mass spectrum mZ: 670.38 (calculated value: 670.30). Theoretical element content (%) C49H38N2O: c, 87.73; h, 5.71; n, 4.18; o, 2.38. Measured elemental content (%): c, 87.75; h, 5.70; n, 4.18; o, 2.37. The above results confirmed that the obtained product was the objective product.
EXAMPLE 4 Synthesis of Compound 108
By replacing the starting material 3-bromo-N-phenylcarbazole in example 1 with an equimolar amount of 4-bromo-dibenzofuran, compound 108(38.63g, 83%) was obtained according to the method for synthesizing compound 2, and the solid purity was 99.9% or more by HPLC.
Mass spectrum m/z: 581.34 (calculated: 581.27). Theoretical element content (%) C43H35NO: c, 88.78; h, 6.06; n, 2.41; o, 2.75. Measured elemental content (%): c, 88.81; h, 5.70; n, 4.16; o, 2.36. The above results confirmed that the obtained product was the objective product.
EXAMPLE 5 Synthesis of Compound 141
Figure BDA0002286295280000201
Figure BDA0002286295280000211
By replacing the starting material 3-bromo-N-phenylcarbazole in example 1 with an equimolar amount of 2-bromo-9, 10-dihydro-9, 9-dimethyl-10-phenylacridine and 4-aminobiphenyl with 4-aminodibenzofuran, compound 141(44.49g, 78%) was obtained according to the method for synthesizing compound 2, and the solid purity by HPLC ≧ 99.9%.
Mass spectrum m/z: 712.42 (calculated value: 712.35). Theoretical element content (%) C52H44N2O: c, 87.61; h, 6.22; n, 3.93; o, 2.24. Measured elemental content (%): c, 87.63; h, 6.21; n, 3.92; o, 2.24. The above results confirmed that the obtained product was the objective product.
EXAMPLE 6 Synthesis of Compound 147
By replacing the starting material 3-bromo-N-phenylcarbazole in example 1 with an equimolar amount of 2-bromo-11, 11-dimethyl-11H-benzo [ B ] fluorene and 4-aminobiphenyl with 4-aminodibenzofuran, compound 147(40.85g, 76%) was obtained according to the method for synthesizing compound 2, and the solid purity was ≧ 99.9% by HPLC.
Mass spectrum m/z: 671.38 (calculated value: 671.32). Theoretical element content (%) C50H41NO: c, 89.38; h, 6.15; n, 2.08; o, 2.38. Measured elemental content (%): c, 89.36; h, 6.15; n, 2.10; o, 2.39.1H-NMR(500MHz,CDCl3) (, ppm): 8.05(dd, J ═ 18.7,1.4Hz,2H),7.99(dd, J ═ 3.6,1.5Hz,2H), 7.89-7.82 (m,2H),7.75(dd, J ═ 6.6,2.4Hz,1H),7.69(d, J ═ 7.5Hz,1H), 7.64-7.58 (m,2H), 7.52-7.40 (m,8H), 7.39-7.29 (m,4H), 7.24-7.18 (m,2H), 2.67-2.59 (m,1H), 2.39-2.25 (m,2H), 1.87-1.80 (m,1H),1.83(s,3H),1.79(s,3H),1.62(dd, J ═ 6, 5H), 1.56, 6H), 1.6, 6H, 7.6H), 7.6H, 7.39-7.6 (m,4H), 7.39-7.29 (m,4H), 7.7.7.7.7.7.6 (m,4H), 7.79 (m, 4H). The above results confirmed that the obtained product was the objective product.
EXAMPLE 7 Synthesis of Compound 152
By replacing the starting material 3-bromo-N-phenylcarbazole in example 1 with an equimolar amount of 2-bromo-2, 7-di-tert-butyl-9, 9-spirobifluorene and 4-aminobiphenyl with 4-aminodibenzofuran, compound 152(52.74g, 77%) was obtained according to the method for synthesizing compound 2, and the solid purity ≧ 99.9% by HPLC.
Mass spectrum m/z: 855.52 (calculated value: 855.44). Theoretical element content (%) C64H57NO: c, 89.78; h, 6.71; n, 1.64; o, 1.87. Measured elemental content (%): c, 89.79; h, 6.70; n, 1.65; o, 1.86. The above results confirmed that the obtained product was the objective product.
EXAMPLE 8 Synthesis of Compound 259
By replacing the raw material 3-bromo-N-phenylcarbazole in example 1 with an equimolar amount of 3-bromobenzo [ B ] naphtho [2,3-D ] furan and 4-aminobiphenyl with 9, 9-diphenyl-2-aminofluorene, compound 259(47.76g, 75%) was obtained according to the synthesis method of compound 2, and the solid purity ≧ 99.9% by HPLC.
Mass spectrum m/z: 796.422 (calculated value: 795.35). Theoretical element content(％)C60H45NO: c, 90.53; h, 5.70; n, 1.76; and O, 2.01. Measured elemental content (%): c, 90.51; h, 5.71; n, 1.76; and O, 2.02.1H-NMR(500MHz,CDCl3) (, ppm): 8.30 to 8.26(m, J ═ 7.5,1.5Hz,1H),7.85(d, J ═ 1.7Hz,2H),7.80(d, J ═ 7.5Hz,1H),7.77 to 7.72(m, J ═ 7.4,1.5Hz,1H),7.58 to 7.44(m,9H),7.42(d, J ═ 1.5Hz,1H),7.41 to 7.37(m, J ═ 7.5,1.5Hz,1H),7.36 to 7.31(m,3H),7.30 to 7.20(m,9H),7.16(dd, J ═ 7.5,1.5Hz,1H),7.13 to 7.07(m,4H),6.97(dd, J ═ 7.5, 1.7.81, 1H), 1.13 to 7.1H, 1.49 (dd, 1.5H), 1.6.7.7.7.1H, 1H, 1.1H, 1.1.6.1H, 49 (dd, 1.5H), 1.1H, 1H, 49 (1.1.6.1H), 1.6.1H, 1H, 49 (1H), 1H, 1.1.1H, 1H, 1.1H, 49(m, 1H), 1.6.6.1H), 1.6, 1H, 1.1., 1H) in that respect The above results confirmed that the obtained product was the objective product.
EXAMPLE 9 Synthesis of Compound 315
Figure BDA0002286295280000221
A toluene solvent was charged into a reaction flask, followed by sequentially adding intermediate 2-3(26.18g, 80mmol), 4-aminodibenzofuran (8.06g, 44mmol) and sodium tert-butoxide (23.06g, 240mmol), vacuum-pumping and replacing three times with nitrogen, and then adding Pd (OAc)2(0.36g, 1.6mmol), vacuum-pumping and nitrogen-filled three times, then adding P (t-Bu)3(6.4mL of a 1.0M toluene solution, 6.4mmol), performing nitrogen replacement three times, performing reflux reaction on the mixture for 2 hours in a nitrogen environment, after the reaction is stopped, cooling the mixture to room temperature, filtering the mixture through diatomite to obtain a filtrate, concentrating the filtrate, adding 20mL of ethanol, standing the filtrate for recrystallization, and filtering the filtrate to obtain compound 315(21.09g, 78%), wherein the solid purity is not less than 99.9% by HPLC (high performance liquid chromatography).
Mass spectrum m/z: 675.41 (calculated value: 675.35). Theoretical element content (%) C50H45NO: c, 88.85; h, 6.71; n, 2.07; o, 2.37. Measured elemental content (%): c, 88.87; h, 6.70; n, 2.06; o, 2.37.
1H-NMR(500MHz,CDCl3)(,ppm)：8.06(dd,J＝7.6,1.4Hz,1H),7.77(dd,J＝7.3,1.7Hz,1H),7.64–7.58(m,5H) 7.47-7.42 (m,5H), 7.42-7.38 (m,5H), 7.38-7.33 (m,4H),7.26(d, J ═ 7.2Hz,1H),7.24(d, J ═ 1.6Hz,1H),2.64(s,2H), 2.36-2.27 (m, J ═ 12.1,7.0,3.3Hz,4H),1.81(s,2H), 1.68-1.58 (m,6H), 1.58-1.51 (m, J ═ 13.7,7.0,3.5Hz,2H), 1.44-1.36 (m,2H),1.31(d, J ═ 6.7Hz, 4H). The above results confirmed that the obtained product was the objective product.
EXAMPLE 10 Synthesis of Compound 349
By replacing the starting material 3-bromo-N-phenylcarbazole with an equimolar amount of 2-bromo-9, 10-dihydro-9, 9-dimethyl-10-phenylacridine and the starting material a-1 with an equimolar amount of 7-bromonorbornane in example 1, compound 349(44.17g, 79%) was obtained according to the synthesis method of compound 2, and the solid purity by HPLC ≧ 99.9%.
Mass spectrum m/z: 698.42 (calculated value: 698.37). Theoretical element content (%) C52H46N2: c, 89.36; h, 6.63; and N, 4.01. Measured elemental content (%): c, 89.38; h, 6.62; and N, 4.00. The above results confirmed that the obtained product was the objective product.
Glass transition temperature (Tg) test of the compounds synthesized in inventive examples 1-10:
test samples: compound 2, 26, 67, 108, 141, 147, 152, 259, 315, 349, tested separately, had a mass of 5mg per sample.
Testing an instrument: DSC 25 type differential scanning calorimeter (TA, USA);
the test method comprises the following steps: the test atmosphere is nitrogen, and the flow rate of the nitrogen is 50 ml/min; the heating rate is 10 ℃/min, and the temperature range is 50-350 DEG C
The glass transition temperature (Tg) test results are shown in table 1:
TABLE 1
Figure BDA0002286295280000222
Figure BDA0002286295280000231
The results in table 1 show that the aromatic amine compound provided by the invention adopts a triarylamine structure formed by combining heteroaryl and bicycloheptane, and the final compound has a higher glass transition temperature and therefore has better thermal stability.
Refractive index (n) test of the compounds synthesized in examples 1 to 10 of the present invention:
test samples: compounds 2, 26, 67, 108, 141, 147, 152, 259, 315, 349, were tested separately.
Testing an instrument: ellipsometer type M-2000 spectrum (j.a. woollam, usa);
the test method comprises the following steps: the instrument scanning range is 245-1000 nm, the size of the glass substrate is 200 x 200mm, the thickness of the compound evaporation film is 30nm, and the measured refractive index (n) at 450nm is shown in Table 2.
TABLE 2
Compound (I) n Compound (I) n
2 1.88 147 1.97
26 1.94 152 1.94
67 1.90 259 1.99
108 1.87 315 1.91
141 1.88 349 1.88
The results in table 2 show that the aromatic amine compound provided by the present invention has a high refractive index.
The invention discloses preparation and performance test of an organic electroluminescent device
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. A joint IVL test system is formed by 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 to test the driving voltage and the luminous efficiency of the organic electroluminescent device. The lifetime was measured using M6000 OL from McScienceED life-span test system. The environment of the test is atmospheric environment, and the temperature is room temperature.
Device comparative example 1
The ITO-Ag-ITO glass substrate is ultrasonically cleaned for 20min by using 5% glass cleaning solution, then is ultrasonically cleaned for 3 times by using distilled water, each time is 5min, the ITO-Ag-ITO glass substrate is ultrasonically cleaned for 20min by using acetone and isopropanol in sequence, is dried at 120 ℃, and then is placed in plasma equipment for cleaning for 5 min. Then, the processed ITO glass substrate is put into a vacuum evaporator, and the system vacuum degree is maintained to be 5 multiplied by 10 in the film preparation process-4And Pa, then sequentially evaporating 60nm of HI1 and 5nm of HATCN as hole injection layers, 60nm of HT-1 as a hole transport layer and 25nm of BH2 on the ITO-Ag-ITO substrate: BD2 was doped at 3% as a light emitting layer, 30nm Alq 3: liq (1: 1) as electron transport layer, LiF at 1nm as electron injection layer, Mg at 15 nm: comparative device 1 was prepared by using an Ag alloy (10:1) as the cathode, BPA 60nm as the cap layer, and sealing the device in a glove box.
Figure BDA0002286295280000241
Device comparative example 2 was obtained by following the method for producing device comparative example 1 by replacing the hole transport layer compound HT-1 in device comparative example 1 with compound a.
Figure BDA0002286295280000242
Device comparative example 3
Device comparative example 3 was obtained by following the method for producing device comparative example 1 by replacing the hole transport layer compound HT-1 in device comparative example 1 with compound B.
Figure BDA0002286295280000243
Device example 1
The hole transport layer compound HT-1 of comparative example 1 was replaced with the compound 2 of example 1, and the device 1 was obtained by following the method for producing the device comparative example 1.
Device example 2
Device 2 was obtained by following the method for producing device comparative example 1 by replacing the hole transport layer compound HT-1 of comparative example 1 with the compound 26 of example 2.
Device example 3
Device 3 was obtained by following the method for producing device comparative example 1 by replacing the hole transport layer compound HT-1 of comparative example 1 with the compound 67 of example 3.
Device example 4
The hole transport layer compound HT-1 of comparative example 1 was replaced with the compound 108 of example 4, and the device 4 was obtained by following the method for producing the device comparative example 1.
Device example 5
Device 5 was obtained by following the method for producing the device of comparative example 1 by replacing the hole transport layer compound HT-1 of comparative example 1 with the compound 141 of example 5.
Device example 6
The hole transport layer compound HT-1 of comparative example 1 was replaced with the compound 147 of example 6, and the device 6 was obtained by following the method for producing the device comparative example 1.
Device example 7
The hole transport layer compound HT-1 of comparative example 1 was replaced with the compound 152 of example 7, and the device 7 was obtained by following the method for producing the device comparative example 1.
Device example 8
The hole transport layer compound HT-1 of comparative example 1 was replaced with the compound 259 of example 8, and the device 8 was obtained by following the method for producing the device comparative example 1.
Device example 9
Device 9 was obtained by following the method for producing the device of comparative example 1 by replacing the hole transport layer compound HT-1 of comparative example 1 with the compound 315 of example 9.
Device example 10
The hole transport layer compound HT-1 of comparative example 1 was replaced with the compound 349 of example 10, and the device 10 was obtained by following the method for producing the device comparative example 1.
Device comparative example 4
Device comparative example 4 was obtained by replacing the cap layer BPA in device comparative example 1 with compound a and following the same procedure.
Figure BDA0002286295280000251
Device comparative example 5
Device comparative example 5 was obtained by replacing the cap layer BPA in device comparative example 1 with compound B and following the same procedure.
Figure BDA0002286295280000252
Device example 11
Device 11 was obtained by following the method of production of comparative example 2 by replacing the cap compound BPA of comparative example 2 with compound 2 of example 1.
Device example 12
Device 12 was obtained by following the method of production of comparative example 2 by replacing the cap compound BPA of comparative example 2 with compound 26 of example 2.
Device example 13
Device 13 was obtained by following the method for the production of comparative example 2 by replacing the cap compound BPA of comparative example 2 with the compound 67 of example 3.
Device example 14
Device 14 was obtained by following the method of preparation of comparative example 2 by replacing the cap compound BPA of comparative example 2 with compound 108 of example 4.
Device example 15
Device 15 was obtained by following the method for the preparation of comparative example 2 by replacing the cap compound BPA of comparative example 2 with the compound 141 of example 5.
Device example 16
Device 16 was obtained by following the method of preparation of comparative example 2 by replacing the cap compound BPA of comparative example 2 with the compound 147 of example 6.
Device example 17
Device 17 was obtained by following the method of preparation of comparative example 2 by replacing the cap compound BPA of comparative example 2 with the compound 152 of example 7.
Device example 18
Device 18 was obtained by following the method of production of comparative example 2 except that the cap compound BPA of comparative example 2 was replaced with the compound 259 of example 8.
Device example 19
Device 19 was obtained by following the method of preparation of comparative example 2 by replacing the cap compound BPA of comparative example 2 with the compound 315 of example 9.
Device example 20
Device 20 was obtained by following the method of production of device comparative example 2 by replacing the cap compound BPA of comparative example 2 with compound 349 of example 10.
Device example 21
Device 21 was obtained by following the method for the production of device comparative example 2 except that the hole transport layer HT-1 of comparative example 2 was replaced with the compound 108 of example 4 and the capping layer compound BPA was replaced with the compound 108 of example 4.
Device example 22
The hole transport layer HT-1 of comparative example 2 was replaced with the compound 108 of example 4, the capping layer compound BPA was replaced with the compound 259 of example 8, and the device 22 was obtained by following the method for the preparation of device comparative example 2.
Device example 23
Device 23 was obtained by following the method for the production of device comparative example 2 by replacing the hole transport layer HT-1 of comparative example 2 with the compound 147 of example 6 and the capping layer compound BPA with the compound 108 of example 4.
Device example 24
The hole transport layer HT-1 of comparative example 2 was replaced with the compound 147 of example 6, the capping layer compound BPA was replaced with the compound 259 of example 8, and the device 24 was obtained by following the method for the production of the device comparative example 2.
The optical performance tests of the devices 1-24 in the device examples and the device comparative examples 1-5 are shown in the following table 3:
TABLE 3
Figure BDA0002286295280000261
Figure BDA0002286295280000271
The results in table 3 show that the aromatic amine compound provided by the invention can be used as a hole transport layer and a covering layer or used as the hole transport layer and the covering layer simultaneously in a top-emission organic electroluminescent device, so that the luminous efficiency of the device can be effectively improved, the service life of the device can be prolonged, and the driving voltage of the device can be reduced.
The aromatic amine compound provided by the invention is an organic electroluminescent material with excellent performance.
It is obvious that the above description of the embodiments is only intended to assist the understanding of the method of the invention and its core ideas. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (2)

1. An organic electroluminescent device comprising an anode, a cathode, and an organic layer, wherein the organic layer is located on a side of the cathode away from the anode, the organic layer contains an aromatic amine compound, and the aromatic amine compound is selected from any one of the following formulas:
Figure FDA0002777426970000011
wherein R is1Any one selected from the following groups:
Figure FDA0002777426970000012
"+" indicates the connection location;
R2is selected from any one of phenyl, biphenyl, terphenyl, naphthyl, anthryl and phenanthryl, a is selected from an integer from 0 to 4, and when a is more than 1, each R2The same or different; r4Any one selected from phenyl, biphenyl, terphenyl, naphthyl, anthryl and phenanthryl;
a is selected from:
Figure FDA0002777426970000013
L1any one selected from the following groups:
Figure FDA0002777426970000014
L2any one selected from the following groups:
Figure FDA0002777426970000015
or L2Selected from single bonds;
ar is selected from any one of the following groups:
Figure FDA0002777426970000021
2. an organic electroluminescent device, comprising an anode, a cathode, and an organic layer, wherein the organic layer is located on a side of the cathode away from the anode, the organic layer contains an aromatic amine compound, and the aromatic amine compound is selected from any one of the following chemical structures:
Figure FDA0002777426970000031
Figure FDA0002777426970000041
Figure FDA0002777426970000051
Figure FDA0002777426970000061
Figure FDA0002777426970000071
Figure FDA0002777426970000081
Figure FDA0002777426970000091
Figure FDA0002777426970000101
CN201911161661.1A 2019-11-25 2019-11-25 Aromatic amine compound and organic electroluminescent device thereof Active CN110845394B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911161661.1A CN110845394B (en) 2019-11-25 2019-11-25 Aromatic amine compound and organic electroluminescent device thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911161661.1A CN110845394B (en) 2019-11-25 2019-11-25 Aromatic amine compound and organic electroluminescent device thereof

Publications (2)

Publication Number Publication Date
CN110845394A CN110845394A (en) 2020-02-28
CN110845394B true CN110845394B (en) 2021-01-01

Family

ID=69604240

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911161661.1A Active CN110845394B (en) 2019-11-25 2019-11-25 Aromatic amine compound and organic electroluminescent device thereof

Country Status (1)

Country Link
CN (1) CN110845394B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4043432A1 (en) * 2021-02-03 2022-08-17 Samsung Display Co., Ltd. Light emitting element and amine compound for the same
EP4174055A1 (en) * 2021-10-29 2023-05-03 Samsung Display Co., Ltd. Light emitting device and amine compound for light emitting device

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110317141A (en) * 2019-07-01 2019-10-11 陕西莱特光电材料股份有限公司 A kind of electroluminescent organic material and its synthetic method and application
CN111018721A (en) * 2019-10-31 2020-04-17 陕西莱特光电材料股份有限公司 Nitrogen-containing compound, electronic component, and electronic device
CN111933818A (en) * 2020-08-12 2020-11-13 长春海谱润斯科技有限公司 Organic light-emitting device
CN115551851A (en) * 2020-08-19 2022-12-30 株式会社Lg化学 Novel compound and organic light emitting device comprising same
WO2022039518A1 (en) * 2020-08-19 2022-02-24 주식회사 엘지화학 Novel compound and organic light-emitting device comprising same
WO2022045743A1 (en) * 2020-08-24 2022-03-03 주식회사 엘지화학 Novel compound and organic light-emitting device using same
CN112341449B (en) * 2020-11-10 2022-03-01 长春海谱润斯科技股份有限公司 Triarylamine organic compound containing spirofluorene and organic light-emitting device thereof
CN115141137A (en) * 2021-03-31 2022-10-04 阜阳欣奕华材料科技有限公司 Benzfluorene compound, organic electroluminescent device and display device
CN113443998B (en) * 2021-06-11 2022-09-09 长春海谱润斯科技股份有限公司 Triarylamine organic compound and organic light-emitting device thereof
CN114436942B (en) * 2022-02-18 2023-11-03 长春海谱润斯科技股份有限公司 Arylamine compound containing carbazole group and organic electroluminescent device thereof
CN114790184A (en) * 2022-06-22 2022-07-26 吉林奥来德光电材料股份有限公司 Luminous auxiliary material and preparation method thereof, light-emitting device and light-emitting device

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6777111B1 (en) * 1999-08-04 2004-08-17 Kabushiki Kaisha Chuo Kenkyusho Electro luminescent element
CN107721907A (en) * 2017-10-31 2018-02-23 长春海谱润斯科技有限公司 A kind of organic compound and its organic luminescent device
CN108933198A (en) * 2018-08-27 2018-12-04 长春海谱润斯科技有限公司 A kind of organic electroluminescence device containing aromatic amine compound
CN108987598A (en) * 2018-07-18 2018-12-11 长春海谱润斯科技有限公司 A kind of organic luminescent device
CN110183332A (en) * 2019-06-17 2019-08-30 陕西莱特光电材料股份有限公司 A kind of aromatic derivant comprising polycyoalkane and the organic electroluminescence device comprising the derivative
CN110437081A (en) * 2019-07-15 2019-11-12 陕西莱特光电材料股份有限公司 Organic compound containing tricycloheptane and preparation method thereof and organic electroluminescence device comprising the compound

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6777111B1 (en) * 1999-08-04 2004-08-17 Kabushiki Kaisha Chuo Kenkyusho Electro luminescent element
CN107721907A (en) * 2017-10-31 2018-02-23 长春海谱润斯科技有限公司 A kind of organic compound and its organic luminescent device
CN108987598A (en) * 2018-07-18 2018-12-11 长春海谱润斯科技有限公司 A kind of organic luminescent device
CN108933198A (en) * 2018-08-27 2018-12-04 长春海谱润斯科技有限公司 A kind of organic electroluminescence device containing aromatic amine compound
CN110183332A (en) * 2019-06-17 2019-08-30 陕西莱特光电材料股份有限公司 A kind of aromatic derivant comprising polycyoalkane and the organic electroluminescence device comprising the derivative
CN110437081A (en) * 2019-07-15 2019-11-12 陕西莱特光电材料股份有限公司 Organic compound containing tricycloheptane and preparation method thereof and organic electroluminescence device comprising the compound

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP4043432A1 (en) * 2021-02-03 2022-08-17 Samsung Display Co., Ltd. Light emitting element and amine compound for the same
EP4174055A1 (en) * 2021-10-29 2023-05-03 Samsung Display Co., Ltd. Light emitting device and amine compound for light emitting device

Also Published As

Publication number Publication date
CN110845394A (en) 2020-02-28

Similar Documents

Publication Publication Date Title
CN110845394B (en) Aromatic amine compound and organic electroluminescent device thereof
CN111808042B (en) Triarylamine compound and organic electroluminescent device thereof
CN110407829B (en) Arylamine compound and organic light-emitting device thereof
CN112341449B (en) Triarylamine organic compound containing spirofluorene and organic light-emitting device thereof
KR101355562B1 (en) Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof
CN113501812B (en) Triarylamine compound and organic electroluminescent device thereof
EP1937616A1 (en) New binaphthalene derivatives, preparation method thereof and organic electronic device using the same
CN111170874B (en) Arylamine compound and organic electroluminescent device thereof
CN111116505B (en) Amine compound and organic light-emitting device thereof
CN113443998A (en) Triarylamine organic compound and organic light-emitting device thereof
CN111205272B (en) Material for organic electroluminescent device and organic electroluminescent device thereof
CN113735808A (en) Triarylamine compound and organic electroluminescent device thereof
TW201920070A (en) Materials for electronic devices
CN111635384B (en) Arylamine organic compound and organic light-emitting device thereof
CN111100126B (en) Compound, display panel and display device
WO2022242521A1 (en) Condensed azacyclic compound, use thereof, and organic electroluminescent device comprising condensed azacyclic compound
CN111892587A (en) Heterocyclic organic compound and organic light-emitting device thereof
CN113735809B (en) Aromatic amine derivative and organic electroluminescent device thereof
CN107226799B (en) Organic compound, organic photoelectric device and display device
CN113387943A (en) Aromatic amine derivative and organic electroluminescent device using same
CN111205293B (en) Heterocyclic compound, display panel and display device
CN112750957A (en) Organic electroluminescent device
CN114426539B (en) Organic compound, organic electroluminescent device and electronic device comprising the same
CN114230564B (en) Heterocyclic compound and organic electroluminescent device thereof
CN112510160B (en) Organic light-emitting device

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
CB02 Change of applicant information

Address after: 130000 A5, North Lake Science and Technology Park, 3333 North Sheng street, Beihu science and Technology Development Zone, Jilin, Changchun

Applicant after: Changchun hiprunsi Technology Co., Ltd

Address before: 130000 A5, North Lake Science and Technology Park, 3333 North Sheng street, Beihu science and Technology Development Zone, Jilin, Changchun

Applicant before: CHANGCHUN HAIPURUNSI TECHNOLOGY Co.,Ltd.

CB02 Change of applicant information
GR01 Patent grant
GR01 Patent grant