CN112341449A

CN112341449A - Triarylamine organic compound containing spirofluorene and organic light-emitting device thereof

Info

Publication number: CN112341449A
Application number: CN202011244745.4A
Authority: CN
Inventors: 韩春雪; 孙月; 赵倩; 刘辉
Original assignee: Changchun Hyperions Technology Co Ltd
Current assignee: Changchun Hyperions Technology Co Ltd
Priority date: 2020-11-10
Filing date: 2020-11-10
Publication date: 2021-02-09
Anticipated expiration: 2040-11-10
Also published as: CN112341449B

Abstract

The invention provides a triarylamine organic compound containing spirofluorene and an organic light-emitting device thereof, relating to the technical field of organic photoelectric materials. The organic compound is characterized in that triarylamine is taken as a center, a spirofluorene group and a benzo five-membered heteroaryl are connected, and a dibenzothiophene group or a dibenzofuran group is connected, three different substituent groups are mutually crossed and separated by taking triarylamine N as the center, so that the mutual accumulation of molecules is avoided, and the organic compound has the advantages of high Tg, molecular thermal stability and the like; the organic compound has higher refractive index, effectively solves the problem of total emission of the interface between the ITO film and the glass substrate and the interface between the glass substrate and the air, reduces the total reflection loss and waveguide loss in the OLED device, and improves the light extraction efficiency, thereby improving the luminous efficiency of the organic light-emitting device; meanwhile, the organic compound has good film forming property, is simple to synthesize and easy to operate, and can be widely applied to the fields of panel display, lighting sources, organic solar cells, organic photoreceptors or organic thin film transistors and the like.

Description

Triarylamine organic compound containing spirofluorene and organic light-emitting device thereof

Technical Field

The invention relates to the technical field of organic photoelectric materials, in particular to a triarylamine organic compound containing spirofluorene and an organic light-emitting device thereof.

Background

Organic Light Emitting Diodes (OLEDs) are regarded by the scientific and industrial fields because of their advantages of light weight, low cost, wide viewing angle, fast response speed, active light emission, and full color display. It can be said that OLEDs have almost all of the excellent features required for the manufacture of lighting and information display devices and are considered by industry as one of the most desirable and promising next generation lighting display technologies. Due to the potential huge application value of the OLED, how to prepare a high-efficiency device attracts more and more attention of people, and meanwhile, the performance requirement of people on the OLED is improved.

The development of OLED materials has reached a relatively mature stage, in which a hole transport Layer, an electron transport Layer, a host material, a fluorescent light emitting material, and a phosphorescent light emitting material have been developed, but the development of a Capping Layer material (Capping Layer) has been paid attention to.

The cover layer is a very important functional layer in an OLED, in particular a layer of an organic or inorganic transparent material with a high refractive index, which is substantially non-absorbing in the visible range. The light emitting device with the covering layer can improve the light emitting mode, so that light originally limited in the device can be emitted out of the device, and higher light extraction efficiency is shown. Under the same device structure, the OLED device with the covering layer can improve the light extraction efficiency and reduce the operating voltage. However, the type of the current covering layer material is single, and the effect is not ideal.

Due to the huge difference between the external quantum efficiency and the internal quantum efficiency of the OLED, the development of the OLED is greatly restricted. Total reflection occurs at the interface between the ITO thin film and the glass substrate and the interface between the glass substrate and the air, the light emitted to the front external space of the OLED device accounts for about 20% of the total amount of the organic material thin film EL, and the remaining about 80% of the light is mainly confined in the organic material thin film, the ITO thin film and the glass substrate in the form of a waveguide. It can be seen that the light extraction efficiency of the conventional OLED device is low (about 20%), which severely restricts the development and application of the OLED. How to reduce the total reflection effect in the OLED device and improve the ratio of light coupled to the forward external space of the device (light extraction efficiency) has attracted much attention. Since the inorganic cover layer material deforms due to the heat released by the high evaporation temperature, so that the alignment accuracy is poor, and the device itself may be damaged, the organic cover layer material has a low evaporation temperature, but the number of the organic cover layer materials to be selected is small, so that a new cover layer material is developed to improve the light extraction efficiency of the device, and the improvement of the light emission efficiency is an urgent matter.

Disclosure of Invention

The invention aims to provide a triarylamine organic compound containing spirofluorene and an organic light-emitting device thereof, wherein the organic light-emitting device prepared by using the triarylamine organic compound containing spirofluorene has good light-emitting efficiency; the above problems are solved as a main constituent of a cap layer in an organic light emitting device, which has a molecular structural formula shown in formula I:

wherein R is₁、R₂、R₃Independently selected from one of hydrogen, deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C20 heteroaryl;

L₁、L₂、L₃independently selected from single bond, substituted or unsubstituted C6-C25 arylene, substituted or unsubstituted C2-C20 aryleneOne of heteroaryl;

X₁selected from O, S or NR₀Wherein R is₀One selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C20 heteroaryl;

R₄one selected from hydrogen, deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C20 heteroaryl;

x is selected from O or S;

R₅one selected from hydrogen, deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C6-C25 aryl and substituted or unsubstituted C2-C20 heteroaryl;

m is selected from 0,1, 2,3 or 4; n is selected from 0,1, 2,3 or 4; p is selected from 0,1, 2,3 or 4; q is selected from 0,1, 2,3 or 4; o is selected from 0,1, 2,3 or 4;

when m is greater than 1, each R₁Same or different, adjacent R₁Can be benzene ring, when n is more than 1, each R₂Same or different, adjacent R₂Can be benzene ring, when p is more than 1, each R₃Same or different, adjacent R₃May form a benzene ring, when q is greater than 1, each R₄Same or different, adjacent R₄Can form a benzene ring or a naphthalene ring; when o is greater than 1, each R₅Same or different, adjacent R₅Can form benzene ring.

The invention also provides an organic light-emitting device, which comprises a cathode, an anode and one or more organic layers arranged between the cathode and the anode and outside the cathode and the anode, wherein the organic layer arranged between the cathode and the anode comprises at least one 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 and an electron injection layer; the organic layer arranged outside the cathode and the anode comprises a covering layer, the organic layer comprises the covering layer, and the covering layer contains any one or the combination of at least two of the triarylamine organic compounds containing spirofluorene.

The invention has the beneficial effects that:

the invention provides a triarylamine organic compound containing spirofluorene and an organic light-emitting device thereof, wherein triarylamine is taken as a center, the triarylamine is connected with spirofluorene groups and benzo five-membered heteroaryl and is connected with a dibenzothiophene group or dibenzofuran group, three different substituent groups are mutually crossed and separated by taking triarylamine N as the center, and the mutual accumulation of molecules is avoided, so that the organic compound has the advantages of high glass transition temperature (Tg), molecular thermal stability and the like, and the high Tg is helpful for ensuring that the material is not crystallized in a film state. And the introduction of linear alkyl, branched alkyl and cycloalkyl as substituents can increase the solubility of the compound, and the energy level of the material cannot be changed by the cycloalkyl with spatial configuration.

The triarylamine organic compound containing spirofluorene has higher refractive index, can effectively solve the problem of total emission of an interface between an ITO film and a glass substrate and an interface between the glass substrate and air, reduces total reflection loss and waveguide loss in an OLED device, and improves light extraction efficiency, thereby improving the luminous efficiency of an organic light-emitting device.

The triarylamine organic compound containing spirofluorene is applied to an organic light-emitting device, can be used as a covering layer material to improve the light-emitting efficiency of the organic light-emitting device, has good film-forming property, simple synthesis and easy operation, and can meet the industrial requirement.

Drawings

FIG. 1 is a drawing showing Compound 1 of the present invention¹H NMR chart; FIG. 2 is a drawing showing Compound 23 of the present invention¹H NMR chart;

FIG. 3 is a drawing showing a preparation of compound 68 of the present invention¹H NMR chart; FIG. 4 is a drawing showing a scheme of Compound 89 of the present invention¹H NMR chart;

FIG. 5 is a drawing showing a scheme of preparing a compound 106 of the present invention¹H 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 alkyl group in the present invention refers to a hydrocarbon group obtained by dropping one hydrogen atom from an alkane molecule, and may be a straight-chain alkyl group or a branched-chain alkyl group, and preferably has 1 to 15 carbon atoms, more preferably 1 to 12 carbon atoms, and particularly preferably 1 to 6 carbon atoms. The straight chain alkyl group includes methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, undecyl, dodecyl and the like, but is not limited thereto; the branched alkyl group includes, but is not limited to, an isomeric group of isopropyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, an isomeric group of n-hexyl, an isomeric group of n-heptyl, an isomeric group of n-octyl, an isomeric group of n-nonyl, an isomeric group of n-decyl, and the like. The alkyl group is preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, or a tert-butyl group.

The cycloalkyl group in the present invention refers to a hydrocarbon group obtained by removing one hydrogen atom from a cycloalkane molecule, and preferably has 3 to 15 carbon atoms, more preferably 3 to 12 carbon atoms, and particularly preferably 3 to 6 carbon atoms, and examples thereof may include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, adamantyl, bornyl, norbornyl, and the like. The alkyl group is preferably a cyclopentyl group, a cyclohexyl group, a 1-adamantyl group, a 2-adamantyl group or a norbornyl group.

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 compound molecule, and may be monocyclic aryl group, polycyclic aryl group or condensed ring aryl group, preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 14 carbon atoms. The monocyclic aryl group means an aryl group having only one aromatic ring in the molecule, for example, phenyl group and the like, but is not limited thereto; the polycyclic aromatic group means an aromatic group having two or more independent aromatic rings in the molecule, for example, biphenyl group, terphenyl group and the like, but is not limited thereto; the fused ring aryl group refers to an aryl group in which two or more aromatic rings are contained in a molecule and are fused together by sharing two adjacent carbon atoms, and examples thereof include, but are not limited to, naphthyl, anthryl, phenanthryl, pyrenyl, perylenyl, fluorenyl, benzofluorenyl, triphenylene, fluoranthenyl, spirobifluorenyl, and the like. The above aryl group is preferably a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group (preferably a 2-naphthyl group), an anthryl group (preferably a 2-anthryl group), a phenanthryl group, a pyrenyl group, a perylenyl group, a fluorenyl group, a benzofluorenyl group, a triphenylene group, or a spirobifluorenyl group.

The heteroaryl group in the present invention refers to a general term of a group obtained by replacing one or more aromatic nucleus carbon atoms in an aryl group with a heteroatom, including but not limited to oxygen, sulfur, nitrogen or phosphorus atom, preferably having 1 to 25 carbon atoms, more preferably 2 to 20 carbon atoms, and particularly preferably 3 to 15 carbon atoms, wherein the attachment site of the heteroaryl group may be located on a ring-forming carbon atom or a ring-forming nitrogen atom, and the heteroaryl group may be a monocyclic heteroaryl group, a polycyclic heteroaryl group or a fused ring heteroaryl group. The monocyclic heteroaryl group includes pyridyl, pyrimidyl, triazinyl, furyl, thienyl, pyrrolyl, imidazolyl and the like, but is not limited thereto; the polycyclic heteroaryl group includes bipyridyl, phenylpyridyl, and the like, but is not limited thereto; the fused ring heteroaryl group includes quinolyl, isoquinolyl, indolyl, benzothienyl, benzofuranyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothienyl, carbazolyl, benzocarbazolyl, acridinyl, 9, 10-dihydroacridinyl, phenoxazinyl, phenothiazinyl, phenoxathiyl and the like, but is not limited thereto. The heteroaryl group is preferably a pyridyl group, a pyrimidyl group, a thienyl group, a furyl group, a benzothienyl group, a benzofuryl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a dibenzofuryl group, a dibenzothienyl group, a dibenzofuryl group, a carbazolyl group, an acridinyl group, a phenoxazinyl group, a phenothiazinyl group or a phenoxathiyl group.

The arylene group in the present invention refers to a general term of a divalent group remaining after two hydrogen atoms are removed from an aromatic core carbon of an aromatic compound molecule, and may be a monocyclic arylene group, a polycyclic arylene group or a condensed ring arylene group, and preferably has 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 14 carbon atoms. The monocyclic arylene group includes phenylene group and the like, but is not limited thereto; the polycyclic arylene group includes, but is not limited to, biphenylene, terphenylene, and the like; the condensed ring arylene group includes naphthylene, anthrylene, phenanthrylene, fluorenylene, pyrenylene, triphenylene, fluoranthenylene, phenylfluorenylene, and the like, but is not limited thereto. The arylene group is preferably a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, a fluorenylene group, or a phenylfluorenylene group.

Heteroarylene as used herein refers to the generic term for groups in which one or more of the aromatic core carbons in the arylene group is replaced with a heteroatom, including, but not limited to, oxygen, sulfur, nitrogen, or phosphorus atoms. Preferably having 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, and particularly preferably 6 to 15 carbon atoms, and the linking site of the heteroarylene group may be located on a ring-forming carbon atom or a ring-forming nitrogen atom, and the heteroarylene group may be a monocyclic heteroarylene group, a polycyclic heteroarylene group, or a fused ring heteroarylene group. The monocyclic heteroarylene group includes a pyridylene group, a pyrimidylene group, a triazinylene group, a furanylene group, a thiophenylene group and the like, but is not limited thereto; the polycyclic heteroarylene group includes bipyridyl idene, phenylpyridyl, etc., but is not limited thereto; the fused ring heteroarylene group includes, but is not limited to, a quinolylene group, an isoquinolylene group, an indolyl group, a benzothiophene group, a benzofuranylene group, a benzoxazolyl group, a benzimidazolylene group, a benzothiazolyl group, a dibenzofuranylene group, a dibenzothiophenylene group, a carbazolyl group, a benzocarbazolyl group, an acridinylene group, a 9, 10-dihydroacridine group, a phenoxazinyl group, a phenothiazinylene group, a phenoxathiin group and the like. The heteroaryl group is preferably a pyridylene group, pyrimidylene group, thienylene group, furylene group, benzothienylene group, benzofuranylene group, benzoxazolyl group, benzimidazolylene group, benzothiazolyl group, dibenzofuranylene group, dibenzothiophenylene group, dibenzofuranylene group, carbazolyl group, acridinylene group, phenoxazinyl group, phenothiazinylene group, phenoxathiin group.

The term "substituted …" as used herein, such as substituted alkyl, substituted cycloalkyl, substituted aryl, substituted heteroaryl, substituted arylene, substituted heteroarylene, refers to mono-or poly-substituted with groups independently selected from deuterium, substituted or unsubstituted C1-C6 alkyl, substituted or unsubstituted C3-C6 cycloalkyl, substituted or unsubstituted C6-C20 aryl, substituted or unsubstituted C2-C15 heteroaryl, substituted or unsubstituted amine, and the like, but not limited thereto, preferably with groups selected from deuterium, methyl, ethyl, isopropyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, anthryl, phenanthryl, benzophenanthryl, perylenyl, pyrenyl, benzyl, fluorenyl, 9-dimethylfluorenyl, dianilinyl, dimethylamino, carbazolyl, 9-phenylcarbazolyl, acridinyl, furyl, thienyl, benzofuranyl, pyrenyl, and the like, Benzothienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuranyl, dibenzothienyl, phenothiazinyl, phenoxazinyl, indolyl.

The bonding to form a cyclic structure according to the present invention means that the two groups are linked to each other by a chemical bond and optionally aromatized. As exemplified below:

in the present invention, the ring formed by the connection may be a five-membered ring or a six-membered ring or a fused ring, such as benzene, naphthalene, cyclopentene, cyclopentane, cyclohexane-acene, quinoline, isoquinoline, dibenzothiophene, phenanthrene or pyrene, but not limited thereto.

The invention provides a triarylamine organic compound containing spirofluorene, which has a molecular structural general formula shown in formula I:

L₁、L₂、L₃independently selected from one of single bond, substituted or unsubstituted C6-C25 arylene, substituted or unsubstituted C2-C20 heteroarylene;

x is selected from O or S;

Preferably, said R is₁、R₂、R₃At least one of the groups is selected from one of methyl, ethyl, isopropyl, tertiary butyl, cyclopentyl, cyclohexyl, adamantyl, bornyl and norbornyl; the rest is one of methyl, ethyl, isopropyl, tertiary butyl, cyclopentyl, cyclohexyl, adamantyl, bornyl, norbornyl, phenyl, pentadeuterated phenyl, tolyl, biphenyl, terphenyl and naphthyl; m is selected from 0,1 or 2; n is selected from 0,1 or 2; p is selected from 0,1 or 2.

Preferably, the

One selected from the following groups:

preferably, the

In (C) X₁Selected from O, S or NR₀Wherein R is₀One selected from methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, tolyl, biphenyl and naphthyl; q is selected from 0,1, 2,3 or 4;

R₄selected from hydrogen, deuterium, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl or one of the following substituents:

preferably, said L₁、L₂、L₃Independently selected from a single bond or any one of the following groups:

preferably, the

One selected from the following groups:

preferably, said R is₅Selected from hydrogen, deuterium, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl or one of the following substituents:

o is selected from 0,1 or 2.

Preferably, the triarylamine-based organic compound containing spirofluorene is selected from any one of the following chemical structures:

the preparation method of the triarylamine organic compound containing spirofluorene of the present invention can be prepared by the coupling reaction conventional in the art, for example, by the following synthetic route, but the present invention is not limited thereto:

the amine compound a and the halogen compound b are subjected to a Buchwald reaction to obtain an intermediate A, and then the intermediate A and the halogen compound c are subjected to the Buchwald reaction to obtain a target compound shown in a chemical formula I, namely, the target compound is obtained by adding raw materials, a catalyst, alkali, a ligand and a solution in a nitrogen atmosphere and reacting at a corresponding temperature, wherein X is₀Represents halogen such as Cl, Br, I.

The present invention is not particularly limited in terms of the source of the raw materials used in the above-mentioned various reactions, and can be obtained using commercially available raw materials or by a preparation method known to those skilled in the art. The present invention is not particularly limited to the above-mentioned reaction, and a conventional reaction known to those skilled in the art may be used. The compound provided by the invention has the advantages of few synthesis steps and simple method, and is beneficial to industrial production.

The invention also provides an organic light-emitting device, which comprises a cathode, an anode, one or more organic layers arranged between the cathode and the anode and one or more organic layers arranged outside the cathode and the anode, wherein the organic layers arranged between the cathode and the anode comprise at least one 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 and an electron injection layer; the organic layer arranged outside the cathode and the anode comprises a covering layer, and the covering layer contains any one or the combination of at least two of the triarylamine organic compounds containing spirofluorene.

The light emitting device of the present invention is generally formed on a substrate. The substrate may be any substrate as long as it does not change when forming an electrode or an organic layer, for example, a substrate of glass, plastic, a polymer film, silicon, or the like. When the substrate is opaque, the electrode opposite thereto is preferably transparent or translucent.

In the light-emitting device of the present invention, at least one of the anode and the cathode is transparent or translucent, and preferably, the cathode is transparent or translucent.

The anode material is preferably a material having a large work function so that holes are smoothly injected into the organic material layer, and a conductive metal oxide film, a translucent metal thin film, or the like is often used. Examples of the method for producing the film include a film (NESA or the like) made of a conductive inorganic compound containing indium oxide, zinc oxide, tin oxide, and a composite thereof, such as indium tin oxide (abbreviated as ITO) or indium zinc oxide (abbreviated as IZO), and a method using gold, platinum, silver, copper, or the like. As the anode, an organic transparent conductive film such as polyaniline or a derivative thereof, polythiophene or a derivative thereof, or the like can be used. The anode may have a laminated structure of 2 or more layers, and preferably, the anode of the present invention is formed of a transparent ITO substrate.

The hole injection layer is to improve the efficiency of hole injection from the anode into the hole transport layer and the light emitting layer. The hole injection material of the present invention may be a metal oxide such as molybdenum oxide, silver oxide, vanadium oxide, tungsten oxide, ruthenium oxide, nickel oxide, copper oxide, or titanium oxide, or a low molecular weight organic compound such as a phthalocyanine-based compound or a polycyano group-containing conjugated organic material, but is not limited thereto. Preferably, the hole injection layer of the present invention is selected from 4,4 '-tris [ 2-naphthylphenylamino ] triphenylamine (abbreviated as 2T-NATA), 2,3,6,7,10, 11-hexacyano-1, 4,5,8,9, 12-hexaazatriphenylamine (abbreviated as HAT-CN), 4' -tris (N, N-diphenylamino) triphenylamine (abbreviated as TDATA), 4 '-tris [ N- (3-methylphenyl) -N-phenylamino ] triphenylamine (abbreviated as MTDATA), copper (II) phthalocyanine (abbreviated as CuPc), N' -bis [4- [ bis (3-methylphenyl) amino ] phenyl ] -N, N '-diphenyl-biphenyl-4, 4' -diamine (abbreviated as DNTPD), etc., it may be a single structure made of a single substance, or a single-layer or multi-layer structure made of different substances.

The hole transport layer is a layer having a function of transporting holes. The hole transport material of the present invention is preferably a material having a good hole transport property, and may be selected from small molecular materials such as aromatic amine derivatives, carbazole derivatives, stilbene derivatives, triphenyldiamine derivatives, styrene compounds, butadiene compounds, and the like, and polymeric materials such as poly-p-phenylene derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, and the like, and the triarylamine organic compound containing spirofluorene provided by the present invention, but is not limited thereto. Preferably, the hole transport layer of the present invention is selected from the group consisting of N, N '-diphenyl-N, N' - (1-naphthyl) -1,1 '-biphenyl-4, 4' -diamine (abbreviated as NPB), N '-di (naphthalene-1-yl) -N, N' -di (phenyl) -2,2 '-dimethylbenzidine (abbreviated as. alpha. -NPD), N' -diphenyl-N, N '-di (3-methylphenyl) -1,1' -biphenyl-4, 4 '-diamine (abbreviated as TPD), 4' -cyclohexyldi [ N, N-di (4-methylphenyl) aniline ] (abbreviated as TAPC), 2,7, 7-tetra (diphenylamino) -9, 9-spirobifluorene (abbreviated as spirobifluorene-TAD) may be a single structure composed of a single substance or a single-layer structure or a multi-layer structure composed of different substances.

The electron-blocking layer is a layer which transports holes and blocks electrons, and is preferably selected from N, N ' -bis (naphthalen-1-yl) -N, N ' -bis (phenyl) -2,2' -dimethylbenzidine (abbreviated as. alpha. -NPD), 4' -tris (N, N-diphenylamino) triphenylamine (abbreviated as TDATA), N ' -diphenyl-N, N ' -bis (3-methylphenyl) -1,1' -biphenyl-4, 4' -diamine (abbreviated as TPD), 4' -cyclohexylbis [ N, N-bis (4-methylphenyl) aniline ] (abbreviated as TAPC), 2,7, 7-tetrakis (diphenylamino) -9, 9-spirobifluorene (abbreviated as Spiro-TAD), and the like, it may be a single structure made of a single substance, or a single-layer structure or a multi-layer structure made of different substances.

The light-emitting layer is a layer having a light-emitting function. As for the light emitting layer of the organic light emitting device of the present invention, a red light emitting material, a green light emitting material, or a blue light emitting material can be used as the light emitting material, and two or more light emitting materials can be mixed and used if necessary. The light-emitting material may be a host material alone or a mixture of a host material and a dopant material, and the light-emitting layer is preferably formed using a mixture of a host material and a dopant material.

Preferably, the host material of the present invention is selected from 4,4' -bis (9-carbazole) biphenyl (abbreviated as CBP), 9, 10-bis (2-naphthyl) anthracene (abbreviated as ADN), 4-bis (9-carbazolyl) biphenyl (abbreviated as CPB), 9' - (1, 3-phenyl) bis-9H-carbazole (abbreviated as mCP), 4' -tris (carbazol-9-yl) triphenylamine (abbreviated as TCTA), 9, 10-bis (1-naphthyl) anthracene (abbreviated as. alpha. -AND), N ' -bis- (1-naphthyl) -N, N ' -diphenyl- [1,1':4', 1':4', 1' -tetrabiphenyl ] -4,4' -diamino (abbreviated as 4P-NPB), 1,3, 5-tris (9-carbazolyl) benzene (abbreviated as TCP) and the like, which may be a single-layer structure composed of a single substance or a single-layer structure or a multi-layer structure composed of different substances.

The guest material of the light-emitting layer of the present invention may include one material or a mixture of two or more materials, and the light-emitting material is classified into a blue light-emitting material, a green light-emitting material, and a red light-emitting material. Preferably, the luminescent material of the present invention is a blue luminescent material, and the object of the blue luminescent layer is selected from (6- (4- (diphenylamino (phenyl) -N, N-diphenylpyrene-1-amine) (DPAP-DPPA for short), 2,5,8, 11-tetra-tert-butylperylene (TBPe for short), 4' -bis [4- (diphenylamino) styryl ] perylene]Biphenyl (BDAVBi for short), 4' -di [4- (di-p-tolylamino) styryl]Biphenyl (DPAVBi for short), bis (2-hydroxyphenyl pyridine) beryllium (Bepp for short)₂) Bis (4, 6-difluorophenylpyridine-C2, N) picolinoyiridium (FIrpic).

The doping ratio of the host material and the guest material of the light-emitting layer is preferably varied depending on the materials used, and the doping film thickness ratio of the guest material of the light-emitting layer is usually 0.01 to 20%, preferably 0.1 to 15%, more preferably 1 to 10%.

The hole-blocking layer is a layer which transports electrons and blocks holes, and is preferably the present inventionThe hole blocking layer is selected from 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP for short), 1,3, 5-tri (N-phenyl-2-benzimidazole) benzene (TPBi for short) and tri (8-hydroxyquinoline) aluminum (III) (Alq for short)₃) 8-hydroxyquinoline-lithium (Liq), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (BAlq), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-Triazole (TAZ), and the like, which may be a single structure composed of a single substance or a single-layer structure or a multi-layer structure composed of different substances.

The electron transport layer is a layer having a function of transporting electrons, and functions to inject electrons and balance carriers. The electron transport material of the present invention may be selected from known oxadiazole derivatives, anthraquinone dimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinone dimethane and its derivatives, fluorenone derivatives, diphenoquinone derivatives, and metal complexes of 8-hydroxyquinoline and its derivatives, and preferably, the electron transport layer is selected from 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (BCP), 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (TPBi), and tris (8-hydroxyquinoline) aluminum (III) (Alq)₃) 1,3, 5-tris [ (3-pyridyl) -3-phenyl)]Benzene (abbreviated as TMPYPB), 8-hydroxyquinoline-lithium (abbreviated as Liq), bis (2-methyl-8-hydroxyquinoline) (4-phenylphenol) aluminum (III) (abbreviated as BAlq), 3- (biphenyl-4-yl) -5- (4-tert-butylphenyl) -4-phenyl-4H-1, 2, 4-triazole (abbreviated as TAZ) and the like, and the structure may be a single structure formed by a single substance or a single-layer structure or a multi-layer structure formed by different substances.

The electron injection layer material is a material that assists the injection of electrons from the cathode into the organic layer. The best choice of material is usually a corrosion resistant high work function metal as the cathode, with Al and Ag being common materials. Electron injection materials have been developed to date and include two types; one type is an alkali metal compound, such as lithium oxide (Li)₂O), lithium boron oxide (LiBO)₂) Cesium carbonate (Cs)₂CO₃) Potassium silicate (K)₂SiO₃) And the optimal thickness is generally 0.3-1.0 nm, and the device formed by the compounds can reduce the driving voltage and improve the deviceThe piece efficiency. In addition, acetate compounds of alkali metals (CH)₃COOM, where M is Li, Na, K, Rb, Cs) also have similar effects. Another class is alkali metal fluorides (MF, where M is Li, Na, K, Rb, Cs), and if Al is used as the cathode material, the optimum thickness of these materials is typically less than 1.0 nm. Preferably, the electron injection layer according to the present invention may be selected from LiF.

In the cathode material, a metal material having a small work function is generally preferable in order to inject electrons into the electron injection/transport layer or the light-emitting layer. For example, metals such as lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, aluminum, scandium, vanadium, zinc, yttrium, indium, cerium, samarium, europium, terbium, ytterbium, and the like, alloys of 2 or more of these metals, or alloys of 1 or more of these metals and 1 or more of gold, silver, platinum, copper, manganese, titanium, cobalt, nickel, tungsten, tin, graphite, or graphite intercalation compounds, and the like can be used. Examples of the alloy include magnesium-silver alloy, magnesium-indium alloy, magnesium-aluminum alloy, indium-silver alloy, lithium-aluminum alloy, lithium-magnesium alloy, lithium-indium alloy, and calcium-aluminum alloy. The cathode may have a laminated structure of 2 or more layers. The cathode can be prepared by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering. Among them, when light emission of the light-emitting layer is extracted from the cathode, the light transmittance of the cathode is preferably more than 10%. It is also preferable that the sheet resistivity of the cathode is several hundred Ω/□ or less, and the film thickness is usually 10nm to 1 μm, preferably 50 to 200 nm.

The covering layer material is used for reducing the total emission loss and waveguide loss in the OLED device and improving the light extraction efficiency. Alq can be used as the cover material of the invention₃TPBi or any one or the combination of at least two of the triarylamine organic compounds containing spirofluorene.

Preferably, the cathode of the invention uses Ag or Mg-Ag alloy or thin Al.

Preferably, the material of the covering layer is selected from any one or a combination of at least two of the triarylamine organic compounds containing spirofluorene.

The film thicknesses of the hole transporting layer and the electron transporting layer may be selected as appropriate depending on the materials used, and may be selected so as to achieve appropriate values of the driving voltage and the light emission efficiency. Therefore, the film thicknesses of the hole transporting layer and the electron transporting layer are, for example, 1nm to 1um, preferably 2nm to 500nm, and more preferably 5nm to 200 nm.

The order and number of layers to be stacked and the thickness of each layer can be appropriately selected in consideration of the light emission efficiency and the lifetime of the device.

The organic light-emitting device of the present invention preferably has a structure in which: substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode/capping layer. However, the structure of the organic light emitting device is not limited thereto. The organic light-emitting 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 method for forming each layer in the organic light-emitting device is not particularly limited, and any one of vacuum evaporation, spin coating, vapor deposition, blade coating, laser thermal transfer, electrospray, slit coating, and dip coating may be used, and in the present invention, vacuum evaporation is preferably used.

The organic light-emitting device can be widely applied to the fields of panel display, lighting sources, flexible OLEDs, electronic paper, organic solar cells, organic photoreceptors or organic thin film transistors, signs, 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.

Preparation and characterization of the Compounds

Description of raw materials, reagents and characterization equipment:

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 mass spectrum uses British Watts G2-Si quadrupole rod series time-of-flight high resolution mass spectrometer, chloroform is used as solvent;

the element analysis uses a Vario EL cube type organic element analyzer of Germany Elementar company, and the mass of a sample is 5-10 mg;

nuclear magnetic resonance (¹H NMR Spectroscopy) A nuclear magnetic resonance spectrometer model Bruker-510 (Bruker, Germany), 600MHz, CDCl was used₃As solvent, TMS as internal standard.

EXAMPLE 1 Synthesis of Compound 1

Step1: synthesis of intermediate A-1

Toluene (600mL), a-1(12.61g, 0.06mol), b-1(30.45g, 0.06mol), palladium acetate (0.19g, 0.86mmol), sodium tert-butoxide (11.53g, 0.12mol), and tri-tert-butylphosphine (10.8mL of a 1.0M solution in toluene) were added sequentially to a 1L reaction flask under nitrogen, and reacted at 100 ℃ for 2 hours. After the reaction is stopped, the mixture is cooled to room temperature, filtered by using kieselguhr, the filtrate is concentrated, recrystallized by using methanol, filtered by suction and eluted by using methanol to obtain a recrystallized solid, and the intermediate A-1(30.19g, the yield is 79%) is obtained, and the purity of the solid is not less than 99.6% by HPLC (high performance liquid chromatography).

Step2: synthesis of Compound 1

Under nitrogen protection, a 1L reaction flask was charged with toluene solvent (600ml), c-1(7.91g, 32mmol), intermediate A-1(20.38g, 32mmol), and Pd in that order₂(dba)₃(990mg, 1.08mmol), BINAP (0.20g, 3.2mmol) and sodium tert-butoxide (9.9g, 100.8mmol), were dissolved with stirring and reacted under reflux under nitrogen for 24 hours, after completion of the reaction, the reaction solution was washed with dichloromethane and distilled water and extracted by separation. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed, followed by washing with cyclohexane: ethyl acetate 10:1 as eluent for column chromatographySeparation, purification and purification are carried out, and finally the solid compound 1(19.79g, the yield is 77%) is obtained, and the purity of the solid is not less than 99.6% by HPLC detection.

Mass spectrum m/z: 802.3565 (theoretical value: 802.3559). Theoretical element content (%) C₅₈H₄₆N₂O₂: c, 86.75; h, 5.77; n, 3.49; o, 3.98 measured elemental content (%): c, 86.77; h, 5.75; n, 3.48; and O, 3.99.¹H NMR(600MHz,CDCl₃) (δ, ppm): 8.06(dd,1H),7.89(dd,1H),7.82(d,1H), 7.78-7.74 (m,4H), 7.66-7.61 (m,6H), 7.59-7.53 (m,3H),7.51(d,1H), 7.49-7.41 (m,3H), 7.44-7.33 (m,7H), 7.30-7.25 (m,1H),1.27(s,18H), and the above results confirmed that the product was obtained as an aimed product.

EXAMPLE 2 Synthesis of Compound 23

Compound 23(21.10g, 75% yield) was obtained by replacing a-1 in Step1 with an equimolar amount of a-23 and c-1 in Step2 with an equimolar amount of c-23 in example 1, and the purity of the solid was ≧ 99.4% by HPLC.

Mass spectrum m/z: 878.3877 (theoretical value: 878.3872). Theoretical element content (%) C₆₄H₅₀N₂O₂: c, 87.44; h, 5.73; n, 3.19; o, 3.64 measured elemental content (%): 87.44, respectively; h, 5.73; n, 3.17; and O, 3.66.¹H NMR(600MHz,CDCl₃) (δ, ppm): 8.14(d,1H),8.10 to 8.08(m,3H),7.89(dd,1H),7.83(d,1H),7.79 to 7.75(m,4H),7.66 to 7.61(m,3H),7.57(m,1H),7.54(dd,1H),7.53 to 7.50(m,2H),7.49 to 7.47(m,2H),7.46 to 7.39(m,8H),7.39 to 7.33(m,3H),7.28 to 7.25(m,2H),1.27(s,18H), and the above results confirm that the product is obtained as an objective product.

EXAMPLE 3 Synthesis of Compound 58

Step1: reaction to 1L under nitrogen protectionThe flask was charged with compound m-58(28.54g, 65mmol), compound n-58(14.62g, 68mmol), K₂CO₃(21.42g, 155mmol), 500mL of toluene solvent was stirred. Adding catalyst Pd (PPh)₃)₄(0.70g, 0.6mmol), 100mL of distilled water, the temperature was raised to reflux and the reaction was stirred for 10 h. After the reaction was completed, 100mL of distilled water was added to terminate the reaction. Filtration under reduced pressure gave crude intermediate A-1, which was washed three times with distilled water and then recrystallized from toluene, ethanol (10: 1) to give intermediate b-58(24.78g, 72% yield). The purity of the solid is not less than 99.8 percent by HPLC detection.

Step2 and Step3 in example 3 were carried out in the same manner except that a-1 in Step1 in example 1 was changed to equimolar a-23 and b-1 was changed to equimolar b-58, and c-1 in Step2 in example 1 was changed to equimolar c-58, to obtain compound 58(18.48g, yield 70%) with a solid purity ≧ 99.2% by HPLC.

Mass spectrum m/z: 824.3408 (theoretical value: 824.3403). Theoretical element content (%) C₆₀H₄₄N₂O₂: c, 87.35; h, 5.38; n, 3.40; o, 3.88 measured element content (%): c, 87.35; h, 5.35; n, 3.40; and O, 3.91.

EXAMPLE 4 Synthesis of Compound 68

The same procedures were repeated except for changing a-1 to equimolar a-23 and b-1 to equimolar b-68 in Step1 in example 1 and changing c-1 to equimolar c-68 in Step2 in example 1 to obtain 68(17.91g, 73% yield) as a compound with a solid purity of 99.3% by HPLC.

Mass spectrum m/z: 766.2629 (theoretical value: 766.2620). Theoretical element content (%) C₅₆H₃₄N₂O₂: c, 87.71; h, 4.47; n, 3.65; o, 4.17 measured elemental content (%): c, 87.73; h, 4.45; n, 3.67; and O, 4.15.¹H NMR(600MHz,CDCl₃)(δ,ppm)：8.12–8.08(m,3H),7.90–7.82(m,4H),7.77(s,2H),7.67(d,1H),7.64–7.57(m,7H),7.56–7.51(m,3H),7.48(dd,1H),7.46–7.40(m,9H),7.35 to 7.32(m,2H),7.30(d,1H),7.27(dd,1H), the above results confirmed that the product was obtained as the objective product.

EXAMPLE 5 Synthesis of Compound 89

Step1 toluene (600mL), a-89(19.88g, 0.06mol), b-89(15.22g, 0.06mol), palladium acetate (0.19g, 0.86mmol), sodium tert-butoxide (11.53g, 0.12mol) and tri-tert-butylphosphine (10.8mL of a 1.0M solution in toluene) were added sequentially to a 1L reaction flask under nitrogen and reacted at 100 ℃ for 2 hours. After the reaction was stopped, the mixture was cooled to room temperature, filtered through celite, the filtrate was concentrated, recrystallized from methanol, filtered with suction and rinsed with methanol to give a recrystallized solid, intermediate a-89(22.93g, 73% yield), and a solid purity of 99.7% or more by HPLC.

Step2 substitution of b-1 for equimolar b-68 gave compound 89(16.70g, 73% yield) with a solid purity ≧ 99.4% by HPLC.

Mass spectrum m/z: 714.2313 (theoretical value: 714.2307). Theoretical element content (%) C₅₂H₃₀N₂O₂: c, 87.37; h, 4.23; n, 3.92; o, 4.48 measured elemental content (%): c, 87.38; h, 4.22; n, 3.93; and O, 4.47.¹H NMR(600MHz,CDCl₃) (δ, ppm): 8.84 to 8.80(m,2H),8.33(dd,1H),8.26(dd,1H),8.10(dd,1H),7.94 to 7.85(m,4H),7.74 to 7.58(m,10H),7.55 to 7.49(m,3H),7.47 to 7.42(m,3H),7.37 to 7.32(m,2H),7.27(d,1H),7.16(dd,1H),6.97(dd,1H), and the above results confirmed that the product was obtained as an objective product.

EXAMPLE 6 Synthesis of Compound 92

Compound 92(15.25g, 69%) was obtained by replacing a-1 in Step1 with an equimolar amount of a-92 and b-1 with an equimolar amount of b-68 in example 1 and carrying out the same procedures, and the purity of the solid was ≧ 99.6% by HPLC.

Mass spectrum m/z: 690.2312 (theoretical value: 690.2307). Theoretical element content (%) C₅₀H₃₀N₂O₂: c, 86.94; h, 4.38; n, 4.06; o, 4.63 measured elemental content (%): c, 86.95; h, 4.38; n, 4.05; and O, 4.63.

EXAMPLE 7 Synthesis of Compound 106

By replacing b-1 in Step1 in example 1 with equimolar b-106 and carrying out the same procedures, compound 106(17.54g, 74% yield) was obtained with a solid purity of 99.5% by HPLC.

Mass spectrum m/z: 740.2477 (theoretical value: 740.2464). Theoretical element content (%) C₅₄H₃₂N₂O₂: c, 87.55; h, 4.35; n, 3.78; o, 4.32 measured elemental content (%): c, 87.55; h, 4.37; n, 3.78; and O, 4.30.¹H NMR(600MHz,CDCl₃) (δ, ppm): 8.14(d,1H), 8.09-8.03 (m,2H),7.99(dd,1H), 7.95-7.92 (m,1H),7.88(m,2H), 7.83-7.78 (m,3H),7.68(d,1H),7.64(m,4H),7.60(d,1H), 7.57-7.50 (m,5H), 7.50-7.43 (m,6H), 7.41-7.34 (m,4H),7.25(dd,1H), and the above results confirmed that the product was obtained as an aimed product.

EXAMPLE 8 Synthesis of Compound 158

Step1: under the protection of nitrogen, compound m-158(13.12g, 65mmol), compound n-158(21.70g, 70mmol), and K were added to a 1L reaction flask₂CO₃(20.73g, 150mmol), 500mL of toluene solvent was stirred. Adding catalyst Pd (PPh)₃)₄(0.70g, 0.6mmol), 100mL of distilled water, the temperature was raised to reflux and the reaction was stirred for 10 h. After the reaction was completed, 100mL of distilled water was added to terminate the reaction. Filtering under reduced pressure to obtain crude intermediate A-1, and purifying withWashed three times with distilled water, then recrystallized from toluene, ethanol (10: 1) to give intermediate c-158(14.22g, 73% yield). The purity of the solid is not less than 99.6 percent by HPLC detection.

Step2 and Step3 in example 8 were carried out in the same manner except that c-1 in Step2 in example 1 was changed to equimolar c-158, to give 158(18.93g, yield 66%) having a solid purity of 99.0% by HPLC.

Mass spectrum m/z: 895.3599 (theoretical value: 895.3596). Theoretical element content (%) C₆₃H₄₉N₃And OS: c, 84.44; h, 5.51; n, 4.69; o, 1.79; s, 3.58 measured element content (%): c, 84.43; h, 5.52; n, 4.68; o, 1.79; and S, 3.59.

EXAMPLE 9 Synthesis of Compound 162

In the same manner as in Step1, a-1 in example 1 was replaced with equimolar a-162, and c-1 in Step1 in example 1 was replaced with equimolar c-162, to give compound 162(19.92g, yield 76%), and purity ≧ 99.2% by HPLC.

Mass spectrum m/z: 818.3340 (theoretical value: 818.3331). Theoretical element content (%) C₅₈H₄₆N₂And OS: c, 85.05; h, 5.66; n, 3.42; o, 1.95; s, 3.91 measured element content (%): c, 85.05; h, 5.65; n, 3.40; o, 1.96; and S, 3.93.

EXAMPLE 10 Synthesis of Compound 189

Compound 189(15.71g, 64% yield) was obtained by replacing a-1 in Step1 of example 1 with equimolar a-23 and equimolar b-1 with equimolar b-189, and the purity of the solid was ≧ 99.2% by HPLC.

Mass spectrum m/z: 766.2628 (theoretical value: 766.2620). Theoretical element content (%) C₅₆H₃₄N₂O₂: c, 87.71; h, 4.47; n, 3.65; o, 4.17 measured elemental content (%): c, 87.75; h, 4.46; n, 3.61; and O, 4.18.

The triarylamine organic compound containing spirofluorene is used as a CP layer material in an organic light-emitting device, and the refractive index (n) is determined by J.A.Woollam company, model: measuring by an M-2000 spectrum ellipsometer, wherein the measurement is in an atmospheric environment, and the scanning range of the ellipsometer 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 results of thermal performance and refractive index tests of the triarylamine organic compound containing spirofluorene and the existing material are shown in the following table 1.

TABLE 1 photophysical characteristic test of light emitting device

Cover material	Refractive index n @450nm	Cover material	Refractive index n @450nm
				Compound 1	2.559	Compound 106	2.506
Compound 23	2.534	Compound 158	2.395
				Compound 58	2.489	Compound 162	2.479
Compound 68	2.541	Compound 189	2.432
				Compound 89	2.456	CP-1	2.163
Compound 92	2.482

As can be seen from the data in the table, compared with a similar compound CP-1, the triarylamine organic compound containing spirofluorene has high refractive index, and can be applied to a covering layer of an OLED device to effectively improve the light extraction efficiency of the device, thereby improving the luminous efficiency of an organic light-emitting device.

Comparative example 1 device preparation example:

comparative example 1: the organic light-emitting device is prepared by a vacuum thermal evaporation method. The experimental steps are as follows: and (3) putting the ITO-Ag-ITO substrate into distilled water for cleaning for 3 times, ultrasonically cleaning for 15 minutes, after the cleaning of the distilled water is finished, ultrasonically cleaning solvents such as isopropanol, acetone, methanol and the like in sequence, drying at 120 ℃, and conveying to an evaporation plating machine.

Evaporating a hole injection layer 2T-NATA/50nm, an alpha-NPD/30 nm hole transport layer and an evaporation main body on the prepared ITO-Ag-ITO electrode in a layer-by-layer vacuum evaporation modeADN: doping DPAP-DPPA 5% mixed/30 nm, then evaporating an electron transport layer Alq₃30nm, an electron injection layer LiF/0.5nm, a cathode Mg-Ag (Mg: Ag doping ratio is 9:1)/20nm, and then a cover layer material CP-1/60nm is evaporated on the cathode layer. And the device was sealed in a glove box, thereby preparing an organic light emitting device. After the organic light-emitting device is manufactured according to the steps, the photoelectric property of the device is measured, and the molecular structural formula of the related material is as follows:

[ examples 1 to 10]

Examples 1 to 10: the capping layer material of the organic light emitting device was sequentially changed to the compounds 1, 23, 58, 68, 89, 92, 106, 158, 162, 189 of the present invention, and the other steps were the same as in comparative example 1.

The test software, computer, K2400 digital source manufactured by Keithley corporation, usa, and PR788 spectral scanning luminance meter manufactured by Photo Research corporation, usa were combined into a combined IVL test system to test the luminous efficiency of the organic light emitting device.

The results of the light emission characteristic test of the obtained organic light emitting device are shown in table 2. Table 2 shows the results of the test of the light emitting characteristics of the light emitting devices prepared by the compounds prepared in the examples of the present invention and the comparative materials.

Table 2 test of light emitting characteristics of light emitting device

As can be seen from the results in table 2, the triarylamine-based organic compound containing spirofluorene of the present invention is applied to an organic light emitting device, particularly as a capping layer material, and exhibits an advantage of higher light emitting efficiency and is an organic light emitting material with good performance, compared to comparative example 1.

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

1. A triarylamine organic compound containing spirofluorene is characterized in that the molecular structure is shown as formula I:

x is selected from O or S;

2. The organic compound of claim 1, wherein R is a compound selected from the group consisting of a chiral aromatic amine, a chiral₁、R₂、R₃At least one of the groups is selected from one of methyl, ethyl, isopropyl, tertiary butyl, cyclopentyl, cyclohexyl, adamantyl, bornyl and norbornyl; the rest is one of methyl, ethyl, isopropyl, tertiary butyl, cyclopentyl, cyclohexyl, adamantyl, bornyl, norbornyl, phenyl, pentadeuterated phenyl, tolyl, biphenyl, terphenyl and naphthyl; m is selected from 0,1 or 2; n is selected from 0,1 or 2; p is selected from 0,1 or 2.

3. The organic compound of claim 1, wherein the triarylamine compound contains spirofluorene

One selected from the following groups:

4. the organic compound of claim 1, wherein the triarylamine compound contains spirofluorene

In (C) X₁Selected from O,S or NR₀Wherein R is₀One selected from methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, phenyl, tolyl, biphenyl and naphthyl; q is selected from 0,1, 2,3 or 4;

5. the triarylamine-based organic compound containing spirofluorene according to claim 1, wherein L is₁、L₂、L₃Independently selected from a single bond or any one of the following groups:

6. the organic compound of claim 1, wherein the triarylamine compound contains spirofluorene

One selected from the following groups:

7. the organic compound of claim 1, wherein R is a compound selected from the group consisting of a chiral aromatic amine, a chiral₅Selected from hydrogen,Deuterium, methyl, ethyl, isopropyl, tert-butyl, cyclohexyl, cyclopentyl or one of the following substituents:

o is selected from 0,1 or 2.

8. The triarylamine organic compound containing spirofluorene according to claim 1, wherein the triarylamine organic compound containing spirofluorene is selected from any one of the following chemical structures:

9. an organic light-emitting device comprising a cathode, an anode, one or more organic layers disposed between the cathode and the anode, and one or more organic layers disposed outside the cathode and the anode, wherein the organic layers disposed between the cathode and the anode comprise at least one 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, and an electron injection layer; the organic layer arranged outside the cathode and the anode comprises a covering layer, wherein the covering layer contains any one or the combination of at least two of the triarylamine organic compounds containing spirofluorene as claimed in any one of claims 1-8.