CN113443998A

CN113443998A - Triarylamine organic compound and organic light-emitting device thereof

Info

Publication number: CN113443998A
Application number: CN202110710145.0A
Authority: CN
Inventors: 韩春雪; 赵倩; 鲁秋
Original assignee: Changchun Hyperions Technology Co Ltd
Current assignee: Changchun Hyperions Technology Co Ltd
Priority date: 2021-06-11
Filing date: 2021-06-25
Publication date: 2021-09-28
Anticipated expiration: 2041-06-25
Also published as: CN113443998B

Abstract

The invention provides a triarylamine organic compound and an organic light-emitting device thereof, and relates to the technical field of organic photoelectric materials. The triarylamine is taken as the center and connected with the benzo aliphatic ring group, so that the electron-donating capability of the compound is further enhanced, the compound has excellent hole transport performance, has the advantages of high luminous efficiency and low driving voltage, and is a good hole transport material; the triarylamine organic compound is used as a covering layer material to be applied to an organic light-emitting device, and can improve the light extraction efficiency, so that the light-emitting efficiency of the organic light-emitting device is improved. The triarylamine organic compound has good film forming property, high glass transition temperature (Tg), good stability and simple and easy synthesis operation, 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 and organic light-emitting device thereof

This application claims priority to chinese patent application CN202110653987.7, filed 2021, 11/06/11. The present application refers to the above-mentioned chinese patent application in its entirety.

Technical Field

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

Background

With the advancement of the information industry, conventional displays have been unable to meet the requirements of people, such as: cathode Ray Tube (CRT) displays are bulky and have high drive voltages; a Liquid Crystal Display (LCD) has low brightness, a narrow viewing angle and a small working temperature range; plasma Display Panels (PDPs) are expensive, have low resolution, and consume a lot of power. Organic Light-Emitting devices (OLEDs) have the characteristics of energy saving, fast response speed, stable color, strong environmental adaptability, no radiation, Light weight, thin thickness and the like, and along with the rapid development of the fields of optoelectronic communication and multimedia in recent years, Organic optoelectronic materials have become the core of information and electronic industries in modern society.

An organic light emitting device is a self light emitting device utilizing the following principle: by applying an electric field, the fluorescent substance emits light by the recombination energy of holes injected from the anode and electrons injected from the cathode. It has the following structure: a cathode, an anode, and one or more layers of organic material disposed between and beyond the cathode and anode. In order to improve efficiency and stability of the organic light emitting device, the organic material layer includes a plurality of layers having different materials, such as a Hole Injection Layer (HIL), a Hole Transport Layer (HTL), a light emitting layer, an Electron Transport Layer (ETL), an Electron Injection Layer (EIL), and a capping layer (CPL).

Since the device is operating to generate joule heat, this heat often causes recrystallization of the material. Crystallization can destroy the uniformity of the film and also destroy the good interfacial contact between the hole transport layer and the anode and the organic layer, resulting in reduced efficiency and lifetime of the device. And the injection of holes and electrons is unbalanced due to the low mobility of the holes, and the holes and the electrons cannot be effectively combined in the light-emitting layer, so that the light-emitting efficiency of the organic light-emitting device is reduced. Therefore, the research on the organic hole transport material focuses on improving the thermal stability and hole mobility of the material.

In general, in the future, the OLED is developed to be a white light device and a full color display device with high efficiency, long lifetime and low cost, but the industrialization process of the technology still faces many key problems, and how to design a hole transport layer material with better performance to adjust is a problem that needs to be solved urgently by those skilled in the art.

Disclosure of Invention

The invention aims to provide a triarylamine organic compound and an organic light-emitting device thereof based on the prior art and aiming at industrialization, and the organic light-emitting device prepared by using the triarylamine organic compound solves the problem of unmatched electron/hole migration in an organic material layer, thereby remarkably improving the comprehensive performance of the device in the aspects of luminous efficiency, voltage, color coordinates and the like; the organic light-emitting device solves the problems by being used as a main composition of a hole transport layer in the organic light-emitting device, and the molecular structure general formula of the organic light-emitting device is shown as the formula I:

wherein C is selected from the group shown as the following formula a:

the R is₀The same or different from each other, and each independently selected from hydrogen, deuterium, a halogen atom, cyano, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl, or adjacent R may be bonded to form a substituted or unsubstituted C3-C7 aliphatic ring; the ring M is a substituted or unsubstituted aliphatic ring of C3-C7; n is selected from 0,1, 2,3. 4,5 or 6;

the x represents a connecting site, wherein one carbon on a benzene ring is the connecting site, or one carbon on an aliphatic ring is the connecting site;

a, B is the same or different and is selected from one of the groups shown in formula b-1 or formula b-2:

in the formulas b-1 and b-2,

the R is the same or different from each other and is independently selected from substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C6-C25 aryl, or adjacent R can be connected to form a substituted or unsubstituted fluorene ring;

the R is_bThe aryl group is the same or different from each other and is independently 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;

l is selected from a single bond or phenylene;

b is selected from 0,1, 2,3 or 4; when b is greater than 1, each R_bSame or different, adjacent R_bCan be bonded to form a ring structure; m is selected from 0,1, 2 or 3; when m is greater than 1, each R_bSame or different, adjacent R_bCan be bonded to form a ring structure;

said L₀Independently selected from a single bond, deuterium substituted or unsubstituted arylene of C6-C25, substituted or unsubstituted heteroarylene of C2-C20;

said L₁、L₂Independently selected from one of single bond, substituted or unsubstituted arylene of C6-C25 and substituted or unsubstituted heteroarylene of C2-C20.

The invention also provides an organic light-emitting device which comprises an anode, a cathode and an organic layer, wherein the organic layer is positioned between the anode and the cathode or positioned outside more than one of the anode and the cathode, and the organic layer contains any one or the combination of at least two of the triarylamine organic compounds.

The invention has the beneficial effects that:

the invention provides a triarylamine organic compound and an organic light-emitting device thereof. In the absence of further electron-donating substituents at the linking group of the benzoalicyclic group to the nitrogen atom, especially when the benzoalicyclic group is directly linked to the nitrogen atom (L)₀The compound is a single bond), the distribution of the electron cloud in the compound is more balanced, and the hole transport performance is improved under the proper HOMO energy level; under a proper LUMO energy level, the recombination efficiency of excitons in a light-emitting layer is improved, and when the organic light-emitting device is used, the exciton utilization rate can be effectively improved, the light-emitting efficiency of the device is improved, and the driving voltage of the device is reduced; therefore, the triarylamine organic compound of the invention shows more excellent performance. The triarylamine organic compound is used as a hole transport layer material to be applied to an organic light-emitting device, and has the advantages of high light-emitting efficiency and low driving voltage.

The triarylamine organic compound is used as a covering layer material to be applied to an organic light-emitting device, 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 the OLED device, and improves light extraction efficiency, thereby improving the light-emitting efficiency of the organic light-emitting device. In addition, the triarylamine organic compound has good film forming property, high glass transition temperature (Tg) and good stability, and can prolong the service life of devices.

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, isopropyl, isobutyl, sec-butyl, tert-butyl, the isomeric form of n-pentyl, the isomeric form of n-hexyl, the isomeric form of n-heptyl, the isomeric form of n-octyl, the isomeric form of n-nonyl, the isomeric form 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 cycloalkyl 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, and preferably has 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, and most preferably 6 to 12 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, particularly preferably 3 to 15 carbon atoms, and most preferably 3 to 12 carbon atoms, 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 alkenyl group in the present invention means a monovalent group obtained by removing one hydrogen atom from an olefin molecule, and includes a monoalkenyl group, a dienyl group, a polyalkenyl group, and the like. Preferably from 2 to 60 carbon atoms, more preferably from 2 to 30 carbon atoms, particularly preferably from 2 to 15 carbon atoms, most preferably from 2 to 6 carbon atoms. Examples of the alkenyl group include vinyl, butadienyl and the like, but are not limited thereto. The alkenyl group is preferably a vinyl group.

The arylene group in the present invention refers to a general term of divalent groups remaining after two hydrogen atoms are removed from the aromatic core carbon of the aromatic compound molecule, and may be monocyclic arylene group, polycyclic arylene group or condensed ring arylene group, and preferably has 6 to 25 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 14 carbon atoms, and most preferably 6 to 12 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, particularly preferably 6 to 15 carbon atoms, and most preferably 3 to 12 carbon atoms, the linking site of the heteroarylene group may be located on a ring-forming carbon atom or on 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 alkenyl, substituted aryl, substituted heteroaryl, substituted arylene, substituted heteroarylene, etc., means mono-or poly-substituted with groups independently selected from, but not limited to, 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, etc., preferably with groups selected from, but not limited to, deuterium, methyl, ethyl, isopropyl, tert-butyl, phenyl, biphenyl, terphenyl, naphthyl, anthracyl, phenanthryl, benzophenanthryl, perylenyl, pyrenyl, benzyl, tolyl, fluorenyl, 9-dimethylfluorenyl, 9-diphenylfluorenyl, 9-methyl-9-phenylfluorenyl, 9-methylfluorenyl, 9-diphenylfluorenyl, etc, Groups of dianilino, dimethylamino, carbazolyl, 9-phenylcarbazolyl, acridinyl, furyl, thienyl, benzofuryl, benzothienyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, dibenzofuryl, dibenzothienyl, phenothiazinyl, phenoxazinyl, indolyl are mono-or polysubstituted. In addition, the above substituents may be substituted by one or more substituents described for deuterium, a halogen atom, a cyano group, an alkyl group, a cycloalkyl group, and an aryl group.

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, fluorene, cyclopentene, cyclopentane, cyclohexane acene, quinoline, isoquinoline, dibenzothiophene, phenanthrene or pyrene, but not limited thereto.

In the present invention, adjacent R groups may be connected to form a substituted or unsubstituted fluorene ring, which means that the fluorene group may be substituted by R, and 2R substituents may be combined with each other to form a substituted or unsubstituted spiro structure, specifically, the ring formation mode is as follows:

the invention provides a triarylamine organic compound, the molecular structural general formula of which is shown as formula I:

wherein C is selected from the group shown as the following formula a:

the R is₀The same or different from each other, and each independently selected from hydrogen, deuterium, a halogen atom, cyano, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkyl, substituted or unsubstituted C2-C30 alkenyl, substituted or unsubstituted C6-C25 aryl, substituted or unsubstituted C2-C20 heteroaryl, or adjacent R may be bonded to form a substituted or unsubstituted C3-C7 aliphatic ring; the ring M is a substituted or unsubstituted aliphatic ring of C3-C7; n is selected from 0,1, 2,3, 4,5 or 6;

in the formulas b-1 and b-2,

l is selected from a single bond or phenylene;

Preferably, said adjacent R₀The two are optionally linked to each other to form a saturated or unsaturated alicyclic mono-or polycyclic ring.

Preferably, said L₀Selected from the group consisting of a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstitutedThe substituted or unsubstituted biphenylene group, the substituted or unsubstituted fluorenylene group, the substituted or unsubstituted anthracenylene group, the substituted or unsubstituted dibenzofuranylene group and the substituted or unsubstituted dibenzothiophenylene group, wherein the substituent is one or more deuterium.

Preferably, the formula a is selected from one of the following groups:

wherein, R is₁One selected from hydrogen, deuterium, a halogen atom, a cyano group, a substituted or unsubstituted C1-C15 alkyl group, a substituted or unsubstituted C3-C15 cycloalkyl group, a substituted or unsubstituted C6-C25 aryl group and a substituted or unsubstituted C2-C20 heteroaryl group;

c is selected from 0 or 1; k is selected from 0,1 or 2; i is selected from 0,1, 2 or 3; j is selected from 0,1, 2,3, 4,5, 6 or 7; d is selected from 0,1, 2,3 or 4; h is selected from 0,1, 2,3, 4 or 5; e is selected from 0,1, 2,3, 4,5 or 6; f is selected from 0,1, 2,3, 4,5, 6,7 or 8; g is selected from 0,1, 2,3, 4,5, 6,7, 8,9 or 10.

More preferably, the formula a is selected from one of the following groups:

preferably, the formula b-1 is selected from any one of the following groups:

the formula b-2 is selected from any one of the following groups:

wherein R is_bThe substituent group in the "substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group" is selected from one or more of deuterium, methyl group, isopropyl group, tert-butyl group, adamantyl group, norbornyl group, substituted or unsubstituted phenyl group, phenanthryl group, anthryl group, triphenylene group, deuterated biphenyl group, 9-dimethylfluorenyl group, 9-diphenylfluorenyl group, 9-methyl-9-phenylfluorenyl group, dibenzofuranyl group, dibenzothiophenyl group, and the substituent group in the "substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group" is selected from one or more of deuterium, methyl group, isopropyl group, tert-butyl group, adamantyl group, norbornyl group, phenyl group, biphenyl group, and naphthyl group, and in the case of being substituted with a plurality of substituent groups, the plurality of substituent groups are the same as or different from each other.

More preferably, the formula b-1 is selected from any one of the following groups:

the formula b-2 is selected from any one of the following groups:

preferably, said L₁、L₂Independently selected from a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted fluorenylene, substituted or unsubstituted anthrylene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenylene, and substituted or unsubstituted naphthylene, wherein the substituent is one or more of deuterium, ethyl, isopropyl, tert-butyl, phenyl, and pentadeuterated phenyl, and in the case of substitution with a plurality of substituents, the plurality of substituents are the same as or different from each other.

Preferably, the first and second liquid crystal materials are,said L₀、L₁、L₂Independently selected from a single bond or one of the following groups:

more preferably, said L₀、L₁、L₂Independently selected from a single bond or one of the following groups:

preferably, said R is_bOne selected from hydrogen, deuterium or a group shown below:

more preferably, R is_bSelected from hydrogen, deuterium or one of the following groups:

most preferably, the triarylamine organic compound is selected from any one of the following chemical structures:

the triarylamine organic compound of formula I of the present invention can be prepared by conventional Buchwald reaction in the art, i.e. under nitrogen atmosphere, amine compound a and halogen compound b are subjected to Buchwald reaction to obtain intermediate A, then the intermediate A and halogen compound c are subjected to Buchwald reaction, and the intermediate A and halogen compound c are reacted under corresponding catalyst, organic base, ligand, solution and corresponding temperature to obtain the corresponding compound of formula I, wherein the halogen compound is a compound containing Cl, Br or 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.

Preferably, the organic layer comprises a hole transport layer, and the hole transport layer contains any one or a combination of at least two of the triarylamine organic compounds.

Preferably, the organic layer includes a capping layer containing any one or a combination of at least two of the triarylamine organic compounds according to the present invention.

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., the hole injection layer may be a single structure made of a single substance, or a single-layer or multi-layer structure made of different substances, and the hole injection layer material may include other known materials suitable for the hole injection layer, in addition to the above materials and combinations thereof.

The hole transport layer is a layer having a function of transporting holes, and the hole transport layer may include a first hole transport layer material and a second hole transport layer material. 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 polymer materials such as poly-p-phenylene derivatives, polyaniline and derivatives thereof, polythiophene and derivatives thereof, polyvinylcarbazole and derivatives thereof, polysilane and derivatives thereof, 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) and the like, which may be a single structure composed of a single substance or a single-layer structure or a multi-layer structure formed of different substances, and the hole transport layer may include other known materials suitable for the hole transport layer in addition to the above materials and combinations thereof. More preferably, the hole transport layer is selected from any one or a combination of at least two of the triarylamine organic compounds described in the present invention. .

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, the electron blocking layer material may be a single structure made of a single substance, or a single-layer structure or a multi-layer structure made of different substances, and may include other known materials suitable for an electron blocking layer in addition to the above materials and combinations thereof.

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 (CBP), 9, 10-bis (2-naphthyl) Anthracene (ADN), 4-bis (9-carbazolyl) biphenyl (CPB), 9' - (1, 3-phenyl) bis-9H-carbazole (mCP), 4',4 ″ -tris (carbazol-9-yl) triphenylamine (TCTA), 9, 10-bis (1-naphthyl) anthracene (α -AND), N' -bis- (1-naphthyl) -N, N '-diphenyl- [1,1':4',1 ": 4', 1' -tetrabiphenyl ] -4,4' -diamino (4PNPB), 1,3, 5-tris (9-carbazolyl) benzene (TCP), and the like. In addition to the above materials and combinations thereof, the light-emitting layer host material may also include other known materials suitable for use as a light-emitting layer, such as red light-emitting layer host materials represented by RH-1 to RH-12 below:

the light-emitting layer guest can be selected from 9, 10-di [ N- (p-tolyl) anilino]Anthracene (TPA), 4- (dicyanomethylene) -2-methyl-6- (4-dimethylaminostyryl) -4H-pyran (DCM), tris [ 1-phenylisoquinoline-C2, N]Iridium (III) (Ir (piq)₃) Bis (1-phenylisoquinoline) (acetylacetonato) iridium (Ir (piq))₂(acac)) and the like. In addition to the above materials, the light-emitting layer guest material may include other known materials suitable for use as a light-emitting layer, such as red light-emitting layer guest materials as represented by RD-1 to RD-14 below:

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

The hole-blocking layer is for transporting electrons and for blocking holesThe hole blocking layer is preferably selected from the group consisting of 2, 9-dimethyl-4, 7-diphenyl-1, 10-phenanthroline (abbreviated as BCP), 1,3, 5-tris (N-phenyl-2-benzimidazole) benzene (abbreviated as TPBi), and tris (8-hydroxyquinoline) aluminum (III) (abbreviated as Alq)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. In addition to the above materials, the hole blocking layer material may include other known materials suitable for use as a hole blocking layer.

The electron transport layer is a layer having a function of transporting electrons, and plays a role of injecting electrons and balancing carriers, and the electron transport layer may include a first electron transport layer material and a second electron transport layer material. The electron transport material can be selected from metal complexes of known oxadiazole derivatives, anthraquinone dimethane and derivatives thereof, benzoquinone and derivatives thereof, naphthoquinone and derivatives thereof, anthraquinone and derivatives thereof, tetracyanoanthraquinone dimethane and derivatives thereof, fluorenone derivatives, diphenoquinone derivatives, 8-hydroxyquinoline and derivatives thereof, and can be a single structure formed by a single substance or a single-layer structure or a multi-layer structure formed by different substances. In addition to the above materials, the electron transport layer material may also include other known materials suitable for use as an electron transport layer. Preferably, the electron transport layer according to the present invention is selected from a mixture of one or more of the following compounds.

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 compound can reduce the driving voltage and improve the efficiency of the device. 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 the triarylamine organic compound provided by the invention or the combination of at least two of the TPBi and the triarylamine organic compound.

Preferably, the material of the covering layer according to the present invention is selected from any one or a combination of at least two of the organic compounds for the covering layer according to the present invention.

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.

(1) Anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/cathode/capping layer;

(2) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/cathode;

(3) anode/hole injection layer/hole buffer layer/hole transport layer/light emitting layer/hole blocking layer/cathode;

(4) anode/hole transport layer/light emitting layer/electron transport layer/cathode;

(5) anode/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode;

(6) anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode;

(7) anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode;

(8) anode/hole injection layer/hole buffer layer/hole transport layer/light emitting layer/electron transport layer/cathode;

(9) anode/hole injection layer/hole buffer layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode;

(10) anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode;

(11) anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode;

(12) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode;

(13) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode;

(14) anode/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/cathode;

(15) anode/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;

(16) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/cathode;

(17) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;

(18) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron transport layer/cathode/capping layer;

(19) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode;

(20) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode;

(21) anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode;

(22) anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/electron injection layer/cathode;

(23) anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode/capping layer;

(24) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode;

(25) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer;

(26) anode/hole injection layer/hole buffer layer/hole transport layer/electron blocking layer/luminescent layer/hole blocking layer/electron transport layer/electron injection layer/cathode;

(27) anode/hole injection layer/hole buffer layer/hole transport layer/electron blocking layer/luminescent layer/hole blocking layer/electron transport layer/electron injection layer/cathode/capping layer;

(28) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/cathode;

(29) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/electron injection layer/cathode;

(30) anode/hole injection layer/hole transport layer/light emitting layer/hole blocking layer/cathode/capping layer;

(31) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/cathode;

(32) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/electron injection layer/cathode;

(33) anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/hole blocking layer/cathode/capping layer;

(34) anode/hole injection layer/hole transport layer/light emitting layer/cathode/capping layer;

(35) anode/hole injection layer/hole transport layer/light emitting layer/cathode;

(36) anode/hole injection layer/hole buffer layer/hole transport layer/light emitting layer/cathode;

(37) 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 electronic 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. For example, an electron buffer layer can be added between the electron transport layer and the electron injection layer; the organic layer having the same function may be formed in a stacked structure of two or more layers, for example, the electron transport layer may have a first electron transport layer and a second electron transport layer.

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;

EXAMPLE 1 Synthesis of Compound 1

Synthesis of intermediate A-1

To a 1L reaction flask, toluene (600mL), a-1(8.83g, 60mmol), b-1(23.84g, 60mmol), palladium acetate (0.20g, 0.90mmol), sodium tert-butoxide (11.53g, 120mmol), and tri-tert-butylphosphine (8mL in toluene) were added in that order under nitrogen. And reacted under reflux 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-1(21.70g, yield 78%), and purity ≧ 99.7% by HPLC.

Synthesis of Compound 1

Under nitrogen protection, a 1L reaction flask was charged with toluene solvent (600mL), c-1(9.83g, 36mmol), intermediate A-1(16.69g, 36mmol), and Pd in that order₂(dba)₃(0.33g, 0.36mmol), BINAP (0.67g, 1.08mmol) and sodium tert-butoxide (6.92g, 72mmol), 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 subjected to liquid separation and extraction. The organic layer was dried over anhydrous magnesium sulfate, filtered, and then the solvent was removed, followed by washing with cyclohexane: separating, purifying and refining ethyl acetate 10:1 by column chromatography as eluent to obtain compound 1(16.06g, yield 68%), and purity ≧ 99.3% by HPLC.

Mass spectrum m/z: 655.3256 (theoretical value: 655.3239). Theoretical element content (%) C₅₀H₄₁N: c, 91.56; h, 6.30; and N, 2.14. Measured elemental content (%): c, 91.49; h, 6.26; and N, 2.19.

EXAMPLE 2 Synthesis of Compound 9

Compound 9(17.26g) was synthesized in the same manner as in Synthesis example 1 except that c-1 was replaced with an equal mole of c-9, and the purity of the solid was ≧ 99.8% by HPLC. Mass spectrum m/z: 705.3361 (theoretical value: 705.3396). Theoretical element content (%) C₅₄H₄₃N: c, 91.88; h, 6.14; n, 1.98. Measured elemental content (%): c,91.93H, 6.10; and N, 2.03.

EXAMPLE 3 Synthesis of Compound 22

To a 1L reaction flask, toluene (600mL), a-1(4.42g, 30mmol), b-1(23.83g, 60mmol), palladium acetate (0.26g, 1.2mmol), sodium tert-butoxide (11.53g, 120mmol), and tri-tert-butylphosphine (7mL in toluene) were added in that order under nitrogen. And reacted under reflux for 3 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, compound 22(16.37g, 70% yield) was synthesized, and the purity of the solid was ≧ 99.7% by HPLC.

Mass spectrum m/z: 779.3529 (theoretical value: 779.3552). Theoretical element content (%) C₆₀H₄₅N: c, 92.39; h, 5.82; and N, 1.80. Measured elemental content (%): c, 94.44; h, 5.75; n, 1.75.

EXAMPLE 4 Synthesis of Compound 85

Compound 85(19.62g) was synthesized in the same manner as in Synthesis example 1 except that b-1 was replaced with an equal mole of b-2 and c-1 was replaced with an equal mole of c-85, and the purity of the solid was 99.7% or more by HPLC. Mass spectrum m/z: 777.3371 (theoretical value: 777.3396). Theoretical element content (%) C₆₀H₄₃N: c, 92.63; h, 5.57; and N, 1.80. Measured elemental content (%): c, 92.58; h, 5.61; n, 1.77.

EXAMPLE 5 Synthesis of Compound 89

Compound 89(21.11g) was synthesized in the same manner as in Synthesis example 1 except that b-1 was replaced with an equal mole of b-2 and c-1 was replaced with an equal mole of c-89, and its solid purity was determined by HPLC, ≧ 99.4%. Mass spectrum m/z: 825.3357 (theoretical value: 825.3396). Theoretical element content (%) C₆₄H₄₃N: c, 93.06; h, 5.25; and N, 1.70. Measured elemental content (%): c, 92.59; h, 5.28; n, 1.68.

EXAMPLE 6 Synthesis of Compound 135

Compound 135(22.80g) was synthesized in the same manner as in Synthesis example 3 except that b-1 was replaced with an equimolar amount of b-3, and the purity of the solid was ≧ 99.5% by HPLC. Mass spectrum m/z: 999.5789 (theoretical value: 999.5743). Theoretical element content (%) C₇₆H₇₃N: c, 91.24; h, 7.36; and N, 1.40. Measured elemental content (%): c, 91.30; h, 7.31; n, 1.43.

EXAMPLE 7 Synthesis of Compound 139

Compound 139(18.56g) was synthesized in the same manner as in Synthesis example 3 except that b-1 was replaced with an equimolar amount of b-4, and the purity of the solid was ≧ 99.6% by HPLC. Mass spectrum m/z: 835.4199 (theoretical value: 835.4178). Theoretical element content (%) C₆₄H₅₃N: c, 91.94; h, 6.39; n, 1.68. Measured elemental content (%): c, 92.00; h, 6.34; n, 1.69.

EXAMPLE 8 Synthesis of Compound 175

Compound 175(20.55g) was synthesized in the same manner as in Synthesis example 1 except that b-1 was replaced with an equal mole of b-5 and c-1 was replaced with an equal mole of c-175, and the purity of the solid was determined by HPLC (HPLC) and was not less than 99.3%. Mass spectrum m/z: 731.3526 (theoretical value: 731.3552). Theoretical element content (%) C₅₆H₄₅N: c, 91.89; h, 6.20; and N, 1.91. Measured elemental content (%): c, 91.96; h, 6.24; n, 1.87.

EXAMPLE 9 Synthesis of Compound 203

Synthesis of intermediate a-2

Under the protection of nitrogen, a three-neck flask is sequentially added with a compound E-1(10.56g,60mmol), a compound F-1(10.32g,60mmol) and a compound K₂CO₃(16.58g,120mmol)、Pd(PPh₃)₄(1.38g,1.2mmol), 500mL of a toluene/ethanol/water (3:1:1) mixed solvent was added, the mixture was stirred, and the above reactant system was heated under reflux for 8 hours. After the reaction was completed, the reaction mixture was cooled to room temperature, and extracted with deionized water and toluene to obtain an organic layer, and the organic layer was washed with 400mL of deionized water for 3 times, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized from toluene to obtain intermediate a-2(10.05g, yield 75%).

Compound 203(14.77g) was synthesized in the same manner as in Synthesis example 3 except that a-1 was replaced with an equal mole of a-2 and b-1 was replaced with an equal mole of c-1, and its solid purity was determined by HPLC, ≧ 99.9%. Mass spectrum m/z: 607.3207 (theoretical value: 607.3239). Theoretical element content (%) C₄₆H₄₁N: c, 90.90; h, 6.80; and N, 2.30. Measured elemental content (%): c, 90.83; h, 6.75; n, 2.33.

EXAMPLE 10 Synthesis of Compound 223

According to the same method as that of synthesis example 1, intermediate a-4 was synthesized in the same manner as a-2 in example 9, by replacing a-1 with an equal mole of a-4 and replacing b-1 with an equal mole of b-3, and compound 223(19.37g) was synthesized with a solid purity of 99.3% or more by HPLC. Mass spectrum m/z: 779.3516 (theoretical value: 779.3552). Theoretical element content (%) C₆₀H₄₅N: c, 92.39; h, 5.82; and N, 1.80. Measured elemental content (%): c, 92.45; h, 5.86; n, 1.83.

EXAMPLE 11 Synthesis of Compound 233

Using the same procedure as in Synthesis example 3, intermediate a-5 was synthesized in the same manner as a-2 in example 9, replacing a-1 with an equimolar amount of a-5 and an equimolar amount of c-233 in place of b-1, compound 233(16.21g) was synthesized, and purity of the solid was ≧ 99.8% by HPLC. Mass spectrum m/z: 683.3525 (theoretical value: 683.3552). Theoretical element content (%) C₅₂H₄₅N: c, 91.32; h, 6.63; and N, 2.05. Measured elemental content (%): c, 91.26; h, 6.58; and N, 2.10.

EXAMPLE 12 Synthesis of Compound 237

Compound 237(18.49g) was synthesized in the same manner as in Synthesis example 1 except that a-1 was replaced with an equal mole of a-6 and c-1 was replaced with an equal mole of c-233, and its solid purity was determined by HPLC ≧ 99.4%. Mass spectrum m/z: 641.3098 (theoretical value: 641.3083). Theoretical element content (%) C₄₉H₃₉N: c, 91.69; h, 6.12; and N, 2.18. Measured elemental content (%): c, 91.75; h, 6.06; and N, 2.15.

EXAMPLE 13 Synthesis of Compound 264

Compound 264(16.48g) was synthesized in the same manner as in Synthesis example 3 except that a-1 was replaced with an equal mole of a-6 and b-1 was replaced with an equal mole of c-175, and its solid purity was determined by HPLC, ≧ 99.5%. Mass spectrum m/z: 669.3409 (theoretical value: 669.3396). Theoretical element content (%) C₅₁H₄₃N: c, 91.44; h, 6.47; and N, 2.09. Measured elemental content (%): c, 91.48; h, 6.43; and N, 2.12.

EXAMPLE 14 Synthesis of Compound 278

Compound 278(21.78g) was synthesized in the same manner as in Synthesis example 1 except that a-1 was replaced with an equal mole of a-6, b-1 was replaced with an equal mole of b-6, and c-1 was replaced with an equal mole of c-85, and the solid purity was 99.8% or more by HPLC. Mass spectrum m/z: 765.3413 (theoretical value: 765.3396). Theoretical element content (%) C₅₉H₄₃N: c, 92.51; h, 5.66; n, 1.83. Measured elemental content (%): c, 92.59; h, 5.60; n, 1.85.

EXAMPLE 15 Synthesis of Compound 312

Using the same method as that of Synthesis example 3 and the same method as that of Synthesis example 9 for intermediate a-8, a-1 was replaced with an equal mole of a-8 to synthesize compound 312(19.03g) with a solid purity of 99.6% or more by HPLC. Mass spectrum m/z: 845.3986 (theoretical value: 845.3960). Theoretical element content (%) C₆₅H₄₃D₄N: c, 92.27; h, 6.07; n, 1.66. Measured elemental content (%): c, 92.30; h, 6.02; n, 1.63.

EXAMPLE 16 Synthesis of Compound 332

Compound 332(19.74g) was synthesized in the same manner as in Synthesis example 1 except for using a-8 in place of a-1 in an equimolar amount, and had a solid purity of 99.4% by HPLC. Mass spectrum m/z: 711.3897 (theoretical value: 711.3865). Theoretical element content (%) C₅₄H₄₉N: c, 91.10; h, 6.94; and N, 1.97. Measured elemental content (%): c, 91.03; h, 6.99; and N, 1.99.

EXAMPLE 17 Synthesis of Compound 422

Compound 422(18.05g) was synthesized in the same manner as in Synthesis example 1 except for replacing a-1 with an equimolar amount of a-9, and its solid purity by HPLC ≧ 99.3%. Mass spectrum m/z: 659.3473 (theoretical value: 659.3490). Theoretical element content (%) C₅₀H₃₇D₄N: c, 91.00; h, 6.87; and N, 2.12. Measured elemental contentAmount (%): c, 91.07; h, 6.83; and N, 2.10.

EXAMPLE 18 Synthesis of Compound 525

Compound 525(20.55g) was synthesized using the same method as in Synthesis example 1, except that a-1 was replaced with an equimolar amount of a-10, and the purity of the solid was ≧ 99.7% by HPLC. Mass spectrum m/z: 731.3536 (theoretical value: 731.3552). Theoretical element content (%) C₅₆H₄₅N: c, 91.89; h, 6.20; and N, 1.91. Measured elemental content (%): c, 91.95; h, 6.17; n, 1.88.

EXAMPLE 19 Synthesis of Compound 589

Compound 589(17.89g) was synthesized in the same manner as in Synthesis example 1 except that a-1 was replaced with an equimolar amount of a-11, and the purity of the solid was ≧ 99.2% by HPLC. Mass spectrum m/z: 709.3725 (theoretical value: 709.3709). Theoretical element content (%) C₅₄H₄₇N: c, 91.35; h, 6.67; and N, 1.97. Measured elemental content (%): c, 91.40; h, 6.62; and N, 1.99.

EXAMPLE 20 Synthesis of Compound 591

Compound 591(21.18g) was synthesized in the same manner as in synthetic example 1, except that a-1 was replaced with an equal mole of a-12 and c-1 was replaced with an equal mole of c-85, and the purity of the solid was ≧ 99.2% by HPLC. Mass spectrum m/z: 805.3721 (theoretical value: 805.3709). Theoretical element content (%) C₆₂H₄₇N: c, 92.38; h, 5.88; n, 1.74. Measured elemental content (%): c, 92.30; h, 5.92; n, 1.77.

EXAMPLE 21 Synthesis of Compound 625

Compound 625(19.78g) was synthesized in the same manner as in Synthesis example 1 except that c-1 was replaced with an equal mole of c-625, and its purity by HPLC was ≧ 99.7%. Mass spectrum m/z: 789.4206 (theoretical value: 789.4180). Theoretical element content (%) C₆₀H₃₅D₁₀N: c, 91.21; h, 7.01; n, 1.77. Measured elemental content (%): c, 91.28; h, 6.96; n, 1.75.

EXAMPLE 22 Synthesis of Compound 630

Compound 630(16.38g) was synthesized in the same manner as in Synthesis example 1 except that b-1 was replaced with an equimolar amount of b-7, and the purity of the solid was ≧ 99.6% by HPLC. Mass spectrum m/z: 665.3875 (theoretical value: 665.3836). Theoretical element content (%) C₅₀H₂₇D₁₂N: c, 90.18; h, 7.72; and N, 2.10. Measured elemental content (%): c, 90.25; h, 7.69; and N, 2.08.

EXAMPLE 23 Synthesis of Compound 634

Compound 634(21.84g) was synthesized in the same manner as in Synthesis example 1 except that c-1 was replaced with an equal mole of c-634, and the purity of the solid was ≧ 99.4% by HPLC. Mass spectrum m/z: 819.3638 (theoretical value: 819.3601). Theoretical element content (%) C₆₂H₄₅NO: c, 90.81; h, 5.53; n, 1.71. Measured elemental content (%): c, 90.86; h, 5.50; n, 1.69.

EXAMPLE 24 Synthesis of Compound 641

Use ofCompound 641(21.67g) was synthesized in the same manner as in Synthesis example 1 except that c-1 was replaced with an equimolar amount of c-641 and the purity of the solid was ≧ 99.5% by HPLC. Mass spectrum m/z: 911.4463 (theoretical value: 911.4491). Theoretical element content (%) C₇₀H₅₇N: c, 92.17; h, 6.30; n, 1.54. Measured elemental content (%): c, 92.15; h, 6.23; n, 1.58.

Comparative examples 1-2 device preparation examples:

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 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 m-MTDATA/20nm, a hole transport layer HT-1/40nm and main bodies RH-1 and RH-2 on the prepared ITO transparent electrode in a layer-by-layer vacuum evaporation mode: doping RD-9 (48%: 48%: 4% mixed) mixture/30 nm, then evaporating an electron transport layer ET-9/25nm, an electron injection layer LiF/1nm and a cathode Al/140 nm. 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:

comparative example 2: the hole transport layer material HT-1 in comparative example 1 was replaced with HT-2, and an organic light emitting device of comparative example 2 was fabricated in the same manner as in comparative example 1.

[ examples 1 to 24]

Examples 1 to 24: the hole transport layer material HT-1 of the organic light emitting device was sequentially changed to the compounds 1, 9, 22, 85, 89, 135, 139, 175, 203, 223, 233, 237, 264, 278, 312, 332, 422, 525, 589, 591, 625, 630, 634, 641 of the present invention, and the other steps were the same as in comparative example 1.

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 light-emitting device. The results of the light emission characteristic test of the obtained organic light emitting device are shown in table 1. Table 1 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 1 test of light emitting characteristics of light emitting device

As can be seen from the results in table 1, the triarylamine organic compound of the present invention, when applied to an organic light emitting device, as a hole transport layer material, exhibits the advantage of high light emission efficiency as compared to comparative examples 1-2, and is a hole transport material for an organic light emitting device with good performance. In particular, the triarylamine-based organic compound of the present invention exhibits more excellent properties when the group of formula a is directly attached to the nitrogen atom.

Comparative example 3 device preparation example:

comparative example 3: 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 m-MTDATA/20nm, a hole transport layer TPD/40nm and an evaporation main body BH-1 on the prepared ITO transparent electrode in a layer-by-layer vacuum evaporation mode: doping BD (96%: 4%: mixed)/30 nm, then evaporating an electron transport layer ET-11/25nm, an electron injection layer LiF/1nm, a cathode Mg-Ag/20nm, and evaporating a cap layer CP-1/60nm on the cathode. 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 21 to 25]

Examples 21 to 25: the capping layer material CP-1 of the organic light emitting device was sequentially changed to the compounds of the present invention 9, 85, 89, 135, 223, and the other steps were the same as in comparative example 3.

The driving voltage and the luminous efficiency of the organic electroluminescent device were tested by combining test software, a computer, a K2400 digital source manufactured by Keithley, usa, and a PR788 spectral scanning luminance meter manufactured by Photo Research, usa, into a combined IVL test system. The lifetime was measured using the M6000 OLED lifetime test system from McScience. The environment of the test is atmospheric environment, and the temperature is room temperature. The 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 organic compound of the present invention, when applied to an organic light emitting device as a capping layer material, can effectively improve the light extraction efficiency and further improve the light emitting efficiency of the organic light emitting device, compared to comparative example 3, and is a capping layer material for an organic light emitting device with good performance.

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 is characterized in that the molecular structure is shown as formula I:

wherein C is selected from the group shown as the following formula a:

in the formulas b-1 and b-2,

the R is_bAre the same or different from each other and are each independently selected from hydrogen, deuterium, substituted or unsubstituted C1-C15 alkyl, substituted or unsubstituted C3-C15 cycloalkaneOne of a group, a substituted or unsubstituted aryl group of C6-C25, a substituted or unsubstituted heteroaryl group of C2-C20;

l is selected from a single bond or phenylene;

2. A triarylamine based organic compound according to claim 1 wherein L is₀One selected from a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted dibenzofuranyl group, and a substituted or unsubstituted dibenzothiophenyl group, wherein the substituent is one or more deuterium.

3. A triarylamine organic compound according to claim 1, wherein formula a is selected from one of the following groups:

wherein, R is₁Selected from hydrogen, deuterium, halogen atoms, cyano groups, substituted or unsubstituted C1-C15 alkyl groups, substituted or unsubstituted C3-C15 cycloalkyl groups, substituted or unsubstitutedOne of substituted C6-C25 aryl and substituted or unsubstituted C2-C20 heteroaryl;

4. A triarylamine organic compound according to claim 1, wherein said formula b-1 is selected from any one of the following groups:

the formula b-2 is selected from any one of the following groups:

5. A triarylamine organic compound according to claim 1A compound characterized in that L is₁、L₂Independently selected from a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted fluorenylene, substituted or unsubstituted anthrylene, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted dibenzothiophenylene, and substituted or unsubstituted naphthylene, wherein the substituent is one or more of deuterium, ethyl, isopropyl, tert-butyl, phenyl, and pentadeuterated phenyl, and in the case of substitution with a plurality of substituents, the plurality of substituents are the same as or different from each other.

6. A triarylamine organic compound according to claim 1 wherein R is an aryl group_bOne selected from hydrogen, deuterium or a group shown below:

7. a triarylamine organic compound according to claim 1, wherein the triarylamine organic compound is selected from any one of the following chemical structures:

8. an organic light-emitting device comprising an anode, a cathode, and an organic layer disposed between the anode and the cathode or outside one or more electrodes selected from the anode and the cathode, wherein the organic layer contains any one or a combination of at least two of the triarylamine organic compounds according to any one of claims 1 to 7.

9. An organic light-emitting device according to claim 8, wherein the organic layer comprises a hole transport layer containing any one or a combination of at least two of the triarylamine organic compounds according to any one of claims 1 to 7.

10. The organic light-emitting device according to claim 8, wherein the organic layer comprises a capping layer containing any one or a combination of at least two of the triarylamine organic compounds according to any one of claims 1 to 7.