一种芳胺类有机化合物及包含该化合物的有机电致发光器件

Arylamine organic compound and organic electroluminescent device containing same

文档序号：2401 发布日期：2021-09-17 浏览：71次中文

1. An arylamine organic compound is characterized in that the structure of the compound is shown as a general formula (I):

in the general formula (I), L represents a direct bond, phenylene or naphthylene;

said L₃、L₄Each independently represents a direct bond, phenylene, naphthylene, or biphenylene;

a, B are respectively and independently represented by a hydrogen atom, a deuterium atom or a structure shown in a general formula (II), and A, B has and only has one structure shown in the general formula (II);

f represents a hydrogen atom, a deuterium atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a benzofuryl group, an indenyl group or a piperonyl group;

e, D each independently represents a hydrogen atom, a deuterium atom, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted benzofuryl group, a substituted or unsubstituted dibenzofuryl group, a substituted or unsubstituted spirofluorenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted piperonyl group, a structure represented by the general formula (III) or the general formula (IV), and when D, E, F has and only one does not represent a hydrogen atom, and A represents a structure represented by the general formula (II), D represents a hydrogen atom;

in the general formula (II), L₁、L₂Each independently represents a direct bond, phenylene, naphthylene, or biphenylene;

the R is₁-R₄Each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted dimethylfluorenyl group, a substituted or unsubstituted diphenylfluorenyl group, a substituted or unsubstituted spirofluorenyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted naphthospirofluorenyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted naphthofuranyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted naphthocarbazolyl group, a substituted or unsubstituted indenyl group, or a substituted or unsubstituted piperonyl group, and R is a group represented by₁-R₄At least one of them is selected from a substituted or unsubstituted spirofluorenyl group, a substituted or unsubstituted diphenylfluorenyl group or a substituted or unsubstituted dimethylfluorenyl group;

when R is₁-R₄When at least one is selected from the group consisting of dimethylfluorenyl, R₁-R₄Neither is represented as heteroaryl and E and D are not selected from formula (III) and formula (IV);

in the general formulas (III) and (IV), when L represents a direct bond or naphthylene group, the L₄、L₅Each independently represents a direct bond, phenylene, naphthylene, or biphenylene;

in the general formulas (III) and (IV), when L represents phenylene, the L₄Represented by a direct bond, phenylene, naphthylene or biphenylene, said L₅Represented by phenylene, naphthylene or biphenylene;

the R is₁₁、R₁₂Each independently represents a deuterium atom, a phenyl group or a naphthyl group, R₁₁、R₁₂The connection mode of (A) is mono-substitution or forming a parallel ring structure; ar is represented by C₆-C₃₀Aryl, C containing one or more hetero atoms₂-C₃₀A heteroaryl group;

m and n are respectively independent integers of 0, 1 or 2;

the substituent of the substituent group is optionally selected from deuterium atom, methyl group, ethyl group, isopropyl group, butyl group, tert-butyl group, pentyl group, adamantyl group, phenyl group, naphthyl group, biphenyl group, phenanthryl group, furyl group, benzofuryl group, dibenzofuryl group, indenyl group or piperonyl group;

the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.

2. An arylamine organic compound according to claim 1, wherein the arylamine organic compound of the general formula (I) is represented by a structure represented by a general formula (I-9):

f represents phenyl, naphthyl, biphenyl, furyl, benzofuryl, indenyl or piperonyl;

l represents a direct bond, phenylene or naphthylene;

said L₁To L₄Each independently represents a direct bond or a phenylene group;

the R is₁To R₄Independently represent phenyl, biphenyl, naphthyl, phenanthryl, dimethylfluorenyl, diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, phenyl-substituted naphthyl, naphthospirofluorenyl, phenyl-substituted dimethylfluorenyl, naphthodiphenylfluorenyl, furanyl, naphthobenzofuranyl, benzophenanthryl, phenyl-substituted phenanthryl, phenyl-substituted furanyl, benzofuranyl, phenyl-substituted benzofuranyl, indenyl, or piperonyl, and at least one is selected from spirofluorenyl or diphenylfluorenyl.

3. An arylamine organic compound according to claim 1, wherein the arylamine organic compound of the general formula (I) is represented by a structure represented by general formula (I-10):

in the general formula (I-10), L is₁To L₄Each independently represents a direct bond or a phenylene group;

and E represents phenyl, biphenyl, naphthyl, phenanthryl, furyl, benzofuryl, dibenzofuryl, spirofluorenyl, indenyl or piperonyl.

4. An arylamine organic compound according to claim 1, wherein the arylamine organic compound of the general formula (I) is represented by a structure represented by a general formula (I-11):

in the general formula (I-11), L is₁To L₄Each independently represents a direct bond or a phenylene group;

and E represents phenyl, biphenyl, naphthyl, phenanthryl, furyl, benzofuryl, dibenzofuryl, spirofluorenyl, indenyl or piperonyl.

5. An arylamine organic compound according to claim 2, wherein the arylamine organic compound of the general formula (I) is represented by a structure represented by general formula (I-12):

f represents phenyl, naphthyl, biphenyl, furyl, benzofuryl, indenyl or piperonyl;

l represents a direct bond, phenylene or naphthylene;

said L₁To L₄Each independently represents a direct bond or a phenylene group;

the R is₁To R₃Each independently represents phenyl, biphenyl, naphthyl, phenanthryl, dimethylfluorenyl, diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, phenyl-substituted naphthyl, naphthospirofluorenyl, phenyl-substituted dimethylfluorenyl, naphthodiphenylfluorenyl, furanyl, naphthobenzofuranyl, benzophenanthryl, phenyl-substituted phenanthryl, phenyl-substituted furanyl, benzofuranyl, phenyl-substituted benzofuranyl, indenyl, or piperonyl.

6. An arylamine organic compound according to claim 3, wherein the arylamine organic compound of the general formula (I) has a structure represented by a general formula (I-13):

in the general formula (I-13), L is₁To L₄Each independently represents a direct bond or a phenylene group;

the R is₂To R₄Each independently represents phenyl, biphenyl, naphthyl, phenanthryl, dimethylfluorenyl, diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, phenyl-substituted naphthyl, naphthospirofluorenyl, phenyl-substituted dimethylfluorenyl, naphthodiphenylfluorenyl, furanyl, naphthobenzofuranyl, benzophenanthryl, phenyl-substituted phenanthryl, phenyl-substituted furanyl, benzofuranyl, phenyl-substituted benzofuranyl, indenyl, or piperonyl;

and E represents phenyl, biphenyl, naphthyl, phenanthryl, furyl, benzofuryl, dibenzofuryl, spirofluorenyl, indenyl or piperonyl.

7. An arylamine organic compound according to claim 4, wherein the arylamine organic compound represented by the general formula (I) has a structure represented by general formula (I-14):

in the general formula (I-14), L is₁To L₄Each independently represents a direct bond or a phenylene group;

and E represents phenyl, biphenyl, naphthyl, phenanthryl, furyl, benzofuryl, dibenzofuryl, spirofluorenyl, indenyl or piperonyl.

8. An arylamine organic compound according to claim 2, wherein the arylamine structure of the general formula (I) is represented by a structure represented by a general formula (I-15):

f represents phenyl, naphthyl, biphenyl, furyl, benzofuryl, indenyl or piperonyl;

l represents a direct bond, phenylene or naphthylene;

said L₁To L₄Each independently represents a direct bond or a phenylene group;

the R is₁To R₃Each independently represents phenyl, biphenyl, naphthyl, phenanthryl, or biphenylMethyl fluorenyl, diphenyl fluorenyl, spirofluorenyl, dibenzofuranyl, phenyl substituted naphthyl, naphthospirofluorenyl, phenyl substituted dimethylfluorenyl, naphthodiphenylfluorenyl, furanyl, naphthobenzofuranyl, benzophenanthryl, phenyl substituted phenanthryl, phenyl substituted furanyl, benzofuranyl, phenyl substituted benzofuranyl, indenyl, or piperonyl.

9. An arylamine organic compound according to claim 1, wherein the arylamine structure of the general formula (I) is represented by a structure represented by a general formula (I-16):

in the general formula (I-16), L represents a direct bond, a phenylene group or a naphthylene group;

said L₁To L₄Each independently represents a direct bond or a phenylene group;

d is phenyl, biphenyl, naphthyl, phenanthryl, furyl, benzofuryl, dibenzofuryl, spirofluorenyl, indenyl or piperonyl.

10. An arylamine organic compound according to claim 1, wherein the arylamine organic compound of the general formula (I) has a structure represented by general formula (I-17):

in the general formula (I-17), L is₁To L₄Each independently represents a direct bond or a phenylene group;

and E represents phenyl, biphenyl, naphthyl, phenanthryl, furyl, benzofuryl, dibenzofuryl, spirofluorenyl, indenyl or piperonyl.

11. An arylamine organic compound according to claim 1, wherein the arylamine structure of the general formula (I) is represented by a structure represented by general formula (I-18):

in the general formula (I-18), F represents phenyl, naphthyl, biphenyl, furyl, benzofuryl, indenyl or piperonyl;

l represents a direct bond, phenylene or naphthylene;

said L₁To L₄Each independently represents a direct bond or a phenylene group;

the R is₁、R₃、R₄Each independently represents phenyl, biphenyl, naphthyl, phenanthryl, dimethylfluorenyl, diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, phenyl-substituted naphthaleneA naphthyl group, a naphthospirofluorenyl group, a phenyl-substituted dimethylfluorenyl group, a naphthodiphenylfluorenyl group, a furyl group, a naphthobenzofuryl group, a benzophenanthryl group, a phenyl-substituted phenanthryl group, a phenyl-substituted furyl group, a benzofuryl group, a phenyl-substituted benzofuryl group, an indenyl group, or a piperonyl group.

12. An arylamine organic compound according to claim 1, wherein the arylamine structure of the general formula (I) is represented by a structure represented by general formula (I-19):

in the general formula (I-19), L represents a direct bond, a phenylene group or a naphthylene group;

said L₁To L₄Each independently represents a direct bond or a phenylene group;

the R is₁、R₃、R₄Each independently represents phenyl, biphenyl, naphthyl, phenanthryl, dimethylfluorenyl, diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, phenyl-substituted naphthyl, naphthospirofluorenyl, phenyl-substituted dimethylfluorenyl, naphthodiphenylfluorenyl, furanyl, naphthobenzofuranyl, benzophenanthryl, phenyl-substituted phenanthryl, phenyl-substituted furanyl, benzofuranyl, phenyl-substituted benzofuranyl, indenyl, or piperonyl;

d is phenyl, biphenyl, naphthyl, phenanthryl, furyl, benzofuryl, dibenzofuryl, spirofluorenyl, indenyl or piperonyl.

13. An arylamine organic compound according to claim 1, wherein the specific structure of the compound is as follows:

14. an organic electroluminescent device comprising an anode, a hole transporting region, a light emitting region, an electron transporting region and a cathode in this order, wherein the hole transporting region comprises the arylamine-based organic compound according to any one of claims 1 to 13; preferably, the hole transport region includes a hole injection layer, a first hole transport layer, and a second hole transport layer, and more preferably, the first hole transport layer and the hole injection layer include the arylamine-based organic compound according to any one of claims 1 to 13; more preferably, the first hole transport layer is composed of the arylamine organic compound according to any one of claims 1 to 13, and the hole injection layer is composed of the arylamine organic compound according to any one of claims 1 to 113 and other doping materials conventionally used for the hole injection layer.

15. The organic electroluminescent device according to claim 14, wherein the electron transport region comprises a nitrogen heterocyclic compound represented by the following general formula (III):

wherein Ar is₅、Ar₆、Ar₇Independently of one another, from substituted or unsubstituted C₆-C₃₀Aryl, substituted or unsubstituted C containing one or more hetero atoms₅-C₃₀(ii) heterocyclyl, said heteroatom selected from N, O or S;

L₃selected from single bond, substituted or unsubstituted C₆-C₃₀Arylene radical, substituted or unsubstituted C containing one or more hetero atoms₂-C₃₀(ii) heterocyclylene, each of said heteroatoms being independently selected from N, O or S;

X₁、X₂、X₃independently of one another, N or CH, X₁、X₂、X₃Represents N.

Background

Carriers (holes and electrons) in an organic electroluminescent device (OLED) are injected into the device from two electrodes of the device respectively under the driving of an electric field, and meet recombination to emit light in an organic light emitting layer. High performance organic electroluminescent devices require various organic functional materials to have good photoelectric properties. For example, as a charge transport material, it is required to have good carrier mobility. The hole injection layer material and the hole transport layer material used in the existing organic electroluminescent device have relatively weak injection and transport characteristics, and the hole injection and transport rate is not matched with the electron injection and transport rate, so that the composite region has large deviation, and the stability of the device is not facilitated. In addition, reasonable energy level matching between the hole injection layer material and the hole transport layer material is an important factor for improving the efficiency and the service life of the device, and therefore, how to adjust the balance between holes and electrons and adjust the recombination region is an important subject in the field.

Blue organic electroluminescent devices are always soft ribs in the development of full-color OLEDs, and the efficiency, the service life and other properties of blue light devices are difficult to be comprehensively improved at present, so that how to improve the properties of the blue light devices is still a crucial problem and challenge in the field. Most of blue host materials currently used in the market are electron-biased hosts, and therefore, in order to adjust the carrier balance of the light-emitting layer, a hole-transporting material is required to have excellent hole-transporting performance. The better the hole injection and transmission, the more the composite region will shift to the side far away from the electron blocking layer, so as to far away from the interface to emit light, thus improving the performance of the device and prolonging the service life. Therefore, the hole transport region material is required to have high hole injection property, high hole mobility, high electron blocking property, and high electron weatherability.

Since the hole transport material has a thick film thickness, the heat resistance and amorphousness of the material have a crucial influence on the lifetime of the device. Materials with poor heat resistance are easy to decompose in the evaporation process, pollute the evaporation cavity and damage the service life of devices; the material with poor film phase stability can crystallize in the use process of the device, and the service life of the device is reduced. Therefore, the hole transport material is required to have high film phase stability and decomposition temperature during use. However, the development of materials for stable and effective organic material layers for organic electroluminescent devices has not been sufficiently realized. Therefore, there is a continuous need to develop a new material to better meet the performance requirements of the organic electroluminescent device.

Disclosure of Invention

In order to solve the above problems, the present invention provides an aromatic amine-based organic compound having excellent hole transporting ability and stability. When the arylamine organic compound is used for forming a hole transport material of an organic electroluminescent device, the effects of improving the efficiency of the device, reducing the driving voltage and prolonging the service life can be simultaneously displayed.

The specific technical scheme of the invention is as follows: an arylamine organic compound, the structure of which is shown in the general formula (I):

in the general formula (I), L represents a direct bond, phenylene or naphthylene;

said L₃、L₄Each independently represents a direct bond, phenylene, naphthylene, or biphenylene;

the R is₃、R₄Each independently represents a substituted or substituted C6-C30 aryl group, a substituted or unsubstituted C containing one or more heteroatoms₂-C₃₀A heteroaryl group;

f represents a hydrogen atom, a deuterium atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a benzofuryl group, an indenyl group or a piperonyl group;

in the general formula (II), L₁、L₂Each independently represents a direct bond, phenylene, naphthylene, or biphenylene;

the R is₁、R₂Each independently represents a substituted or substituted C6-C30 aryl group, a substituted or unsubstituted C containing one or more heteroatoms₂-C₃₀A heteroaryl group;

in the general formulas (III) and (IV), when L represents a direct bond or naphthylene group, the L₄、L₅Each independently represents a direct bond, phenylene, naphthylene, or biphenylene;

in the general formulas (III) and (IV), when L represents phenylene, the L₄To representIs a direct bond, phenylene, naphthylene or biphenylene, said L₅Represented by phenylene, naphthylene or biphenylene;

the R is₁₁、R₁₂Each independently represents a deuterium atom, a phenyl group or a naphthyl group, R₁₁、R₁₂The connection mode is single substitution or forming a parallel ring structure; ar is represented by C₆-C₃₀Aryl, C containing one or more hetero atoms₂-C₃₀A heteroaryl group;

m and n are respectively independent integers of 0, 1 or 2;

the substituent of the substituent group is optionally selected from deuterium atom, methyl group, t-butyl group, adamantyl group, phenyl group, naphthyl group, biphenyl group, phenanthryl group, furyl group, benzofuryl group, dibenzofuryl group, indenyl group or piperonyl group;

the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.

Preferably, the structure of the compound is shown as the general formula (I):

in the general formula (I), L represents a direct bond, phenylene or naphthylene;

said L₃、L₄Each independently represents a direct bond, phenylene, naphthylene, or biphenylene;

f represents a hydrogen atom, a deuterium atom, a phenyl group, a naphthyl group, a biphenyl group, a furyl group, a benzofuryl group, an indenyl group or a piperonyl group;

in the general formula (II), L₁、L₂Each independently represents a direct bond, phenylene, naphthylene, or biphenylene;

in the general formulas (III) and (IV), when L represents a direct bond or naphthylene group, the L₄、L₅Each independently represents a direct bond, phenylene, naphthylene, or biphenylene;

m and n are respectively independent integers of 0, 1 or 2;

the heteroatom is one or more selected from oxygen atom, sulfur atom or nitrogen atom.

Preferably, R₁-R₄Wherein only one of them is represented by a substituted or unsubstituted spirofluorenyl group or a substituted or unsubstituted diphenylfluorenyl group, and the others are represented by a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted naphthospirofluorenyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted naphthofuranyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted naphthocarbazolyl group, a substituted or unsubstituted indenyl group, or a substituted or unsubstituted piperonyl group.

Preferably, R₁Expressed as the following structure:

preferably, R₃Expressed as the following structure:

preferably, the arylamine organic compound of the general formula (I) may be represented by a structure represented by general formula (I-9):

f represents phenyl, naphthyl, biphenyl, furyl, benzofuryl, indenyl or piperonyl;

l represents a direct bond, phenylene or naphthylene;

said L₁To L₄Each independently represents a direct bond or a phenylene group;

Preferably, the arylamine organic compound of the general formula (I) may be represented by a structure represented by general formula (I-10):

in the general formula (I-10), L is₁To L₄Each independently represents a direct bond or a phenylene group;

and E represents phenyl, biphenyl, naphthyl, phenanthryl, furyl, benzofuryl, dibenzofuryl, spirofluorenyl, indenyl or piperonyl.

Preferably, the arylamine organic compound of the general formula (I) may be represented by a structure represented by general formula (I-11):

in the general formula (I-2), L is₁To L₄Each independently represents a direct bond or a phenylene group;

and E represents phenyl, biphenyl, naphthyl, phenanthryl, furyl, benzofuryl, dibenzofuryl, spirofluorenyl, indenyl or piperonyl.

Preferably, the arylamine organic compound of the general formula (I) may be represented by a structure represented by general formula (I-12):

f represents phenyl, naphthyl, biphenyl, furyl, benzofuryl, indenyl or piperonyl;

l represents a direct bond, phenylene or naphthylene;

said L₁To L₄Each independently represents a direct bond or a phenylene group;

Preferably, the arylamine organic compound of the general formula (I) may be represented by a structure represented by general formula (I-13):

in the general formula (I-13), L is₁To L₄Each independently represents a direct bond or a phenylene group;

and E represents phenyl, biphenyl, naphthyl, phenanthryl, furyl, benzofuryl, dibenzofuryl, spirofluorenyl, indenyl or piperonyl.

Preferably, the arylamine organic compound of the general formula (I) may be represented by a structure represented by general formula (I-14):

in the general formula (I-14), L is₁To L₄Each independently represents a direct bond or a phenylene group;

and E represents phenyl, biphenyl, naphthyl, phenanthryl, furyl, benzofuryl, dibenzofuryl, spirofluorenyl, indenyl or piperonyl.

Preferably, the arylamine structure of the general formula (I) can be represented by a structure represented by a general formula (I-15):

f represents phenyl, naphthyl, biphenyl, furyl, benzofuryl, indenyl or piperonyl;

l represents a direct bond, phenylene or naphthylene;

said L₁To L₄Each independently represents a direct bond or a phenylene group;

the R is₁To R₃Separate watchesShown as phenyl, biphenyl, naphthyl, phenanthryl, dimethylfluorenyl, diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, phenyl-substituted naphthyl, naphthospirofluorenyl, phenyl-substituted dimethylfluorenyl, naphthodiphenylfluorenyl, furanyl, naphthobenzofuranyl, benzophenanthryl, phenyl-substituted phenanthryl, phenyl-substituted furanyl, benzofuranyl, phenyl-substituted benzofuranyl, indenyl, or piperonyl.

Preferably, the arylamine structure of the general formula (I) can be represented by a structure shown in a general formula (I-16):

in the general formula (I-16), L represents a direct bond, a phenylene group or a naphthylene group;

said L₁To L₄Each independently represents a direct bond or a phenylene group;

d is phenyl, biphenyl, naphthyl, phenanthryl, furyl, benzofuryl, dibenzofuryl, spirofluorenyl, indenyl or piperonyl.

Preferably, the arylamine organic compound of the general formula (I) may be represented by a structure represented by general formula (I-17):

in the general formula (I-17), L is₁To L₄Each independently represents a direct bond or a phenylene group;

and E represents phenyl, biphenyl, naphthyl, phenanthryl, furyl, benzofuryl, dibenzofuryl, spirofluorenyl, indenyl or piperonyl.

Preferably, the arylamine structure of the general formula (I) can be represented by a structure shown in a general formula (I-18):

in the general formula (I-18), F represents phenyl, naphthyl, biphenyl, furyl, benzofuryl, indenyl or piperonyl;

l represents a direct bond, phenylene or naphthylene;

said L₁To L₄Each independently represents a direct bond or a phenylene group;

the R is₁、R₃、R₄Each independently represents phenyl, biphenyl, naphthyl, phenanthryl, dimethylfluorenyl, diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, phenyl-substituted naphthyl, naphthospirofluorenyl, phenyl-substituted dimethylfluorenyl, naphthodiphenylfluorenyl, furanyl, naphthobenzofuranyl, benzophenanthryl, phenyl-substituted phenanthryl, phenyl-substituted furanyl, benzofuranyl, phenyl-substituted benzofuranyl, indenyl, or piperonyl.

Preferably, the arylamine structure of the general formula (I) can be represented by a structure shown in a general formula (I-19):

in the general formula (I-19), L represents a direct bond, a phenylene group or a naphthylene group;

said L₁To L₄Each independently represents a direct bond or a phenylene group;

the R is₁、R₃、R₄Each independently represents phenyl, biphenyl, naphthyl, phenanthryl, dimethylfluorenyl, diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, phenyl-substituted naphthyl, naphthospirofluorenyl, phenyl-substituted dimethylfluorenyl, naphthodiphenylfluorenyl, furanyl, naphthobenzofuranyl, benzophenanthryl, phenyl-substituted phenanthryl, phenyl-substituted furanyl, benzofuranyl, phenyl-substituted benzofuranyl, indenyl, or piperonyl;

d is phenyl, biphenyl, naphthyl, phenanthryl, furyl, benzofuryl, dibenzofuryl, spirofluorenyl, indenyl or piperonyl.

Preferably, the arylamine organic compound of the general formula (I) may be represented by a structure represented by general formula (I-20):

e represents phenyl, biphenyl, naphthyl, phenanthryl, furyl, benzofuryl, dibenzofuryl, spirofluorenyl, indenyl or piperonyl;

l represents a direct bond, phenylene or naphthylene;

said L₁To L₄Each independently represents a direct bond or a phenylene group;

the R is₃To R₄Each independently represents phenyl, biphenyl, naphthyl, phenanthryl, dimethylfluorenylA diphenyl fluorenyl group, a spirofluorenyl group, a dibenzofuranyl group, a phenyl-substituted naphthyl group, a naphthospirofluorenyl group, a phenyl-substituted dimethylfluorenyl group, a naphthodiphenylfluorenyl group, a furanyl group, a naphthobenzofuranyl group, a benzophenanthrenyl group, a phenyl-substituted phenanthrenyl group, a phenyl-substituted furanyl group, a benzofuranyl group, a phenyl-substituted benzofuranyl group, an indenyl group, or a piperonyl group, and at least one group selected from the spirofluorenyl group or the diphenylfluorenyl group.

Preferably, the arylamine organic compound of the general formula (I) may be represented by a structure represented by general formula (I-21):

e represents phenyl, biphenyl, naphthyl, phenanthryl, furyl, benzofuryl, dibenzofuryl, spirofluorenyl, indenyl or piperonyl;

l represents a direct bond, phenylene or naphthylene;

said L₁To L₄Each independently represents a direct bond or a phenylene group;

the R is₁、R₄Independently represent phenyl, biphenyl, naphthyl, phenanthryl, dimethylfluorenyl, diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, phenyl-substituted naphthyl, naphthospirofluorenyl, phenyl-substituted dimethylfluorenyl, naphthodiphenylfluorenyl, furanyl, naphthobenzofuranyl, benzophenanthryl, phenyl-substituted phenanthryl, phenyl-substituted furanyl, benzofuranyl, phenyl-substituted benzofuranyl, indenyl, or piperonyl, and at least one is selected from spirofluorenyl or diphenylfluorenyl.

Preferably, the specific structure of the compound is as follows:

an organic electroluminescent device comprising an anode, a hole transport region, a light-emitting region, an electron transport region and a cathode in this order, wherein the hole transport region comprises the arylamine-based organic compound described in any one of the preceding items; preferably, the hole transport region comprises a hole injection layer, a first hole transport layer and a second hole transport layer, and more preferably, the first hole transport layer and the hole injection layer comprise the arylamine organic compound described in any one of the foregoing; more preferably, the first hole transport layer is composed of the arylamine organic compound described in any one of the above, and the hole injection layer is composed of the arylamine organic compound described in any one of the above and other doping materials conventionally used for the hole injection layer.

Preferably, the electron transport region comprises a nitrogen heterocyclic compound represented by the following general formula (III):

L₃selected from single bond, substituted or unsubstituted C₆-C₃₀Arylene radical, substituted or unsubstituted C containing one or more hetero atoms₅-C₃₀(ii) heterocyclylene, each of said heteroatoms being independently selected from N, O or S;

X₁、X₂、X₃independently of one another, N or CH, X₁、X₂、X₃Represents N.

Has the advantages that:

the technical core of the invention is that the intermediate bridging group of the bistriphenylamine hole material has a specific torsion angle, namely, the bridged molecular group has a spatial cross-structural conformation of ortho-position and meta-position, and the cross-structural conformation enables the molecule with the characteristics of the invention to have the following advantages.

(1) The structure of the double triarylamine hole conducting material has three-dimensional asymmetry, and the asymmetric structure is beneficial to keeping stable amorphous film phase state of molecules during film forming, so that the physical and chemical stability of the film phase state and the film phase state stability under the action of point formation are ensured, and the service life stability of a device is further beneficial to obtaining.

(2) Due to the asymmetry of the middle bridging group in the double triarylamine structure, the formation of different carrier conduction energy levels in the molecular structure of the double triarylamine is ensured, so that different carrier conduction channels are formed, carrier injection and conduction among different energy level material combinations are facilitated, the interface stability between the arylamine material and adjacent materials is facilitated, and the good high-low temperature driving service life of an application device is facilitated.

(3) It is known that, for a hole-type carrier-conducting material, the wider the HOMO distribution in the molecule means that the higher the proportion of fragments participating in HOMO conduction in the molecule, and thus the higher hole carrier-conducting efficiency can be easily obtained. Based on the intensive research of the inventor, the stereo bridging group characterized by the invention is more beneficial to the distribution of HOMO on the whole molecule, so that the high carrier mobility of the material is easily obtained, and the low-voltage driving effect of the device is easily obtained.

(4) Because the bistriarylamine intermediate bridging group has the structural characteristics of ortho position and meta position, the structural characteristics are favorable for improving the glass transition temperature of molecules and reducing the evaporation temperature of the molecules, namely, even if the molecular weight of the molecules is higher, the evaporation temperature can be ensured to be lower, and the excellent performance is not only favorable for thermal evaporation of materials and controlling the thermal decomposition rate of the materials, thereby improving the application stability of the materials in devices.

Moreover, for the double triarylamine molecular structural formula with the characteristics of the invention, except for a double triarylamine bridging group, the ligand connected to the triarylamine is optimized, which is beneficial to further improving the performance of the material. For example, spirofluorene, diphenylfluorene, carbazole, triphenylene, pyrene, phenanthrene and the like are selected, or groups or group derivatives (containing a fused ring structure or similar groups with a substituted structure) with larger structural radiuses are selected, so that the stability and the mobility of the material are improved, and meanwhile, the accurate regulation and control of the HOMO energy level of the material are facilitated, and further, the good device application effect of the material is obtained.

The organic functional materials for forming the OLED device not only comprise hole injection conducting materials, but also comprise electron injection conducting materials and light-emitting layer materials, so that the OLED device has a good device application effect, and needs a good carrier balance degree for protection, therefore, in order to obtain the best device application effect, the double triarylamine materials matched with the characteristic structure also need specific electronic materials for matching. Based on the intensive research of the present inventors, the electronic-type material is preferably a material containing structural characteristics of azabenzene, such as triazine-based material, pyridine-based material, pyrazine-based material, and the like, or a derivative containing these characteristic groups. The arylamine organic compound is combined with the aza-benzene ring electronic transmission material, so that electrons and holes are easy to obtain the optimal balance state, the arylamine organic compound has higher efficiency and excellent service life, and particularly, the arylamine organic compound is easy to obtain a good high-temperature service life effect of a device.

Drawings

Fig. 1 is a cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.

1 represents a substrate layer; 2 represents an anode layer; 3 represents a hole injection layer; 4 represents a hole transport layer; 5 represents an electron blocking layer; 6 represents a light-emitting layer; 7 represents a hole blocking layer; 8 denotes an electron transport layer; 9 denotes an electron injection layer; 10 is denoted as cathode layer; and 11 denotes a cover layer.

FIG. 2 shows the nuclear magnetic spectrum of Compound 1 of the present invention.

FIG. 3 is a nuclear magnetic spectrum of inventive compound 206.

FIG. 4 is a nuclear magnetic spectrum of inventive compound 115.

FIG. 5 is a nuclear magnetic spectrum of compound 54 of the present invention.

FIG. 6 shows a nuclear magnetic spectrum of inventive compound 518.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in 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 of the embodiments. The following description of at least one exemplary embodiment is merely illustrative in nature and is in no way intended to limit the invention, its application, or uses. 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 protection scope of the present invention.

It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.

In the present invention, unless otherwise specified, HOMO means the highest occupied orbital of a molecule, and LUMO means the lowest unoccupied orbital of a molecule. Further, in the present invention, HOMO and LUMO energy levels are expressed in absolute values, and the comparison between the energy levels is also a comparison of the magnitude of the absolute values thereof, and those skilled in the art know that the larger the absolute value of an energy level is, the lower the energy of the energy level is.

In the present invention, when a layer or element is referred to as being "on" another layer or substrate, it can be directly on the other layer or substrate, or intervening layers may also be present. In addition, it will also be understood that when a layer is referred to as being "between" two layers, it can be the only layer between the two layers, or one or more intervening layers may also be present. Like reference numerals refer to like elements throughout.

In the present invention, when describing electrodes and organic electroluminescent devices, and other structures, "upper", "lower", "top", and "bottom" and the like used to indicate orientation only indicate orientation in a certain specific state, and do not mean that the related structures can exist only in the orientation; conversely, if the structure is repositioned, e.g., inverted, the orientation of the structure is changed accordingly. Specifically, in the present invention, the "bottom" side of the electrode refers to the side of the electrode that is closer to the substrate during fabrication, while the opposite side that is further from the substrate is the "top" side.

In this specification, the term "substituted" means that one or more hydrogen atoms on the designated atom or group are replaced with the designated group, provided that the designated atom's normal valency is not exceeded in the present case.

In this specification, the term "C₆-C₃₀Aryl "or" C₆-C₃₀Arylene "refers to a fully unsaturated monocyclic, polycyclic, or fused polycyclic (i.e., rings that share a pair of adjacent carbon atoms) system having 6 to 30 ring carbon atoms.

In this specification, the term "C₂-C₃₀Heterocyclyl "refers to a saturated, partially saturated, or fully unsaturated cyclic group having 2 to 30 ring carbon atoms and containing at least one heteroatom selected from N, O and S, including but not limited to heteroaryl, heterocycloalkyl, fused rings, or combinations thereof. When the heterocyclyl is a fused ring, each or all of the rings of the heterocyclyl may contain at least one heteroatom.

More precisely, substituted or unsubstituted C_6-C30Aryl and/or substituted or unsubstituted C₂-C₃₀The heterocyclic group means a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthryl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted tetracenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenylyl group, a substituted or unsubstituted terphenylyl group, a substituted or unsubstituted m-terphenylyl group, a substituted or unsubstituted terphenylyl groupA group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted perylene group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furyl group, a substituted or unsubstituted thienyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted oxazolyl group, a substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidyl group, a substituted or unsubstituted pyrazinyl group, or unsubstitutedA triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted indolyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted isoquinolyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinolyl group, a substituted or unsubstituted naphthyridinyl group, a substituted or unsubstituted benzoxazinyl group, a substituted or unsubstituted benzothiazinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted phenothiazinyl group, a substituted or unsubstituted phenazinyl group, a substituted or unsubstituted fluorene group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazolyl group, a combination thereof, or a fused ring of a combination of the foregoing groups, but not limited thereto.

In the present specification, substituted or unsubstituted C₆-C₃₀Arylene or substituted or unsubstituted C₂-C₃₀Heterocyclylene means, respectively, a substituted or unsubstituted C as defined above and having two linking groups₆-C₃₀Aryl or substituted or unsubstituted C₅-C₃₀A heterocyclic group such as a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthrylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted tetracylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted paratriphenylene group, a substituted or unsubstituted metatriphenylene group, a substituted or unsubstituted phenylene groupA group, a substituted or unsubstituted triphenylene alkylene group, a substituted or unsubstituted perylene group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanylene group, a substituted or unsubstituted thiophenylene group, a substituted or unsubstituted pyrrolylene group, a substituted or unsubstituted pyrazolyl ene group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolylene group, a substituted or unsubstituted oxazolylene group, a substituted or unsubstituted thiazolyl ene group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted perylene groupSubstituted or unsubstituted thiadiazolylene, substituted or unsubstituted pyridinylene, substituted or unsubstituted pyrimidinylene, substituted or unsubstituted pyrazinylene, substituted or unsubstituted triazinylene, substituted or unsubstituted benzofuranylene, substituted or unsubstituted benzothiophenylene, substituted or unsubstituted benzimidazolene, substituted or unsubstituted indolyl, substituted or unsubstituted quinolylene, substituted or unsubstituted isoquinolylene, substituted or unsubstituted quinazolinylene, substituted or unsubstituted quinolinylene, substituted or unsubstituted naphthyridine, substituted or unsubstituted benzoxazinyl, substituted or unsubstituted benzothiazinyl, substituted or unsubstituted phenothiazinylene, substituted or unsubstituted acridinylene, substituted or unsubstituted phenazinylene, substituted or unsubstituted phenothiazinyl, substituted or unsubstituted phenoxazinyl, substituted or unsubstituted fluorenylene, Substituted or unsubstituted dibenzofuranylene, substituted or unsubstituted dibenzothiophenylene, substituted or unsubstituted carbazolyl, a combination thereof, or a fused ring of a combination of the foregoing, but is not limited thereto.

In this specification, the hole characteristics refer to characteristics that are capable of supplying electrons when an electric field is applied and holes formed in the anode are easily injected into and transported in the light emitting layer due to the conductive characteristics according to the Highest Occupied Molecular Orbital (HOMO) level.

In the present specification, the electron characteristics refer to characteristics that can accept electrons when an electric field is applied and electrons formed in the cathode are easily injected into and transported in the light emitting layer due to the conductive characteristics according to the Lowest Unoccupied Molecular Orbital (LUMO) level.

Organic electroluminescent device

The invention provides an organic electroluminescent device using arylamine compounds of general formula (I).

In one exemplary embodiment of the present invention, an organic electroluminescent device may include an anode, a hole transport region, a light emitting region, an electron transport region, and a cathode.

The organic electroluminescent device of the present invention may be a bottom emission organic electroluminescent device, a top emission organic electroluminescent device, and a stacked organic electroluminescent device, which is not particularly limited.

In the organic electroluminescent device of the present invention, any substrate commonly used in organic electroluminescent devices may also be used. Examples thereof are transparent substrates such as glass or transparent plastic substrates; opaque substrates, such as silicon substrates; a flexible Polyimide (PI) film substrate. Different substrates have different mechanical strength, thermal stability, transparency, surface smoothness, water resistance. The direction of use varies depending on the nature of the substrate. In the present invention, a transparent substrate is preferably used. The thickness of the substrate is not particularly limited.

Anode

Preferably, the anode may be formed on the substrate. In the present invention, the anode and the cathode are opposed to each other. The anode may be made of a conductor having a high work function to aid hole injection, and may be, for example, a metal such as nickel, platinum, copper, zinc, silver, or an alloy thereof; metal oxides such as zinc oxide, Indium Tin Oxide (ITO), and Indium Zinc Oxide (IZO); combinations of metals and metal oxides, such as ZnO with Al or ITO with Ag; conductive polymers such as poly (3-methylthiophene), poly (3,4- (ethylene-1, 2-dioxy) thiophene), and polyaniline, but are not limited thereto. The thickness of the anode depends on the material used and is typically 50-500nm, preferably 70-300nm, and more preferably 100, 1 or 200nm, with the use of ITO and Ag in combination of metals and metal oxides being preferred in the present invention.

Cathode electrode

The cathode may be made of a conductor having a lower work function to aid in electron injection, and may be, for example, a metal or alloy thereof, such as magnesium, calcium, sodium, potassium, titanium, indium, aluminum, silver, tin, and combinations thereof; materials of multilayer structure, e.g. LiF/Al, Li₂O/Al and BaF₂But not limited thereto,/Ca. The thickness of the cathode depends on the material used and is generally from 10 to 50nm, preferably from 15 to 20 nm.

Light emitting area

In the present invention, the light emitting region may be disposed between the anode and the cathode, and may include at least one host material and at least one guest material. As the host material and the guest material of the light emitting region of the organic electroluminescent device of the present invention, light emitting layer materials for organic electroluminescent devices known in the art can be used. The host material may be, for example, a thiazole derivative, a benzimidazole derivative, a polydialkylfluorene derivative, or 4,4' -bis (9-Carbazolyl) Biphenyl (CBP). As the host material, a compound containing an anthracene group can be used. The guest material may be, for example, quinacridone, coumarin, rubrene, perylene and derivatives thereof, benzopyran derivatives, rhodamine derivatives or aminostyrene derivatives.

In a preferred embodiment of the present invention, one or two host material compounds are contained in the light-emitting region.

In a preferred embodiment of the present invention, two host material compounds are contained in the light emitting region, and the two host material compounds form an exciplex.

In a preferred embodiment of the present invention, the host material of the light emitting region used is selected from one or more of the following compounds BH1-BH 11:

in the present invention, the light emitting region may include a phosphorescent or fluorescent guest material to improve the fluorescent or phosphorescent characteristics of the organic electroluminescent device. Specific examples of the phosphorescent guest material include metal complexes of iridium, platinum, and the like, and for the fluorescent guest material, those generally used in the art may be used. In a preferred embodiment of the present invention, the guest material of the light-emitting film layer used is selected from one of the following compounds BD-1 to BD-10:

in the light emitting region of the present invention, the ratio of the host material to the guest material is used in a range of 99:1 to 70:30, preferably 99:1 to 85:15 and more preferably 97:3 to 87:13 by mass.

The thickness of the light emitting region may be 10 to 50nm, preferably 15 to 30nm, but the thickness is not limited to this range.

Hole transport region

In the organic electroluminescent device of the present invention, a hole transport region is provided between the anode and the light emitting region, and includes a hole injection layer, a hole transport layer, and an electron blocking layer.

Hole injection layer

The hole injection material used in the hole injection layer (also referred to as an anode interface buffer layer) is a material that can sufficiently accept holes from the anode at a low voltage, and the Highest Occupied Molecular Orbital (HOMO) of the hole injection material is preferably a value between the work function of the anode material and the HOMO of the adjacent organic material layer. In a preferred embodiment of the present invention, the hole injection layer is a mixed film layer of a host organic material and a P-type dopant material. In order to smoothly inject holes from the anode into the organic film layer, the HOMO level of the host organic material must have a certain characteristic with the P-type dopant material, so that the generation of a charge transfer state between the host material and the dopant material is expected, and ohmic contact between the hole injection layer and the anode is realized, thereby realizing efficient injection of holes from the electrode to the hole injection layer. This feature is summarized as: the difference between the HOMO energy level of the host material and the LUMO energy level of the P-type doping material is less than or equal to 0.4 eV. Therefore, for hole-type host materials with different HOMO levels, different P-type doping materials need to be selected to match with the hole-type host materials, so that ohmic contact of an interface can be realized, and the hole injection effect is improved.

Preferably, specific examples of the host organic material include: metalloporphyrin, oligothiophene, organic materials of arylamine, hexanitrile hexaazatriphenylene, organic materials of quinacridone, organic materials of perylene, anthraquinone, polyaniline and polythiophene conductive polymers; but is not limited thereto. Preferably, the host organic material is an arylamine-based organic material.

Preferably, the P-type doping material is a compound having charge conductivity selected from the group consisting of: quinone derivatives or metal oxides such as tungsten oxide and molybdenum oxide, but not limited thereto.

In a preferred embodiment of the present invention, the P-type doping material used is selected from any one of the following compounds P-1 to P-8:

in one embodiment of the invention, the ratio of host organic material to P-type dopant material used is 99:1 to 95:5, preferably 99:1 to 97:3, by mass.

In a preferred embodiment of the present invention, the hole injection layer is a mixed film layer of an arylamine compound and a P-type dopant material, and the arylamine compound is an arylamine compound of the general formula (1).

The thickness of the hole injection layer of the present invention may be 5 to 20nm, preferably 8 to 15nm, but the thickness is not limited to this range.

Hole transport layer

In the organic electroluminescent device of the present invention, the hole transport layer may be disposed on the hole injection layer. The hole transport material is suitably a material having a high hole mobility, which can accept holes from the anode or the hole injection layer and transport the holes into the light-emitting layer. Specific examples thereof include: aromatic amine-based organic materials, conductive polymers, block copolymers having both conjugated and non-conjugated portions, and the like, but are not limited thereto. In a preferred embodiment, the hole transport layer contains the same aromatic amine compound represented by the general formula (I) as the hole injection layer.

The thickness of the hole transport layer of the present invention may be 80, 1 or 200nm, preferably 100-150nm, but the thickness is not limited to this range.

Electron blocking layer

In the organic electroluminescent device of the present invention, the electron blocking layer may be disposed between the hole transport layer and the light emitting layer, and particularly, contacts the light emitting layer. The electron blocking layer is provided to contact the light emitting layer, and thus, hole transfer at the interface of the light emitting layer and the hole transport layer can be precisely controlled. In one embodiment of the present invention, the electron blocking layer material is selected from carbazole-based aromatic amine derivatives. The thickness of the electron blocking layer may be 5 to 20nm, preferably 8 to 15nm, but the thickness is not limited to this range.

Electron transport region

In the organic electroluminescent device of the present invention, the electron transport region is disposed between the light emitting region and the cathode, and includes a hole blocking layer, an electron transport layer, and an electron injection layer, but is not limited thereto.

Electron injection layer

The electron injection layer may be disposed between the electron transport layer and the cathode. The electron injection layer material is generally a material preferably having a low work function so that electrons are easily injected into the organic functional material layer. Preferably, the electron injection layer material is an N-type metal material. As the electron injection layer material of the organic electroluminescent device of the present invention, electron injection layer materials for organic electroluminescent devices known in the art, for example, lithium; lithium salts such as lithium 8-hydroxyquinoline, lithium fluoride, lithium carbonate or lithium azide; or cesium salts, cesium fluoride, cesium carbonate or cesium azide. The thickness of the electron injection layer of the present invention may be 0.1 to 5nm, preferably 0.5 to 3nm, and more preferably 0.8 to 1.5nm, but the thickness is not limited to this range.

Electron transport layer

The electron transport layer may be disposed over the light emitting film layer or, if present, the hole blocking layer. The electron transport layer material is a material that easily receives electrons of the cathode and transfers the received electrons to the light emitting layer. Materials with high electron mobility are preferred. As the electron transport layer of the organic electroluminescent device of the present invention, an electron transport layer material for organic electroluminescent devices known in the art, for example, in Alq, can be used₃Metal complexes of hydroxyquinoline derivatives represented by BAlq and LiQ, various rare earth metal complexes, triazole derivatives, triazine derivatives such as 2, 4-bis (9, 9-dimethyl-9H-fluoren-2-yl) -6- (naphthalen-2-yl) -1,3, 5-triazine (CAS number: 1459162-51-6), 2- (4- (9, 10-di (naphthalen-2-yl) anthracen-2-yl) phenyl) -1-phenyl-1H-benzo [ d]Imidazole derivatives such as imidazole (CAS number: 561064-11-7, commonly known as LG201), oxadiazole derivatives, and the like.

In a preferred organic electroluminescent device of the invention, the electron-transporting layer comprises a nitrogen-heterocyclic derivative of the general formula (III):

wherein Ar is₅、Ar₆And Ar₇Independently of one another, represents substituted or unsubstituted C₆-C₃₀Aryl, substituted or unsubstituted C containing one or more hetero atoms₅-C₃₀Heterocyclyl, said heteroatoms being independently from each other selected from N, O or S;

L₃selected from substituted or unsubstituted C₆-C₃₀Arylene radical, substituted or unsubstituted C containing one or more hetero atoms₅-C₃₀(ii) heterocyclylene, each of said heteroatoms being independently selected from N, O or S;

n represents 1 or 2;

X₁、X₂、X₃independently of one another, N or CH, with the proviso that X₁、X₂、X₃At least one group in (a) represents N.

Preferably, the nitrogen heterocyclic compound of the general formula (III) is represented by the general formula (III-1):

wherein Ar is₅、Ar₆、Ar₇、X₁、X₂、X₃、L₃Each as defined above.

In a preferred embodiment of the present invention, the electron transport layer comprises any one of the compounds selected from the group consisting of:

in a more preferred embodiment of the present invention, the electron transport layer comprises any one of the compounds selected from the group consisting of:

in a preferred embodiment of the invention, the electron transport layer comprises, in addition to the compounds of the general formula (III), further compounds conventionally used in electron transport layers, such as, for example, Alq3, LiQ, preferably LiQ. In a more preferred embodiment of the present invention, the electron transport layer consists of one of the compounds of the general formula (III) and one of the other compounds conventionally used in electron transport layers, preferably LiQ.

The hole injection and transport rates of the hole transport region containing the arylamine compound of the present invention can be well matched to the electron injection and transport rates. Preferably, the hole injection and transport rates of the hole transport region containing the arylamine compound of the present invention can be better matched to the electron injection and transport rates of the electron transport region containing the nitrogen heterocycle derivative of the general formula (III).

Therefore, in a particular embodiment of the present invention, the use of an electron transport region comprising or consisting of one or more nitrogen heterocyclic derivatives of the general formula (III) in combination with a hole transport region comprising the arylamine compounds of the present invention achieves a relatively better technical result.

The thickness of the electron transport layer of the present invention may be 10 to 80nm, preferably 20 to 60nm, and more preferably 25 to 45nm, but the thickness is not limited to this range.

Covering layer

In order to improve the light extraction efficiency of the organic electroluminescent device, a light extraction layer (i.e., a CPL layer, also referred to as a capping layer) may be added on the cathode of the device. According to the principle of optical absorption and refraction, the CPL cover layer material should have a higher refractive index as well as a better refractive index, and the absorption coefficient should be smaller as well. Any material known in the art may be used as the CPL layer material, such as Alq3, or N4, N4' -diphenyl-N4, N4' -bis (9-phenyl-3-carbazolyl) biphenyl-4, 4' -diamine. The CPL capping layer is typically 5-300nm, preferably 20-100nm and more preferably 40-80nm thick.

The organic electroluminescent device of the present invention may further include an encapsulation structure. The encapsulation structure may be a protective structure that prevents foreign substances such as moisture and oxygen from entering the organic layers of the organic electroluminescent device. The encapsulation structure may be, for example, a can, such as a glass can or a metal can; or a thin film covering the entire surface of the organic layer.

Hereinafter, an organic electroluminescent device according to an embodiment of the present invention is described.

In the drawings, the thickness of layers, films, substrates, regions, etc. are exaggerated for clarity. Like reference numerals refer to like elements throughout the specification. It will be understood that when an element such as a layer, film, region, or substrate is referred to as being "on" another element, it can be directly on the other element or intervening elements may also be present. In contrast, when an element is referred to as being "directly on" another element, there are no intervening elements present.

Fig. 1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.

Referring to fig. 1, the organic electroluminescent device according to an embodiment of the present invention includes an anode 2 and a cathode 10 facing each other, a hole transport region including a hole injection layer 3, a hole transport layer 4, and an electron blocking layer 5, a light emitting region 6, and an electron transport region including a hole blocking layer 7, an electron transport layer 8, and an electron injection layer 9, which are sequentially disposed between the anode 2 and the cathode 10, and a capping layer 11 disposed on a substrate 1 and the cathode under the anode 2.

The present invention also relates to a method of preparing an organic electroluminescent device comprising sequentially laminating an anode, a hole injection layer, a hole transport layer, an electron blocking layer, an organic film layer, an electron transport layer, an electron injection layer and a cathode, and optionally a capping layer, on a substrate. In this regard, methods such as vacuum deposition, vacuum evaporation, spin coating, casting, LB method, inkjet printing, laser printing, LITI, or the like may be used, but are not limited thereto. In the present invention, it is preferable that the respective layers are formed by a vacuum evaporation method. The individual process conditions in the vacuum evaporation process can be routinely selected by the person skilled in the art according to the actual requirements.

The material for forming each layer according to the present invention may be used as a single layer by forming a film alone, may be used as a single layer by forming a film in admixture with another material, or may be used as a laminated structure of layers formed alone, layers formed in admixture with each other, or a laminated structure of layers formed alone and layers formed in admixture with each other.

The invention also relates to a full-color display device, in particular a flat panel display device, having three pixels of red, green and blue, comprising the organic electroluminescent device of the invention. The display device may further include at least one thin film transistor. The thin film transistor may include a gate electrode, source and drain electrodes, a gate insulating layer, and an active layer, wherein one of the source and drain electrodes may be electrically connected to an anode of the organic electroluminescent device. The active layer may include crystalline silicon, amorphous silicon, an organic semiconductor, or an oxide semiconductor, but is not limited thereto.

Exemplary embodiments have been disclosed herein, and although specific terms are employed, they are used in a generic and descriptive sense only and not for purposes of limitation. In some instances, features, characteristics and/or elements described in connection with a particular embodiment may be used alone or in combination with features, characteristics and/or elements described in connection with other embodiments, unless specifically indicated otherwise, as will be apparent to one of ordinary skill in the art upon submission of the present application. Accordingly, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.

The following examples are intended to better illustrate the invention, but the scope of the invention is not limited thereto.

Examples

Unless otherwise indicated, various materials used in the following examples and comparative examples are commercially available or may be obtained by methods known to those skilled in the art.

Example 1: synthesis of intermediate M-1

Adding 0.01mol of raw material A-1, 0.012mol of 4-bromochlorobenzene and 150ml of toluene into a 250ml three-necked bottle under the protection of nitrogen, stirring and mixing, and then adding 5 multiplied by 10^-5mol Pd₂(dba)₃，5×10-⁵Heating the tri-tert-butylphosphine and 0.03mol of sodium tert-butoxide to 105 ℃, carrying out reflux reaction for 24 hours, and sampling a sample point plate to show that the non-amino compound remains and the reaction is complete; naturally cooling to room temperature, filtering, rotatably steaming the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain an intermediate P-1. LC-MS: measurement value: 280.25([ M + H)](+) of; accurate quality: 279.08.

0.01mol of intermediate P-1 was weighed out and dissolved in 150ml of Tetrahydrofuran (THF) under nitrogen atmosphere, and 0.03mol of bis (pinacolato) diboron and 1X 10 were added^-4Adding mol (1, 1' -bis (diphenylphosphino) ferrocene) dichloropalladium (II) and 0.03mol of potassium acetate, stirring the mixture, and heating and refluxing the mixed solution of the reactants at the reaction temperature of 80 ℃ for 10 hours; after the reaction is finished, adding water for cooling, filtering the mixture, putting a filter cake in a vacuum drying oven for drying, and separating and purifying the obtained residue through a silica gel column to obtain an intermediate M-1; LC-MS: measurement value: 372.09([ M + H)](+) of; accurate quality: 371.21.

the following intermediate M was prepared in the same manner as in example 1, and the synthetic raw materials are shown in table 1 below;

TABLE 1

Example 2: synthesis of Compound 1

Adding 0.01mol of raw material C-1, 0.012mol of 2-bromo-1-chloro-4-iodobenzene and 150ml of toluene into a 250ml three-necked bottle under the protection of nitrogen, stirring and mixing, and then adding 5X 10^-5mol Pd₂(dba)₃，5×10^-5Heating the tri-tert-butylphosphine and 0.03mol of sodium tert-butoxide to 105 ℃, carrying out reflux reaction for 24 hours, and sampling a sample point plate to show that the non-amino compound remains and the reaction is complete; naturally cooling to room temperature, filtering, rotatably steaming the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain an intermediate N-1. LC-MS: measurement value: 596.31([ M + H)]⁺) (ii) a Accurate quality: 595.07.

to a 250ml three-necked flask, 0.005mol of intermediate M-1, 0.006mol of intermediate N-1, and 5X 10 mol were added under a nitrogen atmosphere^-5mol Pd(OAc)₂40ml of DMF, stirring for 30 minutes by introducing nitrogen, and then adding K₃PO₄Aqueous solution (0.0075mol K₃PO₄Dissolved in 20ml of water), heated to 130 ℃, reacted for 10 hours, and observed by Thin Layer Chromatography (TLC) until the reaction was complete. And naturally cooling to room temperature, adding dichloromethane into the reaction system for extraction, separating liquid, and performing reduced pressure rotary evaporation on the organic phase until no fraction is obtained. The resulting material was purified by silica gel column to give intermediate Q-1. LC-MS: measurement value: 761.14([ M + H)]⁺) (ii) a Accurate quality: 760.26.

0.06mol of the raw material D-1 was charged into a 500ml three-necked flask under a nitrogen atmosphere, and a mixed solvent (300ml of toluene, 90ml of H) was added₂O) dissolving the intermediate, introducing nitrogen, stirring for 1 hour, and slowly adding 0.05mol of intermediate Q-1 and 0.1mol of K₂CO₃、0.005mol Pd(PPh₃)₄The reaction was heated to 90 ℃ for 8 hours, and the reaction was observed by Thin Layer Chromatography (TLC) until the reaction was complete. Naturally cooling to room temperature, adding water into the reaction systemExtracting, separating liquid, and performing reduced pressure rotary evaporation on the organic phase until no fraction is obtained. The obtained substance is purified by a silica gel column to obtain a target product. Elemental analysis Structure (molecular formula C)₆₁H₄₂N₂): theoretical value: c, 91.24; h, 5.27; n, 3.49; test values are: c, 91.16; h, 5.29; and N, 3.52. LC-MS: measurement value: 803.25([ M + H)]⁺) (ii) a Accurate quality: 802.33.

the following compounds were prepared in the same manner as in example 2, and the synthetic raw materials are shown in table 2 below;

TABLE 2

Example 3: synthesis of Compound 104

Adding 0.01mol of raw material A-1, 0.012mol of 2-bromo-1-chloro-4-iodobenzene and 150ml of toluene into a 250ml three-necked bottle under the protection of nitrogen, stirring and mixing, and then adding 5X 10^-5mol Pd₂(dba)₃，5×10^-5Heating the tri-tert-butylphosphine and 0.03mol of sodium tert-butoxide to 105 ℃, carrying out reflux reaction for 24 hours, and sampling a sample point plate to show that the non-amino compound remains and the reaction is complete; naturally cooling to room temperature, filtering, rotatably steaming the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain an intermediate N-12. LC-MS: measurement value: 357.87([ M + H)](+) of; accurate quality: 356.99.

adding 0.01mol of raw material E-1, 0.012mol of intermediate N-12 and 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 5X 10^-5mol Pd₂(dba)₃，5×10^-5Heating the tri-tert-butylphosphine mol and sodium tert-butoxide 0.03mol to 105 ℃, and carrying out reflux reaction for 24 hours at the sampling pointPlate, show no amine compound remaining, reaction complete; naturally cooling to room temperature, filtering, rotatably steaming the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain an intermediate T-1. LC-MS: measurement value: 639.42([ M + H)](+) of; accurate quality: 638.25.

0.06mol of the raw material D-1 was charged into a 500ml three-necked flask under a nitrogen atmosphere, and a mixed solvent (300ml of toluene, 90ml of H) was added₂O) dissolving the intermediate, introducing nitrogen, stirring for 1 hour, and slowly adding 0.05mol of intermediate T-1 and 0.1mol of K₂CO₃、0.005mol Pd(PPh₃)₄The reaction was heated to 90 ℃ for 8 hours, and the reaction was observed by Thin Layer Chromatography (TLC) until the reaction was complete. And naturally cooling to room temperature, adding water into the reaction system for extraction, separating liquid, and performing reduced pressure rotary evaporation on the organic phase until no fraction is obtained. The obtained substance is purified by a silica gel column to obtain a target product. Elemental analysis Structure (molecular formula C)₅₁H₄₀N₂): theoretical value: c, 89.96; h, 5.92; n, 4.11; test values are: c, 89.91; h, 5.95; and N, 4.15. LC-MS: measurement value: 681.27([ M + H)](+) of; accurate quality: 680.32.

the following compounds were prepared in the same manner as in example 3, and the synthetic raw materials are shown in table 3 below;

TABLE 3

Example 4: synthesis of Compound 172

Adding 0.01mol of intermediate Q-1, 0.012mol of carbazole and 150ml of toluene into a 250ml three-neck flask under the protection of nitrogen, stirring and mixing, and then adding 5 multiplied by 10^-5mol Pd₂(dba)₃，5×10^-5Heating the tri-tert-butylphosphine mol and sodium tert-butoxide 0.03mol to 105 ℃, carrying out reflux reaction for 24 hours, and sampling a sample point plate to show that no carbazole remains and the reaction is complete; naturally cooling to room temperature, filtering, and collecting filtrateAnd (4) performing rotary evaporation until no fraction is obtained, and passing through a neutral silica gel column to obtain a target product with the purity of 99.9% and the yield of 75.9%. Elemental analysis Structure (molecular formula C)₆₇H₄₅N₃): theoretical value: c, 90.21; h, 5.08; n, 4.71; test values are: c, 90.11; h, 5.10; and N, 4.75. LC-MS: measurement value: 892.02([ M + H)](+) of; accurate quality: 891.36.

detection method

Glass transition temperature Tg: measured by differential scanning calorimetry (DSC, DSC204F1 differential scanning calorimeter, Nachi company, Germany), the rate of temperature rise was 10 ℃/min.

HOMO energy level: the test was conducted in a vacuum environment by an ionization energy test system (IPS 3).

Eg energy level: the measurement was carried out by means of a two-beam ultraviolet-visible spectrophotometer (model: TU-1901) using a tangent line based on the ultraviolet spectrophotometric (UV absorption) baseline of the material single film and the rising side of the first absorption peak, and calculating the value of the intersection of the tangent line and the baseline.

Hole mobility: the material was fabricated into a single charge device and measured by space charge (induced) limited current method (SCLC).

Triplet energy level T1: the material was tested by a Fluorolog-3 series fluorescence spectrometer from Horiba under 2X 10-5mol/L toluene solution.

The results of the physical property tests are shown in Table 4.

TABLE 4

As can be seen from the data in table 4 above, the compound of the present invention has a suitable HOMO level, a higher hole mobility, and a wider band gap (Eg), and can realize an organic electroluminescent device having high efficiency, low voltage, and long lifetime.

Preparation of organic electroluminescent device

The molecular structural formula of the materials involved in the following preparation is as follows:

comparative device example 1

The organic electroluminescent device was prepared as follows:

as shown in fig. 1, the anode layer 2(Ag (100nm)) is washed, i.e., washed with alkali, washed with pure water, dried, and then washed with ultraviolet rays and ozone, to remove organic residues on the surface of the anode layer, in the substrate layer 1. On the anode layer 2 after the above washing, HT1 and P-1 having a film thickness of 10nm were deposited as the hole injection layer 3 by a vacuum deposition apparatus, and the mass ratio of HT1 to P-1 was 97: 3. HT1 was then evaporated to a thickness of 117nm as hole transport layer 4. EB-1 was then evaporated to a thickness of 10nm as an electron blocking layer 5. After the evaporation of the electron blocking material is finished, the light emitting layer 6 of the OLED light emitting device is manufactured, and the structure of the OLED light emitting device comprises that BH-1 used by the OLED light emitting layer 6 is used as a main material, BD-1 is used as a doping material, the doping proportion of the doping material is 3% by weight, and the thickness of the light emitting layer is 20 nm. After the light-emitting layer 6, HB1 was deposited by vapor deposition to a film thickness of 8nm to form a hole-blocking layer 7. And continuously evaporating ET-1 and Liq on the hole blocking layer 7, wherein the mass ratio of ET-1 to Liq is 1: 1. The vacuum evaporation film thickness of the material was 30nm, and this layer was an electron transport layer 8. On the electron transport layer 8, a LiF layer having a film thickness of 1nm was formed by a vacuum evaporation apparatus, and this layer was an electron injection layer 9. On the electron injection layer 9, a vacuum deposition apparatus was used to produce a 16 nm-thick Mg: the Ag electrode layer, Mg and Ag mass ratio of 1:9, is used as the cathode layer 10. CP-1 was vacuum-deposited on the cathode layer 10 at 70nm to form a capping layer 11.

Comparative device examples 4 to 6

The procedure of comparative device example 1 was followed except that the organic materials in the hole injection layer and the hole transport layer were respectively replaced with organic materials as shown in table 5.

Device examples 1 to 20

Device examples 21 to 29

The procedure of comparative device example 1 was followed except that the organic materials in the hole injection layer, the hole transport layer and the electron transport layer were respectively replaced with organic materials as shown in table 5.

TABLE 5

In the table above, taking example 1 as an example, the "P-1: 1 ═ 3: 9710 nm" in the second column table indicates that the materials used for the hole injection layer are compound 1 and P-type dopant P-1, and 3:97 means that the weight ratio of P-type dopant to compound 1 is 3:97, 10nm indicates the thickness of the layer; "1117 nm" in the third table indicates that the material used is compound 1, the layer thickness being 117 nm. And so on in other tables.

After the OLED light-emitting device was prepared as described above, the cathode and the anode were connected by a known driving circuit, and various properties of the device were measured. The device measurement performance results of examples 1 to 29 and comparative examples 1, 4, 5 and 6 are shown in table 6.

TABLE 6

Note: LT95 refers to the time it takes for the device luminance to decay to 95% of the original luminance at a luminance of 1500 nits;

voltage, current efficiency and color coordinates were tested using the IVL (current-voltage-brightness) test system (frastd scientific instruments, su); the current density is 10mA/cm²；

The life test system is an EAS-62C type OLED life test system of Japan scientific research Co.

The high-temperature service life means that the current density of the device is 10mA/cm at the temperature of 80 DEG C²The time for the brightness of the device to decay to 80% of the original brightness;

as can be seen from table 6, the results of comparative examples 1, 4, 5 and 6 and device examples 1 to 20, the arylamine organic compound of the present invention, which is used as a hole injection and hole transport layer material, effectively reduces the device voltage, improves the device efficiency and lifetime, and significantly improves the high temperature lifetime of the device due to its high carrier transport rate.

Compared with the device embodiments 1 to 20, the device embodiments 21 to 29 adopt the arylamine organic compound of the present invention and the specific electron transport layer material to be used in combination, and the matching manner further effectively improves the lifetime of the device, and the high temperature lifetime of the device is also significantly improved.

The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

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Arylamine organic compound and organic electroluminescent device containing same

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