CN113402399B

CN113402399B - Arylamine organic compound and organic electroluminescent device containing same

Info

Publication number: CN113402399B
Application number: CN202110563717.7A
Authority: CN
Inventors: 王芳; 李崇
Original assignee: Jiangsu Sunera Technology Co Ltd
Current assignee: Jiangsu Sunera Technology Co Ltd
Priority date: 2021-03-03
Filing date: 2021-05-24
Publication date: 2022-10-25
Anticipated expiration: 2041-05-24
Also published as: CN115710187B; CN115710187A; CN113402399A

Abstract

The invention relates to the technical field of semiconductor materials, and particularly discloses an arylamine organic compound and an organic electroluminescent device containing the same. The structure of the compound is shown as a general formula (I). The arylamine organic compound has excellent hole transport capacity and stability. When the hole transport material of an organic electroluminescent device is formed by using the arylamine organic compound of the present invention, the effects of improving device performance, such as improvement in device efficiency, reduction in driving voltage, and prolongation in lifetime, can be exhibited.

Description

Arylamine organic compound and organic electroluminescent device containing same

Technical Field

The invention relates to the technical field of semiconductor materials, in particular to an arylamine organic compound and an organic electroluminescent device containing the same.

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 hole injection and transmission are better, the adjusting composite region can shift towards the side far away from the electronic barrier layer, so that the light is emitted far away from the interface, the performance of the device is improved, and the service life is prolonged. 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 L ₃ 、L ₄ Each independently represents a direct bond, phenylene, naphthylene, or biphenylene;

said R is ₃ 、R ₄ Each independently represents a substituted or substituted C6-C30 aryl group, a substituted or unsubstituted C containing one or more heteroatoms ₂ -C ₃₀ A heteroaryl group;

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

each of E and D is independently represented by 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 one or more of D, E and F is not represented by a hydrogen atom and A is represented by the general formula (II), D is represented by a hydrogen atom;

in the general formula (II), L is ₁ 、L ₂ Each independently represents a direct bond, phenylene, naphthylene, or biphenylene;

said R is ₁ 、R ₂ Each independently represents a substituted or substituted C6-C30 aryl group, a substituted or unsubstituted C containing one or more heteroatoms ₂ -C ₃₀ A heteroaryl group;

in the general formulas (III) and (IV), when L represents a direct bond or naphthylene group, the L ₄ 、L ₅ Each independently represents a direct bond, phenylene, naphthylene, or biphenylene;

in the general formulas (III) and (IV), when L represents phenylene, L represents ₄ Represented by a direct bond, phenylene, naphthylene or biphenylene, said L ₅ Represented by phenylene, naphthylene or biphenylene;

said R is ₁₁ 、R ₁₂ Each independently being deuterium atom, phenyl or naphthyl, R ₁₁ 、R ₁₂ The connection mode is single substitution or forming a parallel ring structure; ar is represented by C ₆ -C ₃₀ Aryl radical, C containing one or more hetero atoms ₂ -C ₃₀ A 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):

said L is ₃ 、L ₄ Each independently represents a direct bond, phenylene, naphthylene, or biphenylene;

each of E and D 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 general formula (III) or general formula (IV), and when D, E and F have and have only one not represented as a hydrogen atom, and A represents a structure represented by general formula (II), D represents a hydrogen atom;

said R is ₁ -R ₄ Each 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 substituted or unsubstituted diphenylfluorenyl, substituted or unsubstituted spirofluorenyl, substituted or unsubstituted phenanthrenyl, substituted or unsubstituted anthracenyl, substituted or unsubstituted fluorenylUnsubstituted naphthospirofluorenyl, substituted or unsubstituted benzofuranyl, substituted or unsubstituted dibenzofuranyl, substituted or unsubstituted naphthofuranyl, substituted or unsubstituted carbazolyl, substituted or unsubstituted naphthocarbazolyl, substituted or unsubstituted indenyl, or substituted or unsubstituted piperonyl, and R is independently selected from the group consisting of ₁ -R ₄ At 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 is ₁ -R ₄ When at least one is selected from the group consisting of dimethylfluorenyl, R ₁ -R ₄ Neither is represented as heteroaryl and E and D are not selected from formula (III) and formula (IV);

the R is ₁₁ 、R ₁₂ Each independently represents a deuterium atom, a phenyl group or a naphthyl group, R ₁₁ 、R ₁₂ The connection mode of (A) is mono-substitution or forming a parallel ring structure; ar is represented by C ₆ -C ₃₀ Aryl, C containing one or more hetero atoms ₂ -C ₃₀ A heteroaryl group;

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

Preferably, R ₁ -R ₄ Wherein 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, R ₁ Expressed as the following structure:

preferably, R ₃ Expressed 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 L ₁ To L ₄ Each independently represents a direct bond or a phenylene group;

the R is ₁ To R ₄ Are respectively independentRepresented by 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 selected from spirofluorenyl or diphenylfluorenyl.

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 is ₁ To L ₄ Each independently represents a direct bond or a phenylene group;

said R is ₁ To R ₄ Independently 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;

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 is ₁ To L ₄ Each 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-12):

l represents a direct bond, phenylene or naphthylene;

the R is ₁ To R ₃ Each 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 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 is ₁ To L ₄ Each independently represents a direct bond or a phenylene group;

the R is ₂ To R ₄ Each 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 organic compound of the general formula (I) can be represented by a structure shown in a general formula (I-14):

in the general formula (I-14), L is ₁ To L ₄ Each independently represents a direct bond or a phenylene group;

the R is ₂ To R ₄ Each independently represents phenyl, biphenyl, naphthyl, phenanthryl, dimethylfluorenyl, diphenylfluorenyl, spirofluorenyl, dibenzofuranyl, phenyl-substituted naphthyl, naphthyl naphthospirofluorenyl group, phenyl-substituted dimethylfluorenyl group, naphthodiphenylfluorenyl group, furyl group, naphthobenzofuryl group, benzophenanthryl group, phenyl-substituted phenanthryl group, phenyl-substituted furyl group,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-15):

l represents a direct bond, phenylene or naphthylene;

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, phenylene or naphthylene;

said L is ₁ To L ₄ Each independently represents a direct bond or a phenylene group;

said R is ₁ To R ₃ Each 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-17):

in the general formula (I-17), L is ₁ To L ₄ Each independently represents a direct bond or a phenylene group;

said R is ₂ To R ₄ Each 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-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 R is ₁ 、R ₃ 、R ₄ Each 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;

the R is ₁ 、R ₃ 、R ₄ Each 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 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-20):

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

l represents a direct bond, phenylene or naphthylene;

the R is ₃ To R ₄ Independently 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 arylamine organic compound of the general formula (I) can be represented by a structure shown in a general formula (I-21):

said L represents a direct bond, phenylene or naphthylene;

the R is ₁ 、R ₄ Independently 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, more preferably, the first hole transport layer and the hole injection layer comprise the arylamine organic compound described in any one of the preceding items; 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):

wherein Ar is ₅ 、Ar ₆ 、Ar ₇ Independently of one another, are selected from substituted or unsubstituted C ₆ -C ₃₀ Aryl, substituted or unsubstituted C containing one or more hetero atoms ₅ -C ₃₀ Heterocyclyl, said heteroatom being selected from N, O or S;

L ₃ selected from single bond, substituted or unsubstituted C ₆ -C ₃₀ Arylene radical, substituted or unsubstituted C containing one or more hetero atoms ₅ -C ₃₀ (ii) heterocyclylene, each of said heteroatoms being independently selected from N, O or S;

X ₁ 、X ₂ 、X ₃ independently of one another, N or CH, X ₁ 、X ₂ 、X ₃ Represents N.

Has the beneficial effects that:

the technical core of the invention is that the intermediate bridging group of the bistriphenylamine cavity material has a specific torsion angle, that is, the bridged molecular group has a spatial cross-structural conformation of ortho-position and meta-position, and the cross-conformation enables the molecules characterized by 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 intermediate bridging group in the bistriarylamine structure, energy levels with differential carrier conduction are ensured to be formed in the bistriarylamine molecular structure, so that different carrier conduction channels are formed, carrier injection and conduction among different energy level material combinations are facilitated, interface stability between the arylamine material and adjacent materials is facilitated, and good high-low temperature driving service life of an application device is facilitated.

(3) It is known that, in the case of 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 hence the higher hole carrier conduction efficiency is 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 as the group or group derivative (containing a parallel ring structure or a similar group of a substituted structure) with stronger planarity, or with larger structure radius, so that the stability and mobility of the material can be improved, and the precise regulation and control of the HOMO energy level of the material can be facilitated, and further, a good device application effect of the material can be obtained.

The organic functional materials 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 application effect, and needs a good carrier balance degree for protection, therefore, in order to obtain the best application effect of the device, 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 electron-type material is preferably a material containing structural characteristics of an azepine, such as a triazine-based material, a pyridine-based material, a 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 shows the nuclear magnetic spectrum of compound 206 of the present invention.

FIG. 4 is a nuclear magnetic spectrum of compound 115 of the present invention.

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 context.

In this specification, the term "C ₆ -C ₃₀ Aryl "or" C ₆ -C ₃₀ Arylene "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 "C ₂ -C ₃₀ Heterocyclyl "refers to saturated, partially saturated, or fully unsaturated cyclic groups 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-C30 Aryl and/or substituted or unsubstituted C ₂ -C ₃₀ Heterocyclic ringsThe group means a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl 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 isophthaltriphenylyl group, a substituted or unsubstituted terphenylyl group

In the present specification, substituted or unsubstituted C ₆ -C ₃₀ Arylene or substituted or unsubstituted C ₂ -C ₃₀ Heterocyclylene means respectively substituted or unsubstituted C as defined above and having two linking groups ₆ -C ₃₀ Aryl or substituted or unsubstituted C ₅ -C ₃₀ Heterocyclic radicals, e.g. substituted or unsubstituted phenylene, substituted or unsubstituted naphthylene, substituted or unsubstituted anthracenylene, substituted or unsubstituted phenanthrenylene, substituted or unsubstituted tetracenylene, substituted or unsubstituted pyrenylene, substituted or unsubstituted biphenylene, substituted or unsubstituted terphenylene, substituted or unsubstituted isophthalyltriphenylene, substituted or unsubstituted naphthylene

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 a conductive characteristic 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 differs 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, such as LiF/Al, li ₂ O/Al and BaF ₂ But 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 20nm.

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 can 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 included 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 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 can 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 used is 99.

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 as the P-type dopant material, and thus it is expected that a charge transfer state between the host material and the dopant material is generated, ohmic contact between the hole injection layer and the anode is realized, and efficient injection of holes from the electrode into the hole injection layer is realized. 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 0.4eV. Therefore, for hole-type host materials with different HOMO levels, different P-type doping materials need to be selected and matched 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, arylamine organic materials, hexanitrile hexaazatriphenylene, quinacridone organic materials, perylene organic materials, 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 present invention, the ratio of the host organic material to the P-type dopant material used is 99.

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 portions 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 to 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 used ₃ Metal 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 No.: 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 LG 201), 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 is ₅ 、Ar ₆ And Ar ₇ Independently of one another, represents substituted or unsubstituted C ₆ -C ₃₀ Aryl, substituted or unsubstituted C containing one or more hetero atoms ₅ -C ₃₀ Heterocyclyl, the heteroatoms being independently from each other selected from N, O or S;

L ₃ selected from substituted or unsubstituted C ₆ -C ₃₀ Arylene radical, substituted or unsubstituted C containing one or more hetero atoms ₅ -C ₃₀ (ii) heterocyclylene, each of said heteroatoms being independently selected from N, O or S;

n represents 1 or 2;

X ₁ 、X ₂ 、X ₃ independent of each otherIs N or CH, with the proviso that X ₁ 、X ₂ 、X ₃ At 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 is ₅ 、Ar ₆ 、Ar ₇ 、X ₁ 、X ₂ 、X ₃ 、L ₃ Each 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 present invention, the electron transport layer comprises, in addition to the compound of the general formula (III), other compounds conventionally used in electron transport layers, such as 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 compounds of the present invention can be better matched to the electron injection and transport rates of the electron transport region containing the azacyclic derivatives of 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.

Cover 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 further 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 as better. 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 one 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, disposed between the anode 2 and the cathode 10 in this order, 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, disposed over a substrate 1 and the cathode below 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, the respective layers are preferably 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 and are to be interpreted 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 ^-5 mol Pd ₂ (dba) ₃ ，5×10- ⁵ Heating the mol of tri-tert-butylphosphine and 0.03mol of sodium tert-butoxide to 105 ℃, performing 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 is weighed out and dissolved in 150ml of Tetrahydrofuran (THF) under nitrogen atmosphere, then 0.03mol of bis (pinacolato) diboron and 1X 10 mol of the mixture are added ^-4 Adding 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-mouth bottle under the protection of nitrogen, stirring and mixing, and then adding 5 x 10 ^-5 mol Pd ₂ (dba) ₃ ，5×10 ^-5 Heating 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.

under a nitrogen atmosphere, 0.005mol of intermediate M-1 and 0.006mol of intermediate were added to a 250ml three-necked flaskBulk N-1, 5X 10 ^-5 mol Pd(OAc) ₂ 40ml of DMF, stirring for 30 minutes by introducing nitrogen, and then adding K ₃ PO ₄ Aqueous solution (0.0075 mol K) ₃ PO ₄ Dissolved 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 in a nitrogen atmosphere, and a mixed solvent (300 ml of toluene, 90ml of H) was added ₂ O) dissolving it, introducing nitrogen, stirring for 1 hour, and slowly adding 0.05mol of intermediate Q-1 and 0.1mol of K ₂ CO ₃ 、0.005mol Pd(PPh ₃ ) ₄ The 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) ₆₁ H ₄₂ N ₂ ): theoretical value: c,91.24; h,5.27; n,3.49; test values: 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-mouth bottle under the protection of nitrogen gas, stirring and mixing, and then adding 5 x 10 ^-5 mol Pd ₂ (dba) ₃ ，5×10 ^-5 Heating the mol of tri-tert-butylphosphine and 0.03mol of sodium tert-butoxide to 105 ℃, performing 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, carrying out rotary evaporation on 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 bottle under the protection of nitrogen gas, stirring and mixing, and then adding 5X 10 ^-5 mol Pd ₂ (dba) ₃ ，5×10 ^-5 Heating the mol of tri-tert-butylphosphine and 0.03mol of sodium tert-butoxide to 105 ℃, performing 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, carrying out rotary evaporation on 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)](+) to a base; accurate quality: 638.25.

0.06mol of the raw material D-1 was charged into a 500ml three-necked flask in a nitrogen atmosphere, and a mixed solvent (300 ml of toluene, 90ml of H) was added ₂ O) dissolving it, introducing nitrogen, stirring for 1 hour, and slowly adding 0.05mol of intermediate T-1 and 0.1mol of K ₂ CO ₃ 、0.005mol Pd(PPh ₃ ) ₄ The 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) ₅₁ H ₄₀ N ₂ ): 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-mouth bottle under the protection of nitrogen, stirring and mixing, and then adding 5 multiplied by 10 ^-5 mol Pd ₂ (dba) ₃ ，5×10 ^-5 Heating 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, carrying out rotary evaporation on the filtrate until no fraction is obtained, and passing through a neutral silica gel column to obtain the target product with the purity of 99.9 percent and the yield of 75.9 percent. Elemental analysis Structure (molecular formula C) ₆₇ H ₄₅ N ₃ ): theoretical values are as follows: c,90.21; h,5.08; n,4.71; test values: c,90.11; h,5.10; and N,4.75.LC-MS: measurement value: 892.02 ([ M + H)](+) to a base; accurate quality: 891.36.

detection method

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

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

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

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

Triplet state 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 (100 nm)) 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. HT1 and P-1 having a film thickness of 10nm were deposited on the anode layer 2 after the above washing by a vacuum deposition apparatus as the hole injection layer 3, and the mass ratio of HT1 to P-1 was 97. Next, HT1 was evaporated to a thickness of 117nm as a 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 20nm. After the light-emitting layer 6, HB1 was deposited by evaporation to a film thickness of 8nm to form a hole-blocking layer 7. And continuing to vapor-deposit ET-1 and Liq on the hole blocking layer 7, wherein the mass ratio of ET-1 to Liq is 1. The vacuum deposition film thickness of this 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 16nm thick Mg: and the mass ratio of Mg to Ag is 1. 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 process of comparative example 1 of the device 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

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 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 above table, taking the example 1 row as an example, the "P-1": 97 10nm indicates the thickness of the layer; "1 117nm" in the third table column indicates that the material used is compound 1, the layer thickness being 117nm. 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/cm ² ；

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 C ² The time for the brightness of the device to decay to 80% of the original brightness;

table 6 results of comparative examples 1, 4, 5, and 6, and device examples 1 to 20 show that, when the arylamine organic compound of the present invention is used as a hole injection and hole transport layer material, the device voltage is effectively reduced, the device efficiency and lifetime are improved, and the high-temperature lifetime of the device is significantly improved due to the higher 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 should not be taken as limiting the scope of the present invention, which is intended to cover any modifications, equivalents, improvements, etc. within the spirit and scope of the present invention.

Claims

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

said L ₃ 、L ₄ Each independently is represented by a direct bond;

a is represented by a structure shown in a general formula (II);

b represents a hydrogen atom;

f represents a hydrogen atom, phenyl, naphthyl or biphenyl;

d represents a hydrogen atom;

e represents a hydrogen atom, phenyl, biphenyl, naphthyl, benzofuranyl or a structure shown in a general formula (III), and only one of E and F is not represented as a hydrogen atom;

in the general formula (II), L ₁ 、L ₂ Each independently is represented as a direct bond;

the R is ₁ -R ₄ Each independently represents a substituted or unsubstituted phenyl, naphthyl, biphenyl, spirofluorenyl, benzofuranyl, or indenyl group, and R is ₁ -R ₄ And only one is selected from spirofluorenyl;

in the general formula (III), L ₄ Expressed as a direct bond;

the R is ₁₁ Represented as a deuterium atom;

m represents 0;

the substituent of the substituent group is optionally selected from deuterium atom, methyl group or tert-butyl group.

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 or biphenyl;

said L represents a direct bond, phenylene or naphthylene;

said L ₁ To L ₄ Each independently is represented as a direct bond;

said R is ₁ To R ₄ Each independently represents phenyl, biphenyl, naphthyl, spirofluorenyl, benzofuranyl, or indenyl, and only one is selected from spirofluorenyl.

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

in the general formula (I-10), L is ₁ To L ₄ Each independently is represented as a direct bond;

the R is ₁ To R ₄ Independently represent phenyl, biphenyl, naphthyl, spirofluorenyl, benzofuranyl or indenyl, and only one is selected from spirofluorenyl;

and E represents phenyl, biphenyl, naphthyl or benzofuranyl.

4. The aromatic amine organic compound according to claim 1, wherein the aromatic amine 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 is ₁ To L ₄ Each independently is represented by a direct bond;

said R is ₁ To R ₄ Each independently represents phenyl, biphenyl, naphthyl, spirofluorenyl, benzofuranyl, or indenyl, and one and only one is selected from spirofluorenyl;

and E represents phenyl, biphenyl, naphthyl or benzofuranyl.

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

f represents phenyl, naphthyl or biphenyl;

l represents a direct bond, phenylene or naphthylene;

said L ₁ To L ₄ Each independently is represented as a direct bond;

the R is ₁ To R ₃ Each independently represents phenyl, biphenyl, naphthyl, spirofluorenyl, benzofuranyl or indenyl.

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

in the general formula (I-13), L is ₁ To L ₄ Each independently is represented by a direct bond;

the R is ₂ To R ₄ Independently represent phenyl, biphenyl, naphthyl, spirofluorenyl, benzofuranyl or indenyl;

and E represents phenyl, biphenyl, naphthyl or benzofuranyl.

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 is ₁ To L ₄ Each independently is represented by a direct bond;

said R is ₂ To R ₄ Independently represent phenyl, biphenyl, naphthyl, spirofluorenyl, benzofuranyl or indenyl;

and E represents phenyl, biphenyl, naphthyl or benzofuranyl.

8. The aromatic amine organic compound according to claim 1, wherein the aromatic amine organic compound of the general formula (I) is represented by a structure represented by general formula (I-17):

in the general formula (I-17), L is ₁ To L ₄ Each independently is represented as a direct bond;

said R is ₂ To R ₄ Each independently represents phenyl, biphenyl, naphthyl, spirofluorenyl or benzofuranylOr indenyl;

and E represents phenyl, biphenyl, naphthyl or benzofuranyl.

9. The aromatic amine organic compound according to claim 1, wherein the compound has the following specific structure:

10. 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, characterized in that the hole transport region comprises an arylamine-based organic compound according to any one of claims 1 to 9.

11. The organic electroluminescent device according to claim 10, wherein the hole transport region comprises a hole injection layer, a first hole transport layer and a second hole transport layer, and the first hole transport layer and the hole injection layer comprise the arylamine-based organic compound according to any one of claims 1 to 9.

12. An organic electroluminescent device according to claim 11, wherein the first hole transport layer is composed of the arylamine organic compound according to any one of claims 1 to 9, and the hole injection layer is composed of the arylamine organic compound according to any one of claims 1 to 9 and other doping materials conventionally used for a hole injection layer.

13. The organic electroluminescent device according to claim 10, wherein the electron transport region comprises a nitrogen heterocyclic compound represented by the following general formula (III):

wherein Ar is ₅ 、Ar ₆ 、Ar ₇ Independently of one another, from C ₆ -C ₃₀ Aryl radical, C containing one or more hetero atoms ₅ -C ₃₀ Heterocyclyl, said heteroatom being selected from N, O or S;

L ₃ selected from the group consisting of single bond, C ₆ -C ₃₀ Arylene radical, C containing one or more hetero atoms ₅ -C ₃₀ (ii) heterocyclylene, each of said heteroatoms being independently selected from N, O or S;