# US 8,771,841 B2 · Organic electroluminescent device

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- Number: US 8,771,841 B2
- Document ID: US8771841B2
- Status: Granted
- Kind: B2
- Application number: 12/993,051
- Filed: 2009-05-15
- Published: 2011-03-31
- Granted: 2014-07-08
- Earliest claimed: 2008-05-16
- Assignees: Hodogaya Chemical Co., Ltd.
- Applicants: Norimasa Yokoyama; Shigeru Kusano; Shuichi Hayashi
- Inventors: Norimasa Yokoyama; Shigeru Kusano; Shuichi Hayashi
- Web page: https://patentgrep.com/patent/US8771841B2

## CPC

- H10K 85/633: {comprising polycyclic condensed aromatic hydrocarbons as substituents on the nitrogen atom}
- C07D 471/04: Ortho-condensed systems
- C09K 11/06: containing organic luminescent materials
- H10K 85/631: {Amine compounds having at least two aryl rest on at least one amine-nitrogen atom, e.g. triphenylamine}
- C09K 2211/1014: bridged by heteroatoms, e.g. N, P, Si or B
- H10K 50/14: Carrier transporting layers
- H10K 85/615: {Polycyclic condensed aromatic hydrocarbons, e.g. anthracene}
- H10K 85/654: {comprising only nitrogen as heteroatom (H10K85/652 takes precedence)}
- H10K 85/6572: {comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole}
- H10K: ORGANIC ELECTRIC SOLID-STATE DEVICES
- C07D: HETEROCYCLIC COMPOUNDS (macromolecular compounds C08)
- C09K: MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE

## Abstract

A problem of the invention is to provide an organic EL device having a high efficiency, a low driving voltage and a long life, by combining various materials for organic EL device, which are excellent in an injection or transportation performance of holes or electrons, and in stability and durability in a thin film, so as to enable the respective materials to effectively reveal their characteristics. The invention relates to an organic electroluminescent device including at least an anode electrode, a hole-injecting layer, a hole-transporting layer, an emitting layer, an electron-transporting layer and a cathode electrode in this order, in which the hole-injecting layer contains an arylamine compound having, in its molecule, a structure in which three or more triphenylamine structures are connected through a single bond or a hetero atom-free divalent group; and the hole-transporting layer contains an arylamine compound having two triphenylamine structures in its molecule.

## Claims

### Claim 1

An organic electroluminescent device comprising, in this order:
an anode electrode;
a hole-injecting layer;
a hole-transporting layer;
an emitting layer;
an electron-transporting layer; and
a cathode electrode,
wherein the electron-transporting layer comprises a third compound having a pyridine ring and a pyridoindole ring in its structure and represented by formula (1):
wherein:
Ar1 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group;
R1 to R11 may be the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group;
B1 represents a substituted or unsubstituted aromatic hydrocarbon divalent group, a substituted or unsubstituted aromatic heterocyclic divalent group, a substituted or unsubstituted condensed polycyclic aromatic divalent group, or a single bond;
m1 and n1 each represent an integer of from 1 to 3; and
W, X, Y, and Z each represent a carbon atom or a nitrogen atom, provided that when m1 is 2, and when m1 is 3, then n1 is 1, and only one of W, X, Y, and Z represents a nitrogen atom, and the nitrogen atom is not substituted with any of R8 to R11;
wherein the hole-injecting layer comprises a first arylamine compound represented by formula (2):
wherein:
R12 to R23 are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic, group or a substituted or unsubstituted condensed polycyclic aromatic group, and when a plurality of these substituents are bonded on the same benzene ring, they may be bonded to each other to form a ring;
r12 to r23 each represent an integer of from 1 to 4; and
A1, A2, and A3 are the same or different and each represents a divalent group represented by one of structural formulae (B) to (F):
wherein n2 represents an integer of from 1 to 3;
or
a single bond, and
wherein the hole-transporting layer comprises a second arylamine compound represented by formula (3):
wherein:
R24 to R29 are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having from 1 to 6 carbon atoms, a linear or branched alkenyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, and when a plurality of these substituents are bonded on the same benzene ring, they may be bonded to each other to form a ring;
r24 to r29 each represent an integer of from 1 to 4; and
A4 represents a divalent group represented by one of structural formulae (B) to (F):
wherein n2 represents an integer of from 1 to 3;
or
a single bond.

### Claim 2 (depends on 1)

The organic electroluminescent device according to claim 1, wherein the hole-transporting layer has a film thickness of from 20 to 300 nm.

### Claim 3

An organic electroluminescent device comprising, in this order:
an anode electrode;
a hole-injecting layer;
a hole-transporting layer;
an emitting layer;
an electron-transporting layer; and
a cathode electrode,
wherein the hole-injecting layer comprises a first arylamine compound having a structure in which three or more triphenylamine structures are connected through a single bond or a hetero atom-free divalent group, and
wherein the hole-transporting layer comprises a second arylamine compound having two triphenylamine structures,
wherein the electron-transporting layer comprises a third compound having a pyridine ring and a pyridoindole ring in its structure and represented by formula (1):
wherein:
Ar1 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group;
R1 to R11 may be the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group;
B1 represents a substituted or unsubstituted aromatic hydrocarbon divalent group, a substituted or unsubstituted aromatic heterocyclic divalent group, a substituted or unsubstituted condensed polycyclic aromatic divalent group, or a single bond;
m1 and n1 each represent an integer of from 1 to 3; and
W, X, Y, and Z each represent a carbon atom or a nitrogen atom, provided that when m1 is 2, and when m1 is 3, then n1 is 1, and only one of W, X, Y, and Z represents a nitrogen atom, and the nitrogen atom is not substituted with any of R8 to R11.

### Claim 4 (depends on 3)

The organic electroluminescent device according to claim 3, wherein the first arylamine compound is represented by formula (2):
wherein:
R12 to R23 are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, and when a plurality of these substituents are bonded on the same benzene ring, they may be bonded to each other to form a ring;
r12 to r23 each represent an integer of from 1 to 4; and
A1, A2, and A3 are the same or different and each represents a divalent group represented by one of structural formulae (B) to (F):
wherein n2 represents an integer of from 1 to 3;
a single bond.

### Claim 5 (depends on 3)

The organic electroluminescent device according to claim 3, wherein the second arylamine compound represented by formula (3):
wherein:
R24 to R29 are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having from 1 to 6 carbon atoms, a linear or branched alkenyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, and when a plurality of these substituents are bonded on the same benzene ring, they may be bonded to each other to form a ring;
r24 to r29 each represent an integer of from 1 to 4; and
A4 represents a divalent group represented by one of structural formulae (B) to (F):
wherein n2 represents an integer of from 1 to 3;
or
a single bond.

### Claim 6 (depends on 3)

The organic electroluminescent device according to claim 3, wherein the third compound is represented by formula (4):
wherein:
Ar2 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group;
R30 to R44 may be the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group;
n3 represents an integer of from 1 to 3; and
W, X, Y, and Z each represents a carbon atom or a nitrogen atom, provided that only one of W, X, Y, and Z represents a nitrogen atom, and the nitrogen atom is not substituted with any of R37 to R40.

### Claim 7 (depends on 3)

The organic electroluminescent device according to claim 3, wherein the third compound is represented by formula (5):
wherein:
Ar3 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group or a substituted or unsubstituted condensed polycyclic aromatic group;
R45 to R55 are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group;
m2 and n4 each represent an integer of from 1 to 3; and
W, X, Y, and Z each represent a carbon atom or a nitrogen atom, provided that when m2 is 2, and when m2 is 3, then n4 is 1, and only one of W, X, Y, and Z represents a nitrogen atom, and the nitrogen atom is not substituted with any of R52 to R55.

### Claim 8 (depends on 1)

The organic electroluminescent device according to claim 1, wherein the second arylamine compound is represented by formula (3):
wherein:
R24 to R29 are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having from 1 to 6 carbon atoms, a linear or branched alkenyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, and when a plurality of these substituents are bonded on the same benzene ring, they may be bonded to each other to form a ring;
r24 to r29 each represent an integer of from 1 to 4; and
A4 represents a divalent group represented by one of structural formulae (B) to (F):
wherein n2 represents an integer of from 1 to 3;
or
a single bond.

### Claim 9 (depends on 1)

The organic electroluminescent device according to claim 1, wherein the hole-transporting layer has a film thickness of from 20 to 300 nm.

### Claim 10 (depends on 8)

The organic electroluminescent device according to claim 8, wherein the hole-transporting layer has a film thickness of from 20 to 300 nm.

### Claim 11 (depends on 4)

The organic electroluminescent device according to claim 4, wherein the second arylamine compound is represented by formula (3):
wherein:
R24 to R29 are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having from 1 to 6 carbon atoms, a linear or branched alkenyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group, and when a plurality of these substituents are bonded on the same benzene ring, they may be bonded to each other to form a ring;
r24 to r29 each represent an integer of from 1 to 4; and
A4 represents a divalent group represented by one of structural formulae (B) to (F):
wherein n2 represents an integer of from 1 to 3;
or
a single bond.

### Claim 12 (depends on 4)

The organic electroluminescent device according to claim 4, wherein the third compound is represented by formula (4):
wherein:
Ar2 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group;
R30 to R44 may be the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group;
n3 represents an integer of from 1 to 3; and
W, X, Y, and Z each represents a carbon atom or a nitrogen atom, provided that only one of W, X, Y, and Z represents a nitrogen atom, and the nitrogen atom is not substituted with any of R37 to R40.

### Claim 13 (depends on 5)

The organic electroluminescent device according to claim 5, wherein the third compound is represented by formula (4):
wherein:
Ar2 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group;
R30 to R44 may be the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group;
n3 represents an integer of from 1 to 3; and
W, X, Y, and Z each represents a carbon atom or a nitrogen atom, provided that only one of W, X, Y, and Z represents a nitrogen atom, and the nitrogen atom is not substituted with any of R37 to R40.

### Claim 14 (depends on 11)

The organic electroluminescent device according to claim 11, wherein the third compound is represented by formula (4):
wherein:
Ar2 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group;
R30 to R44 may be the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group;
n3 represents an integer of from 1 to 3; and
W, X, Y, and Z each represents a carbon atom or a nitrogen atom, provided that only one of W, X, Y, and Z represents a nitrogen atom, and the nitrogen atom is not substituted with any of R37 to R40.

### Claim 15 (depends on 4)

The organic electroluminescent device according to claim 4, wherein the third compound is represented by formula (5):
wherein:
Ar3 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group or a substituted or unsubstituted condensed polycyclic aromatic group;
R45 to R55 are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group;
m2 and n4 each represent an integer of from 1 to 3; and
W, X, Y, and Z each represent a carbon atom or a nitrogen atom, provided that when m2 is 2, and when m2 is 3, then n4 is 1, and only one of W, X, Y, and Z represents a nitrogen atom, and the nitrogen atom is not substituted with any of R52 to R55.

### Claim 16 (depends on 5)

The organic electroluminescent device according to claim 5, wherein the third compound is represented by formula (5):
wherein:
Ar3 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group or a substituted or unsubstituted condensed polycyclic aromatic group;
R45 to R55 are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group;
m2 and n4 each represent an integer of from 1 to 3; and
W, X, Y, and Z each represent a carbon atom or a nitrogen atom, provided that when m2 is 2, and when m2 is 3, then n4 is 1, and only one of W, X, Y, and Z represents a nitrogen atom, and the nitrogen atom is not substituted with any of R52 to R55.

### Claim 17 (depends on 11)

The organic electroluminescent device according to claim 11, wherein the third compound is represented by formula (5):
wherein:
Ar3 represents a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group or a substituted or unsubstituted condensed polycyclic aromatic group;
R45 to R55 are the same or different and each represents a hydrogen atom, a fluorine atom, a chlorine atom, a cyano group, a trifluoromethyl group, a linear or branched alkyl group having from 1 to 6 carbon atoms, a substituted or unsubstituted aromatic hydrocarbon group, a substituted or unsubstituted aromatic heterocyclic group, or a substituted or unsubstituted condensed polycyclic aromatic group;
m2 and n4 each represent an integer of from 1 to 3; and
W, X, Y, and Z each represent a carbon atom or a nitrogen atom, provided that when m2 is 2, and when m2 is 3, then n4 is 1, and only one of W, X, Y, and Z represents a nitrogen atom, and the nitrogen atom is not substituted with any of R52 to R55.

### Claim 18 (depends on 1)

The organic electroluminescent device according to claim 1, wherein the first arylamine compound is Compound 2-1:

### Claim 19 (depends on 1)

The organic electroluminescent device according to claim 1, wherein the second arylamine compound is Compound 3-1:

### Claim 20 (depends on 1)

The organic electroluminescent device according to claim 1, wherein the third compound is Compound 1-10:

### Claim 21 (depends on 1)

The organic electroluminescent device according to claim 1, wherein the first arylamine compound is Compound 2-1:
and the second arylamine compound is Compound 3-1:

### Claim 22 (depends on 1)

The organic electroluminescent device according to claim 1, wherein the first arylamine compound is Compound 2-1:
and the third compound is Compound 1-10:

### Claim 23 (depends on 1)

The organic electroluminescent device according to claim 1, wherein the second arylamine compound is Compound 3-1:
and the third compound is Compound 1-10:

### Claim 24 (depends on 1)

The organic electroluminescent device according to claim 1, wherein the first arylamine compound is Compound 2-1:
the second arylamine compound is Compound 3-1:
and the third compound is Compound 1-10: