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CN109791989B - Organic electroluminescent device - Google Patents

Organic electroluminescent device Download PDF

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Publication number
CN109791989B
CN109791989B CN201780059142.7A CN201780059142A CN109791989B CN 109791989 B CN109791989 B CN 109791989B CN 201780059142 A CN201780059142 A CN 201780059142A CN 109791989 B CN109791989 B CN 109791989B
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CN109791989A (en
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李泰珍
D-H·李
金宾瑞
吴洪世
金荣光
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Rohm and Haas Electronic Materials Korea Ltd
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Abstract

The present disclosure relates to an organic electroluminescent device. The organic electroluminescent device of the present disclosure can provide a low driving voltage and excellent luminous efficiency by including a specific combination of a host compound and a hole transport material.

Description

Organic electroluminescent device
Technical Field
The present disclosure relates to an organic electroluminescent device.
Background
An electroluminescent device (EL device) is a self-luminous display device, which is advantageous in that it provides a wider viewing angle, a greater contrast ratio, and a faster response time. The first organic EL device was developed by Eastman Kodak in 1987 by using a small aromatic diamine molecule and an aluminum complex as a material for forming a light-emitting layer [ appl.phys.lett. ] 51,913,1987.
An organic EL device (OLED) converts electric energy into light by applying the electric energy to an organic light emitting material, and generally includes an anode, a cathode, and a dielectric layer formed between the two electrodes. The dielectric layer of the organic EL device may include a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron buffer layer, a hole blocking layer, an electron transport layer, an electron injection layer, and the like. Materials for the dielectric layer are classified into a hole injection material, a hole transport material, an electron blocking material, a light emitting material, an electron buffer material, a hole blocking material, an electron transport material, an electron injection material, and the like according to functions. In the organic EL device, holes from an anode and electrons from a cathode are injected into a light emitting layer by applying a voltage, and excitons having high energy are generated by recombination of the holes and the electrons. When the organic light emitting compound returns from the excited state to the ground state, the organic light emitting compound moves to the excited state by energy, and light is emitted from the energy.
In 1987, Tang et al of Eastman Kodak developed a low-molecular green light-emitting organic electroluminescent device using a TPD/ALq3 bilayer composed of a light-emitting layer and a charge transport layer. Since then, the development of organic EL devices is rapidly affected, and the devices are now commercialized. Current organic EL devices mainly use phosphorescent materials having excellent luminous efficiency for panel fabrication. For long-term use and high resolution of the display, low driving voltage and high efficiency are required. If the efficiency is high, there are problems of a reduction in lifetime and an increase in driving voltage. If the driving voltage is lowered, there is a problem of low efficiency. In order to obtain a low driving voltage, a hole transport layer having a high hole mobility and a light emitting layer having a low driving voltage may be used. However, this results in a reduction in efficiency.
Korean patent application laid-open No. 2015-0066202 discloses an organic electroluminescent device using a compound in which diarylamine or the like is bonded to the 5-membered ring and the benzene ring of benzo [ b ] fluorene in the hole transport layer, respectively. However, this reference does not specifically disclose a combination of a diarylamine bonded at the fifth carbon position of the naphthalene ring of benzo [ b ] fluorene and a nitrogen-containing heteroaryl group bonded to the nitrogen atom of indolocarbazole in another compound, which is applied to an organic electroluminescent device.
Disclosure of Invention
Problems to be solved
An object of the present disclosure is to provide an organic electroluminescent device having a low driving voltage and excellent luminous efficiency by including a specific combination of compounds in a hole transport region and a light emitting layer.
Solution to the problem
The present inventors have found that the problem of efficiency reduction upon reduction of driving voltage can be improved by an organic electroluminescent device comprising: a first electrode; a second electrode opposed to the first electrode; one or more light emitting layers disposed between the first electrode and the second electrode; and one or more layers of hole transport regions disposed between the first electrode and the light emitting layer, wherein at least one layer of the hole transport regions comprises a compound represented by formula 1 below, and at least one layer of the light emitting layer comprises a compound represented by formula 2 below:
Figure BDA0002006467680000021
wherein
Ar1To Ar6Each independently represents a substituted or unsubstituted (C1-C30) alkyl group, a substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted (5-to 30-membered) heteroaryl group, or a substituted or unsubstituted spiro [ fluorene- (C3-C30) cycloalkane](ii) a Or Ar1And Ar2、Ar3And Ar4And Ar5And Ar6Are linked to each other to form a mono-or polycyclic, (3-to 30-membered) alicyclic or aromatic ring or a combination thereof, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
L1represents a single bond, a substituted or unsubstituted (C6-C30) arylene, or a substituted or unsubstituted (5-to 30-membered) heteroarylene;
L2represents a single bond, a substituted or unsubstituted (C1-C30) alkylene group, a substituted or unsubstituted (C6-C30) arylene group, or a substituted or unsubstituted (5-to 30-membered) heteroarylene group, provided that wherein n is 0, L2Is absent;
R1and R2Each independently represents hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5-to 30-membered) heteroaryl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (3-to 7-membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl (C1-C30) alkyl, -NR11R12、-SiR13R14R15、-SR16、-OR17Cyano, nitro or hydroxy; or are linked to an adjacent substituent(s) to form a mono-or polycyclic, (3-to 30-membered) alicyclic or aromatic ring or a combination thereof, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
R11to R17Each independently represents hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5-to 30-membered) heteroaryl, substituted or unsubstituted (3-to 7-membered) heterocycloalkyl, or substituted or unsubstituted (C3-C30) cycloalkyl; or are linked to an adjacent substituent(s) to form a mono-or polycyclic, (3-to 30-membered) alicyclic or aromatic ring or a combination thereof, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
m represents an integer of 1 to 2, wherein m is 2, each NAr1Ar2May be the same or different;
n represents an integer of 0 to 2, wherein n is 2, and each NAr3Ar4May be the same or different;
a represents an integer of 1 to 5, wherein a is 2Or greater, each R1May be the same or different;
b represents an integer of 1 to 4, wherein b is an integer of 2 or more, and each R2May be the same or different;
ma represents a substituted or unsubstituted nitrogen-containing (3-to 30-membered) heteroaryl group;
L3represents a single bond, a substituted or unsubstituted (C6-C30) arylene, or a substituted or unsubstituted nitrogen-containing (3-to 30-membered) heteroarylene;
formula 2 and formula 2-a are fused at the positions of e and f, f and g or g and h of formula 2, and at the position of x of formula 2-a to form a ring;
R3to R5Each independently represents hydrogen, deuterium, a substituted or unsubstituted (C1-C30) alkyl group, a substituted or unsubstituted (C6-C30) aryl (C1-C30) alkyl group, a substituted or unsubstituted (C6-C6) aryl group, a substituted or unsubstituted (C6-C6) alkyl (C6-C6) aryl group, a substituted or unsubstituted (3-to 30-membered) heteroaryl group, a substituted or unsubstituted (C6-C6) cycloalkyl group, a substituted or unsubstituted tri (C6-C6) alkylsilyl group, a substituted or unsubstituted di (C6-C6) alkyl (C6-C6) arylsilyl group, a substituted or unsubstituted (C6-C6) alkyl di (C6-C6) arylsilyl group, a substituted or unsubstituted tri (C72-C6) arylsilyl group, a substituted or unsubstituted mono (C6-C6) alkyl amino group, a substituted or unsubstituted (C6-C6) amino group, a substituted or unsubstituted (C6) aryl group C30) Alkyl (C6-C30) arylamino;
r represents hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl (C30-C30) alkyl, substituted or unsubstituted (C30-C30) aryl, substituted or unsubstituted (C30-C30) alkyl (C30-C30) aryl, substituted or unsubstituted (3-to 30-membered) heteroaryl, substituted or unsubstituted (C30-C30) cycloalkyl, substituted or unsubstituted tri (C30-C30) alkylsilyl, substituted or unsubstituted di (C30-C30) alkyl (C30-C30) arylsilyl, substituted or unsubstituted (C30-C30) alkyldi (C30-C30) arylsilyl, substituted or unsubstituted tri (C30-C30) arylsilyl, substituted or unsubstituted mono or di (C30-C30) alkylamino, substituted or unsubstituted (C30-C30) arylamino or substituted or unsubstituted (C30-C30) arylamino A group (C6-C30) arylamino;
o and q each independently represent an integer of 1 to 4, and p represents an integer of 1 to 2, wherein o, p and q are integers of 2 or more, and each of R3 to R5 may be the same or different;
heteroaryl (heteroarylene) contains at least one heteroatom selected from B, N, O, S, Si and P; and is
Heterocycloalkyl contains at least one heteroatom selected from O, S and N.
Effects of the invention
According to the present disclosure, an organic electroluminescent device having a low driving voltage and excellent luminous efficiency may be provided, and a display device or an illumination device may be manufactured using the same.
Detailed Description
Hereinafter, the present disclosure will be described in detail. However, the following description is intended to be illustrative of the present disclosure and is not intended to limit the scope of the present disclosure in any way.
The term "organic electroluminescent compound" in the present disclosure refers to a compound that can be used in an organic electroluminescent device, and can be contained in any layer constituting the organic electroluminescent device as needed.
The term "organic electroluminescent material" in the present disclosure refers to a material that may be used in an organic electroluminescent device, and may include at least one compound. The organic electroluminescent material may be contained in any layer constituting the organic electroluminescent device, as necessary. For example, the organic electroluminescent material may be a hole injection material, a hole transport material, a hole assist material, a light emission assist material, an electron blocking material, a light emitting material, an electron buffering material, a hole blocking material, an electron transport material, or an electron injection material.
Hereinafter, the organic electroluminescent device of the present disclosure will be described in detail.
Herein, "(C1-C30) alkyl (alkylene)" means a straight or branched alkyl group having a chain of 1 to 30 carbon atoms, wherein the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl and the like. "(C2-C30) alkenyl" means a straight or branched chain alkenyl group having 2 to 30 carbon atoms constituting the chain, wherein the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-yl and the like. "(C2-C30) alkynyl" is a straight or branched alkynyl group having a chain of 2 to 30 carbon atoms, wherein the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, and the like. "(C3-C30) cycloalkyl" is a monocyclic or polycyclic hydrocarbon having 3 to 30 ring skeleton carbon atoms, wherein the number of carbon atoms is preferably 3 to 20, more preferably 3 to 7, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. "(3-to 7-membered) heterocycloalkyl" is a cycloalkyl group having at least one heteroatom selected from the group consisting of B, N, O, S, Si and P, preferably O, S and N, and 3-7 ring backbone atoms, and includes tetrahydrofuran, pyrrolidine, thiacyclopentane, tetrahydropyran, and the like. "(C6-C30) aryl (arylene)" is a monocyclic or fused ring type group derived from an aromatic hydrocarbon having 6 to 30 ring skeleton carbon atoms, wherein the number of ring skeleton carbon atoms is preferably 6 to 20, more preferably 6, which may be partially saturated, and includes phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthryl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, anthrylenyl, fluoranthenyl, etc. "(5-to 30-membered) heteroaryl (heteroarylene)" is an aryl group having at least 1, preferably 1 to 4 heteroatoms selected from the group consisting of B, N, O, S, Si and P and 5 to 30 ring backbone atoms, wherein the number of ring backbone atoms is preferably 5 to 20, more preferably 5 to 15; which is a monocyclic ring or a fused ring fused to at least one benzene ring; it may be partially saturated; it may be a group formed by connecting at least one heteroaryl group or an aryl group to a heteroaryl group by a single bond; and include monocyclic heteroaryl groups including furyl, thienyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl and the like, and fused heteroaryl groups including benzofuryl, benzothienyl, isobenzofuryl, dibenzofuryl, dibenzothienyl, benzonaphthothiophenyl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazole, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl and the like. "nitrogen-containing (5-to 30-membered) heteroaryl (heteroarylene)" is an aryl group having at least one heteroatom N, preferably 1 to 4 heteroatoms, and 5 to 30 ring skeleton atoms, wherein the number of ring skeleton atoms is preferably 5 to 20, more preferably 5 to 15; which is a monocyclic ring or a fused ring fused to at least one benzene ring; it may be partially saturated; it may be a group formed by connecting at least one heteroaryl group or an aryl group to a heteroaryl group by a single bond; and include monocyclic ring-type heteroaryl groups including pyrrolyl, imidazolyl, pyrazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl and the like, and fused ring-type heteroaryl groups including benzimidazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, quinolyl, quinazolinyl, quinoxalinyl, carbazolyl, phenanthridinyl and the like. "halogen" includes F, Cl, Br and I.
Herein, "substituted" in the expression "substituted or unsubstituted" means that a hydrogen atom in a certain functional group is replaced with another atom or functional group (i.e., substituent). At Ar1To Ar6、L1To L3、R1To R5、R11To R17Substituted alkyl (alkylene), substituted aryl (arylene), substituted heteroaryl (heteroarylene), substituted nitrogen-containing heteroaryl (heteroarylene), substituted cycloalkyl, substituted heterocycloalkyl, substituted trialkylsilyl, substituted dialkyl in R and MaThe substituents of the arylsilyl group, the substituted alkyldiarylsilyl group, the substituted triarylsilyl group, the substituted mono-or dialkylamino group, the substituted mono-or diarylamino group, the substituted alkylarylamino group, the substituted arylalkyl group, the substituted alkylaryl group, and the substituted spiro [ fluorene- (C3-C30) cycloalkane are each independently at least one selected from the group consisting of: deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, (C1-C30) alkyl, halo (C1-C30) alkyl, (C2-C30) alkenyl, (C2-C30) alkynyl, (C1-C30) alkoxy, (C1-C30) alkylthio, (C3-C30) cycloalkyl, (C3-C30) cycloalkenyl, (3-to 7-membered) heterocycloalkyl, (C6-C30) aryloxy, (C6-C30) arylthio, (5-to 30-membered) heteroaryl unsubstituted or substituted with (C6-C30) aryl, (C6-C30) aryl unsubstituted or substituted with (5-to 30-membered) heteroaryl, (C1-C867) alkylsilyl, tri (C6-C30) arylsilyl, di (C30-C30) alkyl (C30-C30) arylsilyl, (C36 30 2-C30) arylsilyl, Amino, mono-or di (C1-C30) alkylamino, mono-or di (C6-C30) arylamino unsubstituted or substituted by (C1-C30) alkyl, (C1-C30) alkyl (C6-C30) arylamino, (C1-C30) alkylcarbonyl, (C1-C30) alkoxycarbonyl, (C6-C30) arylcarbonyl, di (C6-C30) arylboryl, di (C1-C30) alkylboryl, (C1-C30) alkyl (C6-C30) arylboryl, (C6-C30) aryl (C1-C30) alkyl and (C1-C30) alkyl (C6-C30) aryl; preferably selected from the group consisting of: (C1-C6) alkyl, (C6-C18) aryl unsubstituted or substituted with cyano, (C1-C6) alkyl or (C6-C12) aryl, and (5-to 20-membered) heteroaryl unsubstituted or substituted with (C6-C12) aryl.
According to one embodiment of the organic electroluminescent device of the present disclosure, formula 1 may be represented by formula 3 or formula 4 below:
Figure BDA0002006467680000071
Figure BDA0002006467680000081
wherein
Ar1To Ar6、L1、L2、R1、R2A, b, m and n are as defined in formula 1.
According to one embodiment of the organic electroluminescent device of the present disclosure, formula 2 may be represented by any one of formulae 5 to 10 below:
Figure BDA0002006467680000082
wherein Ma and L3、R3To R5R, o, p and q are as defined in formula 2.
In the above formula 1, Ar1To Ar6Each independently represents a substituted or unsubstituted (C1-C30) alkyl group, a substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted (5-to 30-membered) heteroaryl group, or a substituted or unsubstituted spiro [ fluorene- (C3-C30) cycloalkane](ii) a Or Ar1And Ar2、Ar3And Ar4And Ar5And Ar6May be linked to each other to form a mono-or polycyclic, (3-to 30-membered) alicyclic or aromatic ring or a combination thereof, whose carbon atom may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur.
Preferably, Ar1To Ar4Each independently represents a substituted or unsubstituted (C6-C25) aryl group, a substituted or unsubstituted (5-to 15-membered) heteroaryl group, or a substituted or unsubstituted spiro [ fluorene- (C5-C8) cycloalkane]More preferably, Ar1To Ar4Each independently represents a (C6-C25) aryl group unsubstituted or substituted by a (C1-C6) alkyl group or a (C6-C20) aryl group; (5-to 15-membered) heteroaryl unsubstituted or substituted with (C1-C6) alkyl or (C6-C12) aryl; unsubstituted spiro [ fluorene-cyclopentane](ii) a Or unsubstituted spiro [ fluorene-cyclohexane]. Specifically, Ar1To Ar4Each independently represents phenyl, biphenyl, terphenyl, fluorenyl substituted by methyl, fluorenyl substituted by phenyl, benzofluorenyl substituted by methyl, naphthylphenyl, phenyl substituted by fluorene, pyridyl substituted by phenyl, dibenzofuranyl, dibenzothiophenyl, dibenzothiazolyl substituted by methyl, dibenzothiazyl substituted by phenylAzoly, spiro [ fluorene-cyclopentane]Spiro [ fluorene-cyclohexane ]]And the like.
Preferably, Ar5And Ar6Each independently represents a substituted or unsubstituted (C1-C6) alkyl group or a substituted or unsubstituted (C6-C12) aryl group; or may be linked to each other to form a monocyclic or polycyclic, (5-to 15-membered) alicyclic or aromatic ring or a combination thereof, more preferably, Ar5And Ar6Each independently represents an unsubstituted (C1-C6) alkyl group or an unsubstituted (C6-C12) aryl group; or may be linked to each other to form a monocyclic (5-to 15-membered) alicyclic ring. Specifically, Ar5And Ar6May each independently represent methyl, phenyl, etc., or may be linked to each other to form a spirocyclopentane.
In formula 1, L1Represents a single bond, a substituted or unsubstituted (C6-C30) arylene group, or a substituted or unsubstituted (5-to 30-membered) heteroarylene group, preferably a single bond, a substituted or unsubstituted (C6-C20) arylene group, or a substituted or unsubstituted (5-to 15-membered) heteroarylene group, more preferably a single bond, an unsubstituted (C6-C20) arylene group, or an unsubstituted (5-to 15-membered) heteroarylene group. In particular, L1May represent a single bond, phenylene, naphthylene, biphenylene, naphthylene, pyridylphenylene, pyridinylene, phenylenepyridinylene, bipyridyl, dibenzofuranylene, dibenzothiophenylene, or the like.
In formula 1, L2Represents a single bond, a substituted or unsubstituted (C1-C30) alkylene group, a substituted or unsubstituted (C6-C30) arylene group, or a substituted or unsubstituted (5-to 30-membered) heteroarylene group, with the proviso that when n is 0, L2Is absent. L is2Preferably represents a single bond or a substituted or unsubstituted (C6-C12) arylene group, more preferably a single bond or an unsubstituted (C6-C12) arylene group. Specifically, L2May represent a single bond, phenylene group or the like.
In formula 1, R1And R2Each independently represents hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5-to 30-membered) heteroaryl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (3-to 7-membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl (C1)-C30) alkyl, -NR11R12、-SiR13R14R15、-SR16、-OR17Cyano, nitro or hydroxy; or are linked to an adjacent substituent(s) to form a mono-or polycyclic, (3-to 30-membered) alicyclic or aromatic ring or a combination thereof, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur, preferably each independently represents hydrogen or a substituted or unsubstituted (C6-C20) aryl group, more preferably each independently represents hydrogen or an unsubstituted (C6-C20) aryl group. In particular, R1And R2Each independently may represent hydrogen, biphenyl, etc.
Herein, R is11To R17Each independently represents hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5-to 30-membered) heteroaryl, substituted or unsubstituted (3-to 7-membered) heterocycloalkyl, or substituted or unsubstituted (C3-C30) cycloalkyl; or are linked to an adjacent substituent(s) to form a mono-or polycyclic, (3-to 30-membered) alicyclic or aromatic ring or a combination thereof, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur.
In formula 2, Ma represents a substituted or unsubstituted nitrogen-containing (3-to 30-membered) heteroaryl group, preferably a substituted or unsubstituted nitrogen-containing (5-to 15-membered) heteroaryl group. The nitrogen-containing heteroaryl group may be substituted with at least one selected from the group consisting of: (C1-C6) alkyl; specifically, Ma may represent a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted quinazolinyl group, or a substituted or unsubstituted quinoxalinyl group.
In formula 2, L3Represents a single bond, a substituted or unsubstituted (C6-C30) arylene group or a substitutedOr an unsubstituted nitrogen-containing (3-to 30-membered) heteroarylene group, preferably represents a single bond, substituted or unsubstituted (C)6-C15) Arylene or substituted or unsubstituted nitrogen-containing (5-to 15-membered) heteroarylene, more preferably a single bond, (C1-C6) unsubstituted or substituted by (C1-C6) alkyl6-C15) Arylene or unsubstituted nitrogen-containing (5-to 15-membered) heteroarylene. In particular, L3May represent a single bond, phenylene, naphthylene, dimethylfluorenylene or pyridylene.
In formula 2, R3To R5Each independently represents hydrogen, deuterium, a substituted or unsubstituted (C1-C30) alkyl group, a substituted or unsubstituted (C6-C30) aryl (C1-C30) alkyl group, a substituted or unsubstituted (C6-C6) aryl group, a substituted or unsubstituted (C6-C6) alkyl (C6-C6) aryl group, a substituted or unsubstituted (3-to 30-membered) heteroaryl group, a substituted or unsubstituted (C6-C6) cycloalkyl group, a substituted or unsubstituted tri (C6-C6) alkylsilyl group, a substituted or unsubstituted di (C6-C6) alkyl (C6-C6) arylsilyl group, a substituted or unsubstituted (C6-C6) alkyl di (C6-C6) arylsilyl group, a substituted or unsubstituted tri (C72-C6) arylsilyl group, a substituted or unsubstituted mono (C6-C6) alkyl amino group, a substituted or unsubstituted (C6-C6) amino group, a substituted or unsubstituted (C6) aryl group C30) Alkyl (C6-C30) arylamino; preferably each independently represents hydrogen or a substituted or unsubstituted (C6-C12) aryl group, more preferably each independently represents hydrogen or an unsubstituted (C6-C12) aryl group. Specifically, R3To R5May each independently represent hydrogen or phenyl.
In formula 2, R represents hydrogen, deuterium, a substituted or unsubstituted (C1-C30) alkyl group, a substituted or unsubstituted (C6-C30) aryl (C1-C30) alkyl group, a substituted or unsubstituted (C6-C30) aryl group, a substituted or unsubstituted (C1-C30) alkyl (C6-C30) aryl group, a substituted or unsubstituted (3-to 30-membered) heteroaryl group, a substituted or unsubstituted (C3-C30) cycloalkyl group, a substituted or unsubstituted tri (C1-C30) alkylsilyl group, a substituted or unsubstituted di (C1-C30) alkyl (C6-C30) arylsilyl group, a substituted or unsubstituted (C1-C30) alkyl di (C6-C30) arylsilyl group, a substituted or unsubstituted tri (C6-C30) arylsilyl group, a substituted or unsubstituted mono or di (C1-C35 30) alkyl amino group, Substituted or notSubstituted mono-or di (C6-C30) arylamino or substituted or unsubstituted (C1-C30) alkyl (C6-C30) arylamino, preferably represents substituted or unsubstituted (C6-C30)6-C15) Aryl or substituted or unsubstituted nitrogen-containing (5-to 15-membered) heteroaryl, more preferably represents (C1-C6) alkyl substituted or unsubstituted6-C15) Aryl or unsubstituted nitrogen-containing (5-to 15-membered) heteroaryl. Specifically, R may represent phenyl, naphthyl, dimethylfluorenyl or pyridyl.
The compound represented by formula 1 includes the following compounds, but is not limited thereto:
Figure BDA0002006467680000121
Figure BDA0002006467680000131
Figure BDA0002006467680000141
the compound represented by formula 2 includes the following compounds, but is not limited thereto:
Figure BDA0002006467680000151
Figure BDA0002006467680000161
Figure BDA0002006467680000171
the compounds of formulae 1 and 2 of the present disclosure can be prepared by synthetic methods known to those skilled in the art. For example, the compound of formula 1 may be prepared according to the following reaction scheme.
[ reaction formula 1]
Figure BDA0002006467680000172
Wherein Ar is1To Ar6、L1、L2、R1、R2A, b, m and n are as defined in formula 1.
An organic electroluminescent device according to an embodiment of the present disclosure may include a first electrode; a second electrode opposed to the first electrode; one or more light emitting layers disposed between the first electrode and the second electrode; and one or more hole transport regions disposed between the first electrode and the light emitting layer, wherein at least one layer of the hole transport regions comprises a compound represented by formula 1, and at least one layer of the light emitting layer comprises a compound represented by formula 2.
According to one embodiment of the present disclosure, the compounds of formula 1 and formula 2 may be contained in the same layer, or may be each contained in a different layer of the organic electroluminescent device. The compound of formula 1 may be contained in the hole transport region and the compound of formula 2 may be contained in the light emitting layer, more specifically, the compound of formula 1 may be contained in the hole transport layer and the compound of formula 2 may be contained in the light emitting layer, for example, as a host compound, but is not limited thereto.
In addition to the light emitting layer and the hole transport region, at least one layer selected from the group consisting of a light emission auxiliary layer, an electron transport layer, an electron buffer layer, an electron injection layer, an intermediate layer, and a hole blocking layer may be included between the first electrode and the second electrode.
The hole transport region of the present disclosure may be composed of at least one layer selected from the group consisting of: a hole transport layer, a hole injection layer, an electron blocking layer, and a hole assist layer, and each layer may be composed of one or more layers.
According to one embodiment of the present disclosure, the hole transport region includes a hole transport layer. In addition, the hole transport region may include a hole transport layer, and further include one or more layers of a hole injection layer, an electron blocking layer, and a hole auxiliary layer.
Herein, a hole-assist layer or a light-emitting assist layer is interposed between a hole-transport layer and a light-emitting layer, and can be used to control the transport rate of holes. The hole assist layer or the light-emitting assist layer may provide an effect of improving the efficiency and lifetime of the organic electroluminescent device.
The light-emitting auxiliary layer may be disposed between the anode and the light-emitting layer, or between the cathode and the light-emitting layer. When a light-emitting auxiliary layer is disposed between the anode and the light-emitting layer, it can be used to facilitate hole injection and/or hole transport, or to prevent electron overflow. When the light-emitting auxiliary layer is disposed between the cathode and the light-emitting layer, it may be used to facilitate electron injection and/or electron transport, or to prevent hole overflow. Also, a hole assist layer may be interposed between the hole transport layer (or the hole injection layer) and the light emitting layer, and the hole transport rate (or the hole injection rate) may be effectively promoted or blocked, thereby enabling control of charge balance. In addition, an electron blocking layer may be interposed between the hole transport layer (or the hole injection layer) and the light emitting layer, and the exciton may be confined in the light emitting layer by blocking the electron overflow from the light emitting layer, preventing light emission leakage. When the organic electroluminescent device includes two or more hole transport layers, the hole transport layer further included therein may serve as a hole assist layer or an electron blocking layer. The hole assist layer and the electron blocking layer may have the effect of improving the efficiency and/or lifetime of the organic electroluminescent device.
According to one embodiment of the present disclosure, the hole transport layer may be composed of a single layer, and a hole transport material including the compound represented by formula 1 of the present disclosure may be included therein.
According to another embodiment of the present disclosure, the hole transport region may include a hole transport layer, and the hole transport layer may be composed of a multilayer of two or more layers. The hole transport material including the compound represented by formula 1 of the present disclosure may be included in at least one layer of the plurality of layers. In the hole transport layer or other layer containing the compound of formula 1, any compound used for a conventional hole transport material may be contained. For example, a compound of the following formula 11 may be contained.
Figure BDA0002006467680000191
Wherein
L11Represents a single bond, a substituted or unsubstituted (C6-C30) arylene, or a substituted or unsubstituted (5-to 30-membered) heteroarylene;
Ar11and Ar12Each independently represents a substituted or unsubstituted (C6-C30) aryl or a substituted or unsubstituted (5-to 30-membered) heteroaryl, or Ar11And L11May form a nitrogen-containing (5-to 30-membered) heteroaryl group with the bonded nitrogen;
R21to R23Each independently represents hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C2-C30) alkenyl, substituted or unsubstituted (C2-C30) alkynyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C3-C30) cycloalkenyl, substituted or unsubstituted (3-to 7-membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5-to 30-membered) heteroaryl, -NR, hydroxyl, or31R32、-SiR33R34R35、-SR36、-OR37、-COR38OR-B (OR)39)(OR40) Or are linked to an adjacent substituent(s) to form a mono-or polycyclic, (3-to 30-membered) alicyclic or aromatic ring, or a combination thereof, whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
R31to R40Each independently represents hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxyl, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C2-C30) alkenyl, substituted or unsubstituted (C2-C30) alkynyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C3-C30) cycloalkenyl, substituted or unsubstituted (3-to 7-membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (5-to 30-membered) heteroaryl, or is linked to an adjacent substituent to form a monocyclic or polycyclic, (3-to 30-membered) heteroaryl group) An alicyclic or aromatic ring, or a combination thereof, whose carbon atoms may be replaced by at least one heteroatom selected from nitrogen, oxygen and sulfur;
x represents an integer of 1 to 4, wherein x is an integer of 2 or more, and each R21May be the same or different;
y represents an integer of 1 to 3, wherein y is an integer of 2 or more, and each R22May be the same or different;
heteroaryl (heteroarylene) contains at least one heteroatom selected from B, N, O, S, Si and P; and is
Heterocycloalkyl contains at least one heteroatom selected from O, S and N.
The compound of formula 2 of the present disclosure may be included in the light emitting layer. When used in the light emitting layer, the organic electroluminescent compound of formula 2 of the present disclosure may be contained therein as a host material. Preferably, the light emitting layer may further comprise one or more dopants. If desired, the compounds of formula 2 of the present disclosure may be used as co-host materials. That is, the light emitting layer may additionally include a compound other than the organic electroluminescent compound of formula 2 (first host material) of the present disclosure as a second host material. Herein, the weight ratio of the first host material to the second host material is in the range of 1:99 to 99: 1, in the above range.
The second host material may be any known phosphorescent host. In terms of luminous efficiency, a host selected from the group consisting of compounds of the following formulae 12 to 17 is preferred.
H-(Cz-L4)c-M-----------(12)
H-(Cz)d-L4-M-----------(13)
Figure BDA0002006467680000201
Figure BDA0002006467680000211
Wherein
Cz represents the following structure:
Figure BDA0002006467680000212
a represents-O-or-S-; and is
R41To R44Each independently represents hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5-to 30-membered) heteroaryl, or-SiR45R46R47(ii) a Wherein R is45To R47Each independently represents a substituted or unsubstituted (C1-C30) alkyl group or a substituted or unsubstituted (C6-C30) aryl group; l is4Represents a single bond, a substituted or unsubstituted (C6-C30) arylene, or a substituted or unsubstituted (5-to 30-membered) heteroarylene; m represents a substituted or unsubstituted (C6-C30) aryl or a substituted or unsubstituted (5-to 30-membered) heteroaryl; y is1And Y2Each independently represents-O-, -S-, -N (R)51) -or-C (R)52)(R53) Provided that Y is1And Y2Not exist at the same time; r51To R53Each independently represents a substituted or unsubstituted (C1-C30) alkyl group, a substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted (5-to 30-membered) heteroaryl group; r52And R53May be the same or different; c and d each independently represent an integer of 1 to 3; j. k, r and s each independently represent an integer of 0 to 4; i represents an integer of 0 to 3; if c, d, i, j, k, R or s represents an integer of 2 or more, each (Cz-L4), each (Cz), each R41Each R42Each R43Or each R44May be the same or different;
Figure BDA0002006467680000221
wherein
Y3To Y5Each independently represents CR54Or N;
R54represents hydrogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl orSubstituted or unsubstituted (5-to 30-membered) heteroaryl;
B1and B2Each independently represents hydrogen, a substituted or unsubstituted (C6-C30) aryl group, or a substituted or unsubstituted (5-to 30-membered) heteroaryl group;
B3represents a substituted or unsubstituted (C6-C30) aryl or a substituted or unsubstituted (5-to 30-membered) heteroaryl; and is
L5Represents a single bond, a substituted or unsubstituted (C6-C30) arylene group, or a substituted or unsubstituted (5-to 30-membered) heteroarylene group.
Specifically, preferred examples of the second host material are as follows, but not limited thereto.
Figure BDA0002006467680000222
Figure BDA0002006467680000231
Figure BDA0002006467680000241
Figure BDA0002006467680000251
Figure BDA0002006467680000261
Figure BDA0002006467680000271
[ wherein TPS represents a triphenylsilyl group ]
The dopant contained in the organic electroluminescent device according to the present disclosure is preferably at least one phosphorescent dopant. The phosphorescent dopant material applied to the organic electroluminescent device according to the present disclosure is not particularly limited, but is preferably a metallized complex selected from iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), more preferably an ortho-metal complex selected from iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), and even more preferably an iridium complex of ortho-metal.
The dopant included in the organic electroluminescent device of the present disclosure may be selected from the group consisting of compounds represented by the following formulas 101 to 104, but is not limited thereto.
Figure BDA0002006467680000281
Wherein L' is selected from the following structures:
Figure BDA0002006467680000282
R100、R134and R135Each independently represents hydrogen, deuterium, a substituted or unsubstituted (C1-C30) alkyl group, or a substituted or unsubstituted (C3-C30) cycloalkyl group;
R101to R109And R111To R123Each independently represents hydrogen, deuterium, halogen, unsubstituted or deuterium-or halogen-substituted (C1-C30) alkyl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C6-C30) aryl, cyano or substituted or unsubstituted (C1-C30) alkoxy; r106To R109May be linked to each other to form a substituted or unsubstituted fused ring, such as fluorene unsubstituted or substituted with an alkyl group, dibenzothiophene unsubstituted or substituted with an alkyl group, or dibenzofuran unsubstituted or substituted with an alkyl group; r120To R123May be linked to each other to form a substituted or unsubstituted fused ring, such as quinoline which is unsubstituted or substituted with at least one of an alkyl group, an aryl group, an aralkyl group and an alkaryl group;
R124to R133And R136To R139Each independently represents hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, or substituted or unsubstitutedA substituted (C6-C30) aryl group; r124To R127May be linked to each other to form a substituted or unsubstituted fused ring, such as fluorene unsubstituted or substituted with an alkyl group, dibenzothiophene unsubstituted or substituted with an alkyl group, or dibenzofuran unsubstituted or substituted with an alkyl group;
x represents CR61R62O or S;
R61and R62Each independently represents substituted or unsubstituted (C)1-C10) Alkyl or substituted or unsubstituted (C6-C30) aryl;
R201to R211Each independently represents hydrogen, deuterium, halogen, a (C1-C30) alkyl group unsubstituted or substituted with deuterium or halogen, a (C3-C30) cycloalkyl group substituted or unsubstituted, or a (C6-C30) aryl group unsubstituted or substituted with alkyl or deuterium; r208To R211May be linked to each other to form a substituted or unsubstituted fused ring, for example, fluorene unsubstituted or substituted with an alkyl group, dibenzothiophene unsubstituted or substituted with an alkyl group, or dibenzofuran unsubstituted or substituted with an alkyl group;
t and u each independently represent an integer of 1 to 3; wherein t or u is an integer of 2 or more, each R100May be the same or different; and is
w represents an integer of 1 to 3.
Specific examples of the dopant compound are as follows, but are not limited thereto.
Figure BDA0002006467680000291
Figure BDA0002006467680000301
Figure BDA0002006467680000311
Figure BDA0002006467680000321
Figure BDA0002006467680000331
The organic electroluminescent device of the present disclosure may further comprise at least one compound selected from the group consisting of an aromatic amine-based compound and a styryl aromatic amine-based compound.
Further, in the organic electroluminescent device of the present disclosure, the dielectric layer may further include at least one metal selected from the group consisting of organometallic of group 1 metal, group 2 metal, period 4 transition metal, period 5 transition metal, lanthanide and d-transition element of the periodic table of elements, or at least one complex including the metal.
In the organic electroluminescent device of the present disclosure, preferably, at least one layer (hereinafter, "surface layer") selected from a chalcogenide layer, a metal halide layer, and a metal oxide layer may be disposed on one or both inner surfaces of the electrode. Specifically, a layer of a chalcogenide (including oxide) of silicon or aluminum is preferably disposed on the anode surface of the electroluminescent medium layer, and a layer of a metal halide or a metal oxide is preferably disposed on the cathode surface of the electrode light-emitting medium layer. Such a surface layer may provide operational stability to the organic electroluminescent device. Preferably, the chalcogenide comprises SiOX(1≤X≤2)、AlOX(X is more than or equal to 1 and less than or equal to 1.5), SiON, SiAlON and the like; the metal halide comprises LiF, MgF2、CaF2Rare earth metal fluorides, etc.; the metal oxide comprises Cs2O、Li2O, MgO, SrO, BaO, CaO, etc.
The first electrode may be an anode. Between the anode and the light emitting layer, a hole transport region may be included, and the hole transport region may include a hole transport layer. In addition to the hole transport layer, a hole injection layer, an electron blocking layer, or a combination thereof may be used. Multiple layers may be used for the hole injection layer to lower a hole injection barrier (or hole injection voltage) from the anode to the hole transport layer or the electron blocking layer. Two compounds may be used simultaneously for each layer. The electron blocking layer may also be formed of multiple layers.
The second electrode may be a cathode. Between the light emitting layer and the cathode, a layer selected from an electron buffer layer, a hole blocking layer, an electron transport layer, or an electron injection layer, or a combination thereof may be used. Multiple layers may be used for the electron buffer layer to control the injection of electrons and enhance the interfacial properties between the light emitting layer and the electron injection layer. Two compounds may be used simultaneously in each layer. The hole blocking layer or the electron transporting layer may also be formed of multiple layers, and each layer may contain two or more compounds.
Preferably, in the organic electroluminescent device of the present disclosure, a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant may be disposed on at least one surface of the pair of electrodes. In this case, the electron transport compound is reduced to an anion, and thus it is easier to inject and transport electrons from the mixed region to the light emitting medium. In addition, the hole transport compound is oxidized into cations, and thus holes are more easily injected or transported from the mixed region to the light emitting medium. Preferably, the oxidizing dopant includes various lewis acids and acceptor compounds; reducing dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals, and mixtures thereof. The reductive dopant layer may be used as a charge generation layer to produce an organic EL device having two or more light emitting layers and emitting white light.
In order to form each layer constituting the organic EL device of the present disclosure, a dry film forming method such as vacuum deposition, sputtering, plasma, ion plating, or a wet film forming method such as inkjet printing, nozzle printing, slit coating, spin coating, dip coating, flow coating, or the like can be used.
When a wet film formation method is used, a thin film is formed by dissolving or dispersing the materials constituting each layer in a suitable solvent, for example, ethanol, chloroform, tetrahydrofuran, dioxane, or the like. The solvent is not particularly limited, and the material constituting each layer may be soluble or dispersible in the solvent, which does not cause any problem in forming the layer.
By using the organic electroluminescent device of the present disclosure, a display device, for example, for a smart phone, a tablet computer, a notebook computer, a PC, a TV, or a vehicle, or a lighting device, for example, an indoor or outdoor lighting device, can be manufactured.
Hereinafter, a preparation method of the host compound of the present disclosure, physical properties of the compound, and light emitting properties of a device comprising the host material and the hole transport material of the present disclosure will be explained in detail.
Synthesis example 1: preparation of Compound C-4
Figure BDA0002006467680000351
Preparation of Compound 1-1
100g of indanone (757mmol), 111.6g of benzenedialdehyde (832mmol), 10.3g of 20% sodium ethoxide in ethanol (151mmol) and 1300mL of ethanol are added to the reaction vessel. After refluxing the mixture for 2 hours, the mixture was cooled to room temperature and stirred overnight. The reaction solution was cooled to 0 deg.C, and the separated solid was filtered and washed with cold methanol and hexane to obtain 95g of compound 1-1 (yield: 55%).
Preparation of Compounds 1-2
33.3g of iodine (144mmol), 44g of hypophosphorous acid (660mmol, 50% aqueous solution) and 2000mL of acetic acid were added to the reaction vessel, and the mixture was stirred at 80 ℃ for 30 minutes. 95g of Compound 1-1(413mmol) were slowly added dropwise thereto, and the mixture was stirred under reflux overnight. The reaction solution was cooled to room temperature, and the separated solid was filtered and washed with cold methanol and hexane to obtain 73g of compound 1-2 (yield: 82%).
Preparation of Compounds 1-3
30g of Compound 1-2(139mmol), 39g of potassium hydroxide (694mmol), 2.3g of potassium iodide (14mmol), 1.58g of benzyltriethylammonium chloride (7mmol), 70mL of distilled water and 700mL of dimethyl sulfoxide were added to a reaction vessel, and the mixture was stirred at room temperature for 30 minutes. 49g of methyl iodide (347mmol) was added thereto and the mixture was stirred at room temperature overnight. The reaction solution was diluted with ethyl acetate and washed with distilled water. The extracted organic layer was then dried over magnesium sulfate. The solvent was removed by a rotary evaporator, and the obtained product was purified by column chromatography to obtain 34g of the compounds 1 to 3 (yield: 68%).
Preparation of Compounds 1-4
In a reaction vessel, 3g of compound 1-3(12mmol) was dissolved in 50mL of dichloromethane. 1.3g of bromine (16mmol) was dissolved in 10mL of dichloromethane and added to the reaction solution. The mixture was then stirred at room temperature for 2 hours. The reaction solution was diluted with dichloromethane and washed with distilled water. The extracted organic layer was then dried over magnesium sulfate. The solvent was removed by a rotary evaporator, and the separated solid was filtered and washed with cold methanol to obtain 1.8g of the compound 1-4 (yield: 45%).
Compounds 1-4 can also be obtained as follows:
1.3g of the compound 1-3(5mmol), 10mL of dimethylformamide and 1.23g N-bromosuccinimide (7mmol) were added to a reaction vessel, and the mixture was stirred at room temperature overnight. The reaction solution was diluted with ethyl acetate and washed with distilled water. The extracted organic layer was then dried over magnesium sulfate. The solvent was removed by a rotary evaporator, and the separated solid was filtered and washed with cold methanol to obtain 620mg of compound 1-4 (yield: 36%).
Preparation of Compound C-4
10g of the compound 1-4(31mmol), 13.7g of bis-9, 9-dimethyl-9H-fluoren-2-ylamine (31mmol), 1.46g of tris (dibenzylideneacetone) dipalladium (0) (2mmol), 2.2mL of tri-tert-butylphosphine (6mmol, 50% in toluene), 5.9g of sodium tert-butoxide (62mmol) and 223mL of toluene were added to the reaction vessel, and the mixture was refluxed for 4 hours. The reaction solution was cooled to room temperature. The solvent was removed by a rotary evaporator, and the obtained product was purified by column chromatography to obtain 10.5g of Compound C-4 (yield: 52%). Properties of Compound C-4 are shown in Table 1.
Synthesis example 2: preparation of Compound C-5
Figure BDA0002006467680000371
40g of the compound 1-4(124mmol), 44.7g N-1,1' -biphenyl-4-yl-9, 9-dimethyl-9H-fluoren-2-amine (124mmol), 3.4g tris (dibenzylideneacetone) dipalladium (0) (4mmol), 3mL of tri-tert-butylphosphine (7mmol, 50% in toluene), 17.8g of sodium tert-butoxide (186mmol) and 600mL of toluene were added to the reaction vessel and the mixture was refluxed for 3 hours. The reaction solution was cooled to room temperature. The solvent was removed by a rotary evaporator, and the obtained product was purified by column chromatography to obtain 37.8g of Compound C-5 (yield: 51%). Properties of Compound C-5 are shown in Table 1.
Synthesis example 3: preparation of Compound C-7
Figure BDA0002006467680000372
10g of the compound 1-4(31mmol), 16.5g N-1,1' -biphenyl-4-yl-9, 9-diphenyl-9H-fluoren-2-amine (34mmol), 1.4g of tris (dibenzylideneacetone) dipalladium (0) (2mmol), 1.2mL of tri-tert-butylphosphine (3mmol, 50% in toluene), 5.9g of sodium tert-butoxide (62mmol) and 600mL of toluene were added to a reaction vessel and the mixture was refluxed for 3 hours. The reaction solution was cooled to room temperature. The solvent was removed by a rotary evaporator, and the obtained product was purified by column chromatography to obtain 11g of Compound C-7 (yield: 49%). Properties of Compound C-7 are shown in Table 1.
Synthesis example 4: preparation of Compound C-73
Figure BDA0002006467680000381
Preparation of Compound 2-1
10g of 2-bromo-11, 11-dimethyl-11H-benzo [ b ] fluorene (31mmol), 10mL of dimethylformamide and 7.2g N-bromosuccinimide (40mmol) were added to a reaction vessel, and the mixture was stirred at room temperature overnight. The reaction solution was diluted with ethyl acetate and washed with distilled water. The extracted organic layer was then dried over magnesium sulfate. The solvent was removed by a rotary evaporator, and the separated solid was filtered and washed with cold methanol to give 10.5mg of Compound 2-1 (yield: 84%).
Preparation of Compound C-73
10g of the compound 2-1(25mmol), 15.6g N-1,1' -biphenyl-4-yl-9, 9-diphenyl-9H-fluoren-2-amine (55mmol), 2.3g of tris (dibenzylideneacetone) dipalladium (0) (2.5mmol), 2mL of tri-tert-butylphosphine (5mmol, 50% in toluene), 9.6g of sodium tert-butoxide (99mmol) and 240mL of toluene were added to a reaction vessel and the mixture was refluxed for 3 hours. The reaction solution was cooled to room temperature. The solvent was removed by a rotary evaporator, and the obtained product was purified by column chromatography to obtain 9.6g of Compound C-73 (yield: 47%). The properties of Compound C-73 are shown in Table 1.
Synthesis example 5: preparation of Compound C-25
Figure BDA0002006467680000382
4g of the compound 1-4(12mmol), 7.9g N- ([1,1' -biphenyl ] -4-yl) -9, 9-dimethyl-N- (4' - (4,4,5, 5-tetramethyl-1, 3, 2-dioxaborolan-2-yl) - [1,1' -biphenyl ] -4-yl) -9H-fluoren-2-amine (12mmol), 0.72g tetrakis (triphenylphosphine) palladium (0.6mmol), 3.4g potassium carbonate (24mmol), 30mL of toluene and 15mL of ethanol were added to a reaction vessel, 15mL of distilled water was added thereto, and the mixture was stirred at 80 ℃ for 18 hours. After completion of the reaction, ethanol and toluene were removed by a rotary evaporator, and the organic layer was extracted with dichloromethane and distilled water. The organic layer was then dried over magnesium sulfate. The solvent was removed by a rotary evaporator, and the obtained product was purified by column chromatography to obtain 3.1g of Compound C-25 (yield: 33%). The properties of Compound C-25 are shown in Table 1.
Synthesis example 6: preparation of Compound C-102
Figure BDA0002006467680000391
Preparation of Compound 3-1
15g N- (9, 9-dimethyl-9H-fluoren-2-yl) -11, 11-dimethyl-N- (4- (naphthalen-2-yl) phenyl) -11H-benzo [ b ] fluoren-2-amine (23mmol), 120mL dimethylformamide and 5.3g N-bromosuccinimide (30mmol) were added to the reaction vessel and the mixture was stirred at room temperature overnight. The reaction solution was diluted with ethyl acetate and washed with distilled water. The extracted organic layer was then dried over magnesium sulfate. The solvent was removed by a rotary evaporator, and the obtained product was purified by column chromatography to obtain 15g of Compound 3-1 (yield: 89%).
Preparation of Compound C-102
10g of the compound 3-1(14mmol), 2.7g of diphenylamine (16mmol), 0.63g of tris (dibenzylideneacetone) dipalladium (0) (0.68mmol), 0.5mL of tri-tert-butylphosphine (1.4mmol, 50% in toluene), 2.6g of sodium tert-butoxide (28mmol) and 260mL of toluene were added to the reaction vessel and refluxed at 80 ℃ for 3 hours. The reaction solution was cooled to room temperature. The solvent was removed by a rotary evaporator, and the obtained product was purified by column chromatography to obtain 3.1g of Compound C-102 (yield: 28%). The properties of Compound C-102 are shown in Table 1.
Synthesis example 7: preparation of Compound C-103
Figure BDA0002006467680000392
Preparation of Compound 4-1
26g of 2- ([1,1' -biphenyl ] -4-yl) -11, 11-dimethyl-11H-benzo [ b ] fluorene (66mmol), 330mL of dimethylformamide, 200mL of dichloromethane and 15.2g N-bromosuccinimide (85mmol) were added to a reaction vessel, and the mixture was stirred at room temperature overnight. The reaction solution was diluted with ethyl acetate and washed with distilled water. The extracted organic layer was then dried over magnesium sulfate. The solvent was removed by a rotary evaporator, and the obtained product was purified by column chromatography to obtain 26g of Compound 4-1 (yield: 83%).
Preparation of Compound C-103
13g of the compound 4-1(27mmol), 9.9g N-1,1' -biphenyl-4-yl-9, 9-dimethyl-9H-fluoren-2-amine (27mmol), 1.25g of tris (dibenzylideneacetone) dipalladium (0) (1.4mmol), 1.1mL of tri-tert-butylphosphine (2.7mmol, 50% in toluene), 5.3g of sodium tert-butoxide (54mmol) and 136mL of toluene were added to a reaction vessel, and the reaction mixture was refluxed at 80 ℃ for 3 hours. The reaction solution was cooled to room temperature. The solvent was removed by a rotary evaporator, and the obtained product was purified by column chromatography to obtain 4.5g of Compound C-103 (yield: 22%). The properties of Compound C-103 are shown in Table 1.
Synthesis example 8: preparation of Compound C-99
Figure BDA0002006467680000401
10g of the compound 1-4(31mmol), 14.0g N- (9, 9-dimethyl-9H-fluoren-2-yl) -11,11' -dimethyl-11H-benzo [ b ] fluoren-2-amine (31mmol), 1.42g tris (dibenzylideneacetone) dipalladium (0) (1.60mmol), 1.6mL tri-tert-butylphosphine (3.1mmol, 50% in toluene), 5.9g sodium tert-butoxide (62mmol) and 155mL of toluene were added to the reaction vessel and the mixture was refluxed at 80 ℃ for 16 hours. The reaction solution was cooled to room temperature. The solvent was removed by a rotary evaporator, and the obtained product was purified by column chromatography to obtain 9.1g of Compound C-99 (yield: 42%). Properties of Compound C-99 are shown in Table 1.
Synthesis example 9: preparation of Compound C-98
Figure BDA0002006467680000402
8g of the compound 1-4(25mmol), 11.9g N- ([1,1':4',1 "-tert-butyl ] -4-yl) -9, 9-dimethyl-9H-fluoren-2-amine (27mmol), 1.13g tris (dibenzylideneacetone) dipalladium (0) (1.35mmol), 1.0mL tri-tert-butylphosphine (2.7mmol, 50% in toluene), 4.8g sodium tert-butoxide (50mmol) and 125mL of toluene were added to the reaction vessel and the mixture was refluxed at 80 ℃ for 3 hours. The reaction solution was cooled to room temperature. The solvent was removed by a rotary evaporator to obtain a product which was purified by column chromatography to obtain 5.7g of Compound C-98 (yield: 34%). The characteristics of Compound C-98 are shown in Table 1.
Synthesis example 10: preparation of Compound C-10
Figure BDA0002006467680000411
7.4g of the compound 1-4(23mmol), 9.4g of 9, 9-dimethyl-N- (4- (naphthalen-2-yl) phenyl) -9H-fluoren-2-amine (23mmol), 1.05g of tris (dibenzylideneacetone) dipalladium (0) (1.15mmol), 1.2mL of tri-tert-butylphosphine (2.3mmol, 50% in toluene), 4.4g of sodium tert-butoxide (46mmol) and 200mL of toluene were added to a reaction vessel and the reaction mixture was refluxed at 80 ℃ for 3 hours. The reaction solution was cooled to room temperature. The solvent was removed by a rotary evaporator, and the obtained product was purified by column chromatography to obtain 3.7g of Compound C-10 (yield: 25%). Properties of Compound C-10 are shown in Table 1.
[ Table 1]
Figure BDA0002006467680000412
Further, the compounds of formula 2 of the present disclosure are known compounds and can be prepared by synthetic methods known in the art.
Apparatus example 1: preparation of an OLED device comprising a combination of a hole transport material and a host compound of the present disclosure
An OLED device comprising a combination of the hole transport material of the present disclosure and a host compound is prepared. A transparent electrode Indium Tin Oxide (ITO) thin film (10 Ω/sq) on a glass substrate for an Organic Light Emitting Diode (OLED) device (geomantec, japan) was ultrasonically cleaned with acetone and isopropyl alcohol in this order, and then stored in isopropyl alcohol. Next, the ITO substrate was mounted on a substrate holder of a vacuum vapor deposition apparatus. Compound HI-1 was charged into a unit of the vacuum vapor deposition apparatus, and then the pressure in the chamber of the apparatus was controlled to 10-6And (4) supporting. Thereafter, applying to the unitA current was applied to evaporate the above-added materials, thereby forming a first hole injection layer having a thickness of 90nm on the ITO substrate. Then, the compound HI-2 was added to another cell of the vacuum vapor deposition apparatus and evaporated by applying a current to the cell, thereby forming a second hole injection layer having a thickness of 5nm on the first hole injection layer. The compound HT-1 was added to another cell of the vacuum vapor deposition apparatus and evaporated by applying a current to the cell, thereby forming a first hole transport layer having a thickness of 10nm on the second hole injection layer. The second hole transport material of table 2 below was added to another cell of the vacuum vapor deposition apparatus and evaporated by applying a current to the cell, thereby forming a second hole transport layer having a thickness of 60nm on the first hole transport layer. After the hole injection layer and the hole transport layer are formed, a light emitting layer is then deposited as follows. The compound H-17 was added to one unit of the vacuum vapor deposition apparatus as a light-emitting layer host, and the compound D-71 was added to the other unit as follows. The two materials were evaporated at different rates and deposited in a doping amount (amount of dopant) of 2 wt% based on the total amount of the host and the dopant to form a light emitting layer having a thickness of 40nm on the second hole transporting layer. Then compound ET-1 and compound EI-1 were added to the other two cells, evaporated at a ratio of 1:1 and deposited to form an electron transport layer with a thickness of 35nm on the light emitting layer. Next, after depositing the compound EI-1 as an electron injection layer having a thickness of 2nm on the electron transport layer, an Al cathode having a thickness of 80nm was deposited on the electron injection layer by another vacuum vapor deposition apparatus. Thus, an OLED device was prepared.
Examples of the apparatus 2 to 6: preparation of an OLED device comprising a combination of a hole transport material and a host compound of the present disclosure
An OLED device was manufactured in the same manner as in device example 1, except that the compound shown in table 2 was used as the second hole transport material.
The evaluation results of each of the apparatuses in examples 1 to 6 are shown in table 2. The driving voltage, the luminous efficiency and the CIE color coordinates of the OLED device at a luminance of 1,000 nits are provided in table 2 below.
Comparative examples 1 to 3: making OLED devices that do not contain the combination of hole transport materials and host compounds of the present disclosure
An OLED device was manufactured in the same manner as in device example 1, except that the compound shown in table 2 was used as the second hole transport material.
The evaluation results of each apparatus of comparative examples 1 to 3 are shown in table 2 below.
[ Table 2]
Figure BDA0002006467680000431
Device examples 7 to 14: preparation of an OLED device comprising a combination of a hole transport material and a host compound of the present disclosure Device for placing
An OLED device was fabricated in the same manner as in device example 1, except that the compound shown in table 3 was used as the second hole transport material, and compound H-12 was used as the host.
The drive voltage, luminous efficiency and CIE color coordinates for the luminance of 1,000 nits for the OLED devices of device examples 7 to 14 are provided in table 3 below.
Comparative examples 4 and 5: preparation of OLED devices that do not contain the combination of hole transport materials and host compounds of the present disclosure
An OLED device was fabricated in the same manner as in device example 1, except that the compound shown in table 3 was used as the second hole transport material, and compound H-12 was used as the host.
The driving voltage, the light emission efficiency, and the CIE color coordinates at a luminance of 1,000 nits for the OLED devices of comparative examples 4 and 5 are provided in table 3 below.
[ Table 3]
Figure BDA0002006467680000441
Figure BDA0002006467680000442
Figure BDA0002006467680000451
As shown in the above tables 2 and 3, the devices of device examples 1 to 14 have better driving voltage and luminous efficiency characteristics than the device of the comparative example. When device examples 1 to 14 and comparative examples are compared, it is understood that higher luminous efficiency characteristics are obtained due to the low HOMO (highest occupied molecular orbital) energy level of the hole transport material of the present disclosure, and lower driving voltage is obtained due to the fast hole transport ability of fluorene (but not limited by theory). The results show that the problem of an increase in driving voltage when the luminous efficiency is improved is overcome.
In view of the main feature of the Hole Transport Layer (HTL), i.e., hole transport capability, a low driving voltage generally requires fast hole transport. Therefore, a high HOMO energy level is required. At a high HOMO level, the driving voltage is reduced, but it is difficult to obtain high efficiency. In addition, the efficiency of the light-emitting layer decreases at a low driving voltage, and thus high efficiency is not easily obtained. By using the combination of the hole transport layer and the light emitting layer of the present disclosure, a relatively low driving voltage and high efficiency can be obtained.
It is understood that this is because 5(b) benzofluorene has a relatively lower HOMO energy level than 2(b) benzofluorene, thus providing higher efficiency (but not being limited by theory). If the HOMO level is lowered, the driving voltage is increased. However, fluorene cancels the increased driving voltage, and finally can provide a low driving voltage.

Claims (10)

1. An organic electroluminescent device, comprising:
a first electrode;
a second electrode opposite the first electrode;
one or more light emitting layers disposed between the first electrode and the second electrode; and
one or more hole transport regions disposed between the first electrode and the light emitting layer, wherein at least one layer of the hole transport regions comprises a compound represented by formula 1 below, and
at least one layer of the light emitting layers includes a compound represented by the following formula 2:
Figure FDA0003248416400000011
wherein
Ar1To Ar4Each independently represents a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted 5-to 30-membered heteroaryl group, or a substituted or unsubstituted spiro [ fluorene-C3-C30 cycloalkane](ii) a Or Ar1And Ar2And Ar3And Ar4Are linked to each other to form a mono-or polycyclic, 3-to 30-membered aliphatic or aromatic ring or a combination thereof, the carbon atoms of which can be replaced by at least one heteroatom selected from nitrogen, oxygen and sulfur;
Ar5and Ar6Each independently represents a substituted or unsubstituted C1-C6 alkyl group or a substituted or unsubstituted C6-C12 aryl group; or are linked to each other to form a mono-or polycyclic, 5-to 15-membered aliphatic or aromatic ring, or a combination thereof;
L1represents a single bond, a substituted or unsubstituted C6-C30 arylene, or a substituted or unsubstituted 5-to 30-membered heteroarylene;
L2represents a single bond, a substituted or unsubstituted C1-C30 alkylene group, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted 5-to 30-membered heteroarylene group, with the proviso that wherein n is 0, L2Is absent;
R1and R2Each independently represents hydrogen, deuterium, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 5-to 30-membered heteroaryl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted 3-to 7-membered heterocycloalkyl, substituted or unsubstituted C6-C30 aryl C1-C30 alkyl, -NR11R12、-SiR13R14R15、-SR16、-OR17Cyano, nitro or hydroxy; or are linked to an adjacent substituent(s) to form a mono-or polycyclic, 3 to 30-membered alicyclic or aromatic ring or a combination thereof, whose carbon atom(s) can be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
R11to R17Each independently represents hydrogen, deuterium, halogen, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted 5-to 30-membered heteroaryl, substituted or unsubstituted 3-to 7-membered heterocycloalkyl, or substituted or unsubstituted C3-C30 cycloalkyl; or are linked to an adjacent substituent(s) to form a mono-or polycyclic, 3 to 30-membered alicyclic or aromatic ring or a combination thereof, whose carbon atom(s) can be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
m represents an integer of 1 to 2, wherein m is 2, each NAr1Ar2Can be the same or different;
n represents an integer of 0 to 2, wherein n is 2, and each NAr3Ar4Can be the same or different;
a represents an integer of 1 to 5, wherein a is an integer of 2 or more, and each R1Can be the same or different;
b represents an integer of 1 to 4, wherein b is an integer of 2 or more, and each R2Can be the same or different;
ma represents a substituted or unsubstituted nitrogen-containing 3-to 30-membered heteroaryl;
L3represents a single bond, a substituted or unsubstituted C6-C30 arylene group, or a substituted or unsubstituted nitrogen-containing 3-to 30-membered heteroarylene group;
formula 2 and formula 2-a are fused at the positions of e and f, f and g or g and h of formula 2 and the position of formula 2-a to form a ring;
R3to R5Each independently represents hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C30 arylC 1-C30 alkyl group, a substituted or unsubstituted C6-C30 aryl group, a substituted or unsubstituted C1-C30 alkylC 6-C30 aryl group, a substituted or unsubstituted 3-to 30-membered heteroaryl group, a substituted or unsubstituted C3-C30 cycloalkyl group, a substituted or unsubstituted tri-C1-C30 alkylsilyl group, or a substituted or unsubstituted C6326-C3538 arylC 6-C30 arylgroupSubstituted or unsubstituted di-C1-C30 alkyl C6-C30 arylsilyl, substituted or unsubstituted C1-C30 alkyl di-C6-C30 arylsilyl, substituted or unsubstituted tri-C6-C30 arylsilyl, substituted or unsubstituted mono-or di-C1-C30 alkylamino, substituted or unsubstituted mono-or di-C6-C30 arylamino, or substituted or unsubstituted C1-C30 alkyl C6-C30 arylamino;
r represents hydrogen, deuterium, substituted or unsubstituted C1-C30 alkyl, substituted or unsubstituted C6-C30 arylC 1-C30 alkyl, substituted or unsubstituted C6-C30 aryl, substituted or unsubstituted C1-C30 alkylC 6-C30 aryl, substituted or unsubstituted 3-to 30-membered heteroaryl, substituted or unsubstituted C3-C30 cycloalkyl, substituted or unsubstituted tri-C1-C30 alkylsilyl, substituted or unsubstituted di-C1-C30 alkyl C6-C30 arylsilyl, substituted or unsubstituted C1-C30 alkyl di-C6-C30 arylsilyl, substituted or unsubstituted tri-C6-C30 arylsilyl, substituted or unsubstituted mono-or di-C1-C30 alkylamino, substituted or unsubstituted mono-or di-C6-C30 arylamino, or substituted or unsubstituted C1-C30 alkyl C6-C30 arylamino;
o and q each independently represent an integer of 1 to 4, and p represents an integer of 1 to 2, wherein o, p and q are integers of 2 or more, R3To R5Each of which can be the same or different;
the heteroaryl or heteroarylene group contains at least one heteroatom selected from B, N, O, S, Si and P; and is
The heterocycloalkyl group contains at least one heteroatom selected from O, S and N.
2. The organic electroluminescent device according to claim 1, wherein formula 1 is represented by formula 3 or formula 4 below:
Figure FDA0003248416400000041
Figure FDA0003248416400000051
wherein
Ar1To Ar6、L1、L2、R1、R2A, b, m and n are as defined in claim 1.
3. The organic electroluminescent device according to claim 1, wherein in formula 1, Ar1To Ar4Each independently represents a substituted or unsubstituted C6-C25 aryl group, a substituted or unsubstituted 5-to 15-membered heteroaryl group, or a substituted or unsubstituted spiro [ fluorene-C5-C8 cycloalkane]]。
4. The organic electroluminescent device according to claim 1, wherein in formula 1, Ar5And Ar6Each independently represents a methyl group, a phenyl group, or are linked to each other to form a spirocyclopentane.
5. The organic electroluminescent device according to claim 1, wherein formula 2 is represented by any one of formulae 5 to 10 below:
Figure FDA0003248416400000052
Figure FDA0003248416400000061
wherein Ma and L3、R3To R5R, o, p and q are as defined in claim 1.
6. The organic electroluminescent device according to claim 1, wherein, in formula 2, Ma represents a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted quinazolinyl group, or a substituted or unsubstituted quinoxalinyl group.
7. The organic electroluminescence device according to claim 1In the light-emitting device, in formula 2, R represents substituted or unsubstituted C6-C15Aryl or substituted or unsubstituted nitrogen-containing 5 to 15 membered heteroaryl.
8. The organic electroluminescent device according to claim 1, wherein the compound represented by formula 1 is selected from the group consisting of:
Figure FDA0003248416400000062
Figure FDA0003248416400000071
Figure FDA0003248416400000081
Figure FDA0003248416400000091
9. the organic electroluminescent device according to claim 1, wherein the compound represented by formula 2 is selected from the group consisting of:
Figure FDA0003248416400000092
Figure FDA0003248416400000101
Figure FDA0003248416400000111
10. the organic electroluminescent device according to claim 1, wherein the hole transport region comprises a hole transport layer, and further comprises at least one of a hole injection layer, an electron blocking layer, and a hole assist layer.
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