CN103221406A - Novel organic electroluminescent compounds and organic electroluminescent device using the same - Google Patents

Abstract

Provided are novel organic electroluminescent compounds and organic electroluminescent devices using the same. Since the organic electroluminescent compound according to the present invention has good luminous efficiency and excellent life property, it can be used to manufacture an OLED device which is excellent in operation life and consumes less power due to improved power efficiency.

Description

New organic electroluminescent compound and organic electroluminescent device using the same

technical field

The present invention relates to novel organic electroluminescent compounds and organic electroluminescent devices comprising the same.

technical background

Among display devices, electroluminescent (EL) devices of self-emissive display devices are preferred because they provide wide viewing angles, excellent contrast, and fast response rates. Eastman Kodak first developed an organic EL device in 1987, which used low-molecular-weight aromatic diamines and aluminum complexes as materials for forming the electroluminescent layer [Appl.Phys.Lett.51,913, 1987].

The most important factor determining the luminous efficiency of an organic light-emitting diode (OLED) is the electroluminescent material. Although fluorescent materials have been widely used as electroluminescent materials so far, from the perspective of electroluminescence mechanism, developing phosphorescent materials is one of the best ways to theoretically increase the luminous efficiency up to 4 times. So far, iridium(III) complexes are well known as a phosphorescent material, including (acac)Ir(btp) ₂ , Ir(ppy) ₃ and Firpic as red, green and blue phosphorescent materials, respectively. Specifically, many phosphorescent materials are currently being researched in Japan, Europe, and the United States.

Currently, CBP is known to be the most widely used host material for phosphorescent materials. High-efficiency OLEDs using hole-blocking layers comprising BCP, BAlq, etc. have been reported. Pioneer Corporation (Japan) and others have reported high-performance OLEDs using BAlq derivatives as substrates.

Although these materials provide good electroluminescent properties, they are disadvantageous due to their low glass transition temperature and poor thermal stability, which may degrade during high temperature deposition processes in vacuum. Since the power efficiency of an OLED is determined by (π/voltage)×current efficiency, the power efficiency is inversely proportional to the voltage. High power efficiency is required to reduce the power consumption of OLEDs. In fact, OLEDs using phosphorescent materials provide much better current efficiency (cd/A) than OLEDs using fluorescent materials. However, when existing materials such as BAlq, CBP, etc. are used as hosts of phosphorescent materials, there is no obvious advantage in power efficiency (lm/W) compared to OLEDs using fluorescent materials because of higher driving voltage. In addition, the lifetime of OLED devices using such materials is not satisfactory.

On the other hand, International Patent Application No. WO2006/049013 discloses a compound for an organic electroluminescent material, the main chain of which has a fused bicyclic group. However, this document does not specifically disclose a compound having two features: a carbazole main chain substituted with a cycloalkyl or heterocycloalkyl group fused to an aromatic ring and a nitrogen-containing fused bicyclic group.

Contents of the invention

technical problem

Therefore, the present invention has noticed the problems in the related art, and an object of the present invention is to provide an organic electroluminescent compound with a main chain, thereby providing better luminous efficiency and device life with suitable color coordinates compared to conventional materials .

Another object of the present invention is to provide an organic electroluminescent device having high efficiency and long operating life, which uses the organic electroluminescent compound as an electroluminescent material.

Technical solutions

Provided are a compound for an organic electroluminescent compound represented by Chemical Formula 1 below, and an organic electroluminescent device using the compound. Since the organic electroluminescent compound of the present invention has superior luminous efficiency and excellent lifetime properties, it can be used to manufacture OLED devices which have an extremely superior operating lifetime and consume less power due to improved power efficiency.

chemical formula 1

in:

Ring A represents a monocyclic or polycyclic aromatic ring;

X ₁ and X ₂ independently represent N or CR';

_L represents a single bond, a substituted or unsubstituted (C6-C30) arylene group, a substituted or unsubstituted (C2-C30) heteroarylene group or a substituted or unsubstituted (C3-C30) cycloalkylene group;

Ar ₁ represents hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (C2-C30) heteroaryl;

Z is independently selected from the following structures:

And when the ring A is a monocyclic aromatic ring, Z is only selected from the following structures:

Y represents -O-, -S-, -C(R ₁₁ R ₁₂ )-, -Si(R ₁₃ R ₁₄ )- or -N(R ₁₅ )-;

R ₁ to R ₉ independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C2-C30) Heteroaryl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl (C1-C30 ) alkyl, substituted or unsubstituted (C6-C30) aryl fused to one or more (C3-C30) cycloalkyl, 5- fused to one or more substituted or unsubstituted aromatic rings To 7-membered heterocycloalkyl, (C3-C30)cycloalkyl fused with one or more substituted or unsubstituted aromatic rings, -NR ₁₆ R ₁₇ , -SiR ₁₈ R ₁₉ R ₂₀ , -SR ₂₁ , -OR ₂₂ , cyano, nitro or hydroxyl; or R1 to R9 can be substituted or unsubstituted (C3-C30) alkenylene or substituted or unsubstituted (C3-C30) with or without fused rings The alkylene group is connected with adjacent substituents to form an alicyclic ring and a monocyclic or polycyclic aromatic ring, and the carbon atoms of the alicyclic ring and a monocyclic or polycyclic aromatic ring can be replaced by one or more selected from N, O and S Heteroatom substitution;

R' and R ₁₁ to R ₂₂ independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C2 -C30)heteroaryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl or substituted or unsubstituted (C3-C30)cycloalkyl; or they may be substituted or unsubstituted with or without fused rings Unsubstituted (C3-C30) alkenylene or substituted or unsubstituted (C3-C30) alkylene is connected with adjacent substituents to form alicyclic and monocyclic or polycyclic aromatic rings, and the alicyclic and monocyclic Or the carbon atoms of the polycyclic aromatic ring can be replaced by one or more heteroatoms selected from N, O and S;

a, c, e and i independently represent an integer of 1 to 4, and when a, c, e and i are integers greater than or equal to 2, each of R ₁ , R ₃ , R ₅ and R ₉ may be the same or each other different;

b, d and g independently represent an integer of 1 to 3, and when b, d and g are integers greater than or equal to 2, each of R ₂ , R ₄ and R ₇ may be the same or different from each other;

f represents an integer from 1 to 6, and when f is an integer greater than or equal to 2, each R ₆ can be the same or different from each other;

h represents an integer from 1 to 5, and when h is an integer greater than or equal to 2, each _R may be the same or different from each other; and

The heteroaryl ring, heteroarylene, heterocycloalkyl, and heteroaryl include one or more heteroatoms selected from B, N, O, S, P(=O), Si, and P.

基（chrysenyl）、并四苯基（naphthacenyl）、荧蒽基（fluoranthenyl）等。所述萘基包括1-萘基和2-萘基，所述蒽基包括1-蒽基、2-蒽基和9-蒽基，所述菲基包括1-菲基、2-菲基、3-菲基、4-菲基和9-菲基，所述并四苯基(naphthacenyl)包括1-并四苯基、2-并四苯基和9-并四苯基。所述芘基包括1-芘基、2-芘基和4-芘基，所述联苯基包括2-联苯基、3-联苯基和4-联苯基，所述三联苯基包括对-三联苯基-4-基、对-三联苯基-3-基、对-三联苯基-2-基、间-三联苯基-4-基、间-三联苯基-3-基和间-三联苯基-2-基，所述芴基包括1-芴基、2-芴基、3-芴基、4-芴基和9-芴基。As used herein, the terms "alkyl", "alkoxy" and other substituents containing "alkyl" moieties include straight and branched chain moieties, and "cycloalkyl" includes polycyclic hydrocarbon rings (such as substituted or unsubstituted adamantyl or substituted or unsubstituted (C7-C30) bicycloalkyl) and monocyclic hydrocarbon rings. The term "aryl" as used herein refers to an organic group obtained by removing one hydrogen atom from an aromatic hydrocarbon, which may include 4- to 7-membered, especially 5- or 6-membered monocyclic or condensed rings, even Structures in which a plurality of aryl groups are linked by single bonds are also included. Specific examples thereof include, but are not limited to: phenyl, naphthyl, biphenyl, terphenyl, anthracenyl, indenyl, fluorenyl, phenanthrenyl, benzo[9,10]phenanthrenyl (triphenylenyl), pyrenyl, perylenyl,

Chrysenyl, naphthacenyl, fluoroanthenyl, etc. The naphthyl includes 1-naphthyl and 2-naphthyl, the anthracenyl includes 1-anthracenyl, 2-anthracenyl and 9-anthracenyl, and the phenanthrenyl includes 1-phenanthrenyl, 2-phenanthrenyl, 3-phenanthrenyl, 4-phenanthrenyl and 9-phenanthrenyl, the naphthacenyl includes 1-naphthacenyl, 2-naphthacenyl and 9-naphthacenyl. The pyrenyl includes 1-pyrenyl, 2-pyrenyl and 4-pyrenyl, the biphenyl includes 2-biphenyl, 3-biphenyl and 4-biphenyl, and the terphenyl includes P-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, m-terphenyl-4-yl, m-terphenyl-3-yl and m-terphenyl-2-yl, the fluorenyl includes 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl.

The term "heteroaryl" as used herein means comprising 1-4 heteroatoms selected from B, N, O, S, P(=O), Si and P as aromatic ring skeletal atoms, and the other aromatic ring skeletal atoms are carbon aryl group. It may be a 5-membered or 6-membered monocyclic heteroaryl or polycyclic heteroaryl obtained by condensation with one or more benzene rings, and may be partially saturated. In the present invention, "heteroaryl" includes a structure in which one or more heteroaryl groups are linked by a single bond. The heteroaryl groups include divalent aryl groups in which ring heteroatoms can be oxidized or quaternized to form, for example, N-oxides or quaternary ammonium salts. Specific examples thereof include, but are not limited to, monocyclic heteroaryl groups such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazole oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, furazanyl (furazanyl), pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc.; polycyclic heteroaryl For example, benzofuryl, benzothienyl, dibenzofuryl, dibenzothienyl, isobenzofuryl, benzimidazolyl, benzothiazolyl, benzisothiazolyl, benzisoxazole Base, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolinyl, isoquinolyl, cinnolinyl (cinnolinyl), quinazolinyl, quinolinyl quinoxalinyl, carbazolyl, phenanthridinyl, benzodioxolyl, acridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, Phenoxazinyl, etc.; N-oxides thereof (such as pyridyl N-oxide, quinolinyl N-oxide); or quaternary ammonium salts thereof, etc.

Pyrrolyl includes: 1-pyrrolyl, 2-pyrrolyl and 3-pyrrolyl; pyridyl includes 2-pyridyl, 3-pyridyl and 4-pyridyl; indolyl includes 1-indolyl, 2-indolyl Indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, and 7-indolyl; isoindolyl includes 1-isoindolyl, 2-isoindolyl Base, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl and 7-isoindolyl; furyl includes 2-furyl and 3-furyl; Benzofuryl includes 2-benzofuryl, 3-benzofuryl, 4-benzofuryl, 5-benzofuryl, 6-benzofuryl and 7-benzofuryl; isobenzo Furanyl includes 1-isobenzofuryl, 3-isobenzofuryl, 4-isobenzofuryl, 5-isobenzofuryl, 6-isobenzofuryl and 7-isobenzofuryl ; Quinolinyl includes 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl and 8-quinolyl; isoquinolyl includes 1-isoquinolyl Linyl, 3-isoquinolinyl, 4-isoquinolinyl, 5-isoquinolinyl, 6-isoquinolinyl, 7-isoquinolinyl and 8-isoquinolinyl; quinoxalinyl includes 2-quinoxalinyl, 5-quinoxalinyl and 6-quinoxalinyl; carbazolyl includes 1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl and 9 -carbazolyl; phenanthridinyl includes 1-phenanthridinyl, 2-phenanthridinyl, 3-phenanthridinyl, 4-phenanthridinyl, 6-phenanthridinyl, 7-phenanthridinyl, 8-phenanthridinyl , 9-phenanthridinyl and 10-phenanthridinyl; acridinyl includes 1-acridinyl, 2-acridinyl, 3-acridinyl, 4-acridinyl and 9-acridinyl; phenanthroline The base includes 1,7-phenanthrolin-2-yl, 1,7-phenanthrolin-3-yl, 1,7-phenanthrolin-4-yl, 1,7-phenanthrolin-5-yl, 1,7-phenanthrolin-6-yl, 1,7-phenanthrolin-8-yl, 1,7-phenanthrolin-9-yl, 1,7-phenanthrolin-10-yl, 1, 8-phenanthrolin-2-yl, 1,8-phenanthrolin-3-yl, 1,8-phenanthrolin-4-yl, 1,8-phenanthrolin-5-yl, 1,8- Phenanthroline-6-yl, 1,8-phenanthroline-7-yl, 1,8-phenanthroline-9-yl, 1,8-phenanthroline-10-yl, 1,9-phenanthrole Phenanthroline-2-yl, 1,9-phenanthroline-3-yl, 1,9-phenanthroline-4-yl, 1,9-phenanthroline-5-yl, 1,9-phenanthroline- 6-yl, 1,9-phenanthroline-7-yl, 1,9-phenanthroline-8-yl, 1,9-phenanthroline-10-yl, 1,10-phenanthroline-2- Base, 1,10-phenanthrolin-3-yl, 1,10-phenanthrolin-4-yl, 1,10-phenanthrolin-5-yl, 2,9-phenanthrolin-1-yl, 2,9-phenanthrolin-3-yl, 2,9-phenanthrolin-4-yl, 2,9-phenanthrolin-5-yl, 2,9-phenanthrolin-6-yl, 2, 9-phenanthrolin-7-yl, 2,9-phenanthrolin-8-yl, 2,9-phenanthrolin-10-yl, 2,8-phenanthrolin-1-yl, 2,8- Philo Phenanthroline-3-yl, 2,8-phenanthroline-4-yl, 2,8-phenanthroline-5-yl, 2,8-phenanthroline-6-yl, 2,8-phenanthroline- 7-yl, 2,8-phenanthroline-9-yl, 2,8-phenanthroline-10-yl, 2,7-phenanthroline-1-yl, 2,7-phenanthroline-3- Base, 2,7-phenanthrolin-4-yl, 2,7-phenanthrolin-5-yl, 2,7-phenanthrolin-6-yl, 2,7-phenanthrolin-8-yl, 2,7-phenanthrolin-9-yl and 2,7-phenanthrolin-10-yl; phenazinyl includes 1-phenazinyl and 2-phenazinyl; phenothiazinyl includes 1-phenothiazine Base, 2-phenothiazinyl, 3-phenothiazinyl, 4-phenothiazinyl and 10-phenothiazinyl; phenoxazinyl includes 1-phenoxazinyl, 2-phenoxazinyl, 3 - phenoxazinyl, 4-phenoxazinyl and 10-phenoxazinyl; oxazolyl includes 2-oxazolyl, 4-oxazolyl and 5-oxazolyl; oxadiazoles include 2-oxadio Azolyl and 5-oxadiazolyl; Furazanyl includes 3-furazanyl; Dibenzofuryl includes 1-dibenzofuryl, 2-dibenzofuryl, 3-dibenzofuryl and 4-Dibenzofuryl; dibenzothienyl includes 1-dibenzothienyl, 2-dibenzothienyl, 3-dibenzothienyl and 4-dibenzothienyl.

The term "(C1-C30)alkyl" as used herein includes (C1-C20)alkyl or (C1-C10)alkyl, and the term "(C6-C30)aryl" includes (C6-C20)aryl. The term "(C2-C30) heteroaryl" includes (C2-C20) heteroaryl, and the term "(C3-C30) cycloalkyl" includes (C3-C20) cycloalkyl or (C3-C7) cycloalkyl . The term "(C2-C30)alkenyl or alkynyl" includes (C2-C20)alkenyl or alkynyl, or (C2-C10)alkenyl or alkynyl.

In the expression "substituted or unsubstituted" (or "with or without a substituent") used herein, the term "substituted (with a substituent)" means that the unsubstituted substituent is further substituted with a substituent. Each substituent of L ₁ , Ar ₁ , R ₁ to R ₉ , R, and R ₁₁ to R ₂₂ may also be substituted by one or more substituents selected from the group consisting of deuterium, halogen, halogen substituted or unsubstituted ( C1-C30) alkyl, (C6-C30) aryl, (C6-C30) aryl substituted or unsubstituted (C2-C30) heteroaryl, 5- to 7-membered heterocycloalkyl, and one or 5- to 7-membered heterocycloalkyl, (C3-C30)cycloalkyl, (C6-C30)cycloalkyl fused to one or more aromatic rings, R ^a R ^b R ^c Si-, (C2-C30) alkenyl, (C2-C30) alkynyl, cyano, carbazolyl, -NR ^d R ^e , -BR ^f R ^g , -PR ^h R ⁱ , -P(= O)R ^j R ^k , (C6-C30)aryl(C1-C30)alkyl, (C1-C30)alkyl(C6-C30)aryl, R ^l T-, R ^m C(=O)- , R ^m C (= O) O-, carboxyl, nitro and hydroxyl, wherein R ^a to R ^l independently represent (C1-C30) alkyl, (C6-C30) aryl or (C2-C30) heteroaryl base; T is S or O; R ^m represents (C1-C30) alkyl, (C1-C30) alkoxy, (C6-C30) aryl or (C6-C30) aryloxy.

The organic electroluminescent compound may be represented by the following Chemical Formulas 2-9.

chemical formula 2

chemical formula 3

chemical formula 4

chemical formula 5

chemical formula 6

chemical formula 7

chemical formula 8

chemical formula 9

In the formula, X ₂ is N or CH; Y is -O-, -S-, -C(R ₁₁ R ₁₂ )- or -N(R ₁₅ )-; L ₁ represents a single bond, substituted or unsubstituted ( C6-C30) arylene, or substituted or unsubstituted (C2-C30) heteroarylene; Ar ₁ represents hydrogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6- C30) aryl, or substituted or unsubstituted (C2-C30) heteroaryl; R ₁ to R ₉ independently represent hydrogen, deuterium, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C2-C30) Heteroaryl, NR ₁₆ R ₁₇ or SiR ₁₈ R ₁₉ R ₂₀ ; R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ to R ₂₀ independently represent hydrogen, deuterium, substituted or unsubstituted (C1- C30) alkyl, substituted or unsubstituted (C6-C30) aryl or substituted or unsubstituted (C2-C30) heteroaryl; or R ₁₆ and R ₁₇ can be substituted or unsubstituted with or without fused rings A substituted (C3-C30) alkenylene group or a substituted or unsubstituted (C3-C30) alkylene group is connected to form an alicyclic ring or a monocyclic or polycyclic aromatic ring, and the alicyclic ring and the monocyclic or polycyclic aromatic ring The carbon atoms in may be substituted by one or more heteroatoms selected from N, O and S.

Specifically, X ₂ represents N or CH; Y represents -O-, -S-, -C(R ₁₁ R ₁₂ )- or -N(R ₁₅ )-;

_L represents a single bond or is selected from the following structures of arylene:

R ₃₁ and R ₃₂ independently represent methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n- Octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl , phenyl, naphthyl, pyridyl or quinolinyl;

Ar ₁ represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, 2-Ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, phenyl , biphenyl, terphenyl, naphthyl, 9,9-diphenylfluorenyl, 9,9-dimethylfluorenyl, fluoranthene, pyridyl, dibenzofuranyl, dibenzothienyl Or N-phenylcarbazolyl, and the phenyl, biphenyl, terphenyl, naphthyl and carbazolyl of Ar ₁ can also be substituted by one or more substituents selected from the group: deuterium, fluorine, Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl , n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, triphenylsilyl, Trimethylsilyl, Dimethylphenylsilyl, Diphenylmethylsilyl, Phenyl, Naphthyl, 9,9-Diphenylfluorenyl, 9,9-Dimethylfluorenyl , phenylpyridyl, carbazolyl, fluoranthenyl, dibenzofuranyl and dibenzothienyl; and

R ₁ to R ₉ independently represent hydrogen, deuterium, phenyl, pyridyl, dibenzofuryl, dibenzothienyl, amino or carbazolyl; R ₁₁ , R ₁₂ and R ₁₅ independently represent hydrogen, deuterium , methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl Hexyl, n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, phenyl, biphenyl , 9,9-diphenylfluorenyl, 9,9-dimethylfluorenyl, naphthyl, pyridyl, N-phenylcarbazolyl or quinolinyl, and the benzene of R ₁₁ , R ₁₂ and R ₁₅ The group can also be substituted by one or more substituents selected from the group consisting of deuterium, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl , isopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, three Fluoroethyl, perfluoropropyl, perfluorobutyl, phenyl and naphthyl, and R ₁₁ and R ₁₂ may be connected to each other to form a ring.

The organic electroluminescent compound of the present invention can be listed as following compound, but they do not limit the present invention:

The organic electroluminescent compound of the present invention can be prepared, for example, as shown in Scheme 1 below, but is not limited thereto.

[plan 1]

In Scheme 1, rings A, X ₁ , X ₂ , L ₁ , Ar ₁ , R ₁ , R ₂ , R ₃ , a, b, c, and Z are the same as defined in Chemical Formula 1; Hal represents halogen.

An organic electroluminescent device is provided, comprising a first electrode; a second electrode; and one or more organic layers interposed between the first electrode and the second electrode, wherein the organic layer comprises the formula One or more organic electroluminescent compounds represented by 1. The organic layer includes an electroluminescent layer, and the organic electroluminescent compound of Chemical Formula 1 may be used as a host in the electroluminescent layer.

In the electroluminescent layer, when the organic electroluminescent compound of Chemical Formula 1 is used as a host, one or more phosphorescent dopants are contained. The phosphorescent dopant used in the organic electroluminescent device of the present invention is not specifically limited, but can be selected from compounds represented by the following chemical formula 10:

chemical formula 10

M ¹ L ¹⁰¹ L ¹⁰² L ¹⁰³

in:

M ¹ is a metal selected from Group 7, Group 8, Group 9, Group 10, Group 11, Group 13, Group 14, Group 15 and Group 16 of the Periodic Table of the Elements, ligand L ¹⁰¹ , L ¹⁰² , and L ¹⁰³ are independently selected from the following structures:

R ₂₀₁ to R ₂₀₃ independently represent hydrogen, deuterium, halogen substituted or unsubstituted (C1-C30) alkyl, (C1-C30) alkyl substituted or unsubstituted (C6-C30) aryl or halogen;

R ₂₀₄ to R ₂₁₉ independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) ring Alkyl, substituted or unsubstituted (C2-C30)alkenyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted mono-(C1-C30)alkylamino or substituted or unsubstituted Di-(C1-C30)alkylamino, substituted or unsubstituted mono-(C6-C30)arylamino or substituted or unsubstituted di-(C6-C30)arylamino, SF ₅ , substituted or unsubstituted Tri(C1-C30)alkylsilyl, substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, substituted or unsubstituted tri(C6-C30)aryl Silyl, cyano or halogen;

R ₂₂₀ to R ₂₂₃ independently represent hydrogen, deuterium, halogen substituted or unsubstituted (C1-C30) alkyl or (C1-C30) alkyl substituted or unsubstituted (C6-C30) aryl;

R ₂₂₄ and R ₂₂₅ independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or halogen, or R ₂₂₄ and R ₂₂₅ can be represented by having or A (C3-C12) alkenylene group or (C3-C12) alkylene group without a fused ring is connected to form an alicyclic ring and a monocyclic or polycyclic aromatic ring;

R ₂₂₆ represents substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C2-C30) heteroaryl or halogen;

R ₂₂₇ to R ₂₂₉ independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or halogen; and

R ₂₃₁ to R ₂₄₂ independently represent hydrogen, deuterium, halogen substituted or unsubstituted (C1-C30) alkyl, (C1-C30) alkoxy, halogen, substituted or unsubstituted (C6-C30) aryl, Cyano, substituted or unsubstituted (C3-C30) cycloalkyl groups, or they can be connected to adjacent substituents to form spiro or fused rings through alkylene or alkenylene, or they can be connected through alkylene or alkenene The group is connected with _R207 or _R208 to form a saturated or unsaturated condensed ring.

The dopant compound of Chemical Formula 10 can be listed as the following compounds, but not limited thereto:

In the organic electronic device of the present invention, in addition to the organic electroluminescent compound represented by Chemical Formula 1, the organic layer may also include one or more compounds selected from arylamine compounds and styrylarylamine compounds. For examples of the arylamine compound or styrylarylamine compound, see Korean Patent Application No. 10-2008-0123276, 10-2008-0107606, or 10-2008-0118428, but is not limited thereto.

In addition, in the organic electroluminescent device of the present invention, in addition to the organic electroluminescent compound represented by Chemical Formula 1, the organic layer may also include one or more elements selected from Group 1 and Group 2 of the Periodic Table of Elements. metals or complexes of organometallics, fourth and fifth period transition metals, lanthanide metals and d-transition elements. The organic layer may include an electroluminescent layer and a charge generation layer.

In addition, in addition to the organic electroluminescent compound represented by the chemical formula 1, the organic layer may also include one or more organic electroluminescent layers that emit blue light, green light or red light, so as to achieve white light emission. Organic electroluminescent devices. Examples of compounds emitting blue, green, or red light may be compounds described in Korean Patent Application No. 10-2008-0123276, 10-2008-0107606, or 10-2008-0118428, but are not limited thereto.

In the organic electroluminescence device of the present invention, a layer selected from a chalcogenide layer, a metal halide layer, and a metal oxide layer (hereinafter referred to as "surface layer") may be placed on one or both electrodes of the electrode pair on the inner surface. More specifically, a metal chalcogenide (including oxide) layer of silicon or aluminum can be placed on the anode surface of the electroluminescent medium layer, and a metal halide layer or a metal oxide layer can be placed on the electroluminescent medium layer on the cathode surface. resulting in job stability. For example, the chalcogenide may be _SiOx (1≤x≤2), _AlOx (1≤x≤1.5), SiON, SiAlON, or the like. For example, the metal halides may be LiF, MgF ₂ , CaF ₂ , rare earth metal fluorides, and the like. For example, the metal oxide may be _Cs2O , _Li2O , MgO, SrO, BaO, CaO, or the like.

In the organic electroluminescent device of the present invention, it is also preferred that a mixed region of an electron-transport compound and a reducing dopant, or a mixture of a hole-transport compound and an oxidizing dopant is provided on at least one surface of the prepared electrode pair. mixed zone. In this case, electron injection and transport from the mixed region to the electroluminescent medium is facilitated since the electron transport compound is reduced to an anion. In addition, since the hole transport compound is oxidized to form a cation, injection and transport of holes from the mixed region to the electroluminescent medium is facilitated. Preferred oxidative dopants include various Lewis acids and acceptor compounds. Preferred reductive dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals, and mixtures thereof. In addition, white-light emitting electroluminescent devices having two or more electroluminescent layers can be produced by using a reducing dopant layer as a charge generation layer.

Beneficial effect of the present invention

According to the present invention, the organic electroluminescent compound can have high luminous efficiency and excellent material lifetime, and can be used to prepare OLED devices with extremely superior working lifetime.

Embodiments of the present invention

The organic electroluminescent compound of the present invention, its preparation method and the electroluminescent properties of the device are further described below by taking representative compounds of the present invention as examples. However, these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[Preparation Example 1] Preparation of Compound 1

Preparation of compound 1-1

2,4-dichloroquinazoline (8.1 g, 40.6 mmol), phenylboronic acid (5.0 g, 40.6 mmol), 200 ml of toluene, 50 ml of ethanol and 50 ml of water were mixed, and then Pd (PPh ₃ ) ₄ (1.9 g, 1.64 mmol) and K ₂ CO ₃ (12.9 g, 122 mmol). The mixture was stirred at 120°C for 5 hours and cooled to room temperature, then quenched with 200 ml of aqueous ammonium chloride. The mixture was extracted with 500 mL of ethyl acetate (EA), and washed with 50 mL of distilled water. The obtained organic layer was dried with anhydrous MgSO ₄ , and the organic solvent was removed under reduced pressure. Subsequently, silica gel filtration and recrystallization were performed to obtain Compound 1-1 (6.6 g, 68%).

Preparation of compound 1-2

Under reflux, 7H-benzo[c]carbazole (8.9 g, 41.10 mmol), compound 1-1 (11.9 g, 49.32 mmol), Pd(OAc) ₂ (0.46 g, NaOt-bu7.9 g , 82.20 mmol), 100 ml of toluene, P(t-bu) ₃ (2 ml, 4.11 mmol, 50% solution in toluene) were stirred. After 10 hours, the mixture was cooled to room temperature, and distilled water was added thereto. The resulting mixture was extracted with EA, dried over anhydrous _MgSO4 , and dried under reduced pressure. Subsequently, column separation was performed to obtain compound 1-2 (14.5 g, 84%).

Preparation of Compound 1-3

Put compound 1-2 (14.3 g, 33.98 mmol) into a single-necked flask to form a vacuum atmosphere, and then fill the flask with argon. THF (500 mL) was added, and the mixture was stirred at 0°C for 10 minutes. NBS (7.35 g, 40.78 mmol) was added and the mixture was stirred at room temperature for one day. The reaction was terminated, and the resulting mixture was extracted with distilled water and EA. The organic layer was dried with anhydrous MgSO ₄ , the solvent was removed using a rotary evaporator, and column chromatography was performed using hexane and EA as developers to obtain compound 1-3 (14.6 g, 85%).

Preparation of Compound 1-4

Put compound 1-3 (13.2 g, 26.30 mmol) into a single-necked flask to form a vacuum atmosphere, and then fill the flask with argon. 500 mL of THF was added, and the mixture was stirred at -78°C for 10 minutes. n-BuLi (2.5M in hexane) (15.8 mL, 39.45 mmol) was added dropwise, and the mixture was stirred at -78°C for 1 hour 30 minutes. Trimethyl borate (4.85 mL, 39.45 mmol) was added at -78°C. The mixture was stirred at -78°C for 30 minutes, then at room temperature for 4 hours. The reaction was terminated, and the resulting mixture was extracted with distilled water and EA. The organic layer was dried with anhydrous MgSO ₄ , the solvent was removed using a rotary evaporator, and column chromatography was performed using hexane and EA as developers to obtain compound 1-4 (6.9 g, 18.05 mmol, 65%).

Preparation of compound 1

Compound 1-4 (8.1 g, 17.4 mmol), 3-bromo-9-phenyl-9H-carbazole (6.7 g, 20.88 mmol), Pd(PPh ₃ ) ₄ (0.8 g, 0.7 mmol), 20 mL _of 2M aqueous _K2CO3 , 100 mL of toluene and 50 mL of ethanol were stirred for 12 hours. The mixture was washed with distilled water and extracted with EA. Drying with anhydrous MgSO ₄ , distillation under reduced pressure, and column separation gave compound 1 (6.8 g, 10.3 mmol, 58%).

MS/FAB: 663 (measured), 662.78 (calculated)

[Preparation Example 2] Preparation of Compound 2

Preparation of compound 2-1

Mix 2,4-dichloroquinazoline (8.1 g, 40.6 mmol), biphenylphenylboronic acid (8.0 g, 40.6 mmol), 200 mL toluene, 50 mL ethanol and 50 mL water, and add Pd ( _PPh3 ) ₄ (1.9 g, 1.64 mmol) and _K2CO3 (12.9 g, 122 mmol) _. The mixture was stirred at 120°C for 5 hours, cooled to room temperature, and quenched with 200 ml of aqueous ammonium chloride. The mixture was extracted with 500 mL of EA and washed with 50 mL of distilled water. The obtained organic layer was dried with anhydrous MgSO ₄ , and the organic solvent was removed under reduced pressure. Subsequently, silica gel filtration and recrystallization were performed to obtain compound 2-1 (8.2 g, 25.9 mmol, 64%).

Preparation of compound 2-2

Compound 2-2 (9.5 g, 19.1 mmol, 74%) was prepared by the same method as that of compound 1-2.

Preparation of compound 2-3

Compound 2-3 (9.0 g, 15.6 mmol, 82%) was prepared by the same method as that of compound 1-3.

Preparation of Compound 2-4

Compound 2-4 (4.0 g, 7.4 mmol, 47%) was prepared by the same method as that of compound 1-4.

Preparation of compound 2

Compound 2 (2.8 g , 4.6 mmol, 51%).

MS/FAB: 739 (measured), 738.87 (calculated)

[Preparation Example 3] Preparation of Compound 7

Preparation of Compound 7

Compound 7 (2.8 g , 4.6 mmol, 51%).

MS/FAB: 604 (measured), 603.73 (calculated)

[Preparation Example 4] Preparation of Compound 12

Preparation of compound 12

Prepared from compound 1-4 (6.9 g, 18.05 mmol) and 10-bromo-7-phenyl-7H-benzo[c]carbazole (7.8 g, 20.88 mmol) by the same method as compound 1 Compound 12 (6.8 g, 9.5 mmol, 53%).

MS/FAB: 713 (found), 712.84 (calculated).

[Preparation Example 5] Preparation of Compound 16

Preparation of compound 16

Compound 16 ( 7.6 g, 11.0 mmol, 61%).

MS/FAB: 690 (measured), 689.84 (calculated)

[Preparation Example 6] Preparation of Compound 25

Preparation of compound 6-1

7H-Benzo[c]carbazole (20 g, 92 mmol) and 1-bromo-4-iodobenzene (43.5 g, 184 mmol) were dissolved in 500 mL of toluene, and CuI (8.8 g, 46 mmol), diaminoethane (6.2 mL, 92 mmol) and K ₃ PO ₄ (8.7 g, 276 mmol), and the mixture was refluxed for 30 hours. The mixture was cooled to room temperature and quenched with 50 mL of 2.0M aqueous HCl. The resulting mixture was extracted with 1 L of EA and washed with 50 mL of distilled water. The obtained organic layer was dried with anhydrous MgSO ₄ , and the organic solvent was removed under reduced pressure. Silica gel column chromatography was then carried out to obtain compound 6-1 (19 g, 56%).

Preparation of compound 6-2

Compound 6-1 (19 g, 51 mmol) was dissolved in 250 mL of THF, cooled to -78°C, and n-BuLi (2.5M in hexane) (24.5 mL) was added at -78°C. The mixture was stirred at -78°C for 1 hour, B(OMe) ₃ (8.5 mL) was added, then the mixture was stirred for 2 hours, and the reaction was quenched with 100 mL of aqueous ammonium chloride. The resulting mixture was extracted with 500 ml of EA and washed with 100 ml of distilled water. The obtained organic layer was dried with anhydrous MgSO ₄ , and the organic solvent was removed under reduced pressure. Recrystallization was then performed to obtain compound 6-2 (14 g, 81%).

Preparation of compound 6-3

Compound 1-1 (3.3 g, 13.7 mmol) and compound 6-2 (5.5 g, 16.4 mmol) were mixed with 100 ml of toluene, 20 ml of ethanol and 20 ml of water, and Pd(PPh ₃ ) ₄ (1.6 g, 1.4 mmol) and K ₂ CO ₃ (5.7 g, 41.1 mmol). The mixture was stirred at 120°C for 5 hours, cooled to room temperature, and quenched with 20 ml of aqueous ammonium chloride. The mixture was extracted with 250 mL of EA and washed with 30 mL of distilled water. The obtained organic layer was dried with anhydrous MgSO ₄ , and the organic solvent was removed under reduced pressure. Silica gel filtration and recrystallization were then performed to obtain compound 6-3 (4.9 g, 9.8 mmol, 72%).

Preparation of Compound 6-4

Compound 6-4 (4.3 g, 7.5 mmol, 76%) was prepared by the same method as that of compound 1-3.

Preparation of compound 6-5

Compound 6-5 (1.7 g, 3.1 mmol, 43%) was prepared by the same method as that of compound 1-4.

Preparation of compound 25

Compound 25 (7.6 g, 10.3 mmol, 57%).

MS/FAB: 739 (measured), 738.87 (calculated)

[Preparation Example 7] Preparation of Compound 37

Preparation of compound 7-1

7H-Benzo[c]carbazole (50 g, 0.23 mol) was dissolved in 1.4 L of DMF, NBS (41 g, 0.23 mol) was added, and the mixture was stirred at room temperature for 24 hours. After the reaction was terminated, the resulting mixture was extracted with EA, and the organic layer was distilled under reduced pressure. Then silica gel column separation was carried out to obtain compound 7-1 (53.2 g, 78%).

Preparation of compound 7-2

Compound 7-1 (30 g, 0.10 mol), iodobenzene (22.6 ml, 0.20 mmol), CuI (9.6 g, 0.05 mol), Cs ₂ CO ₃ (99 g, 0.030 mol) and EDA (13.7 ml, 0.20 mol) was added to 500 ml of toluene, and stirred under reflux for 24 hours. The mixture was extracted with EA, distilled under reduced pressure, and column separated with MC/Hex to obtain compound 7-2 (20 g, 53%).

Preparation of compound 7-3

Compound 7-2 (18 g, 48.4 mmol) was dissolved in 250 mL of THF, 2.5M n-BuLi (in hexane) (23.2 mL, 58.0 mmol) was added at -78°C, and the mixture Stir for 1 hour. B(Oi-Pr) ₃ (16.7 mL, 72.5 mmol) was added slowly and the solution was stirred for 2 hours. 2M HCl was added and the mixture was quenched and extracted with distilled water and EA. Then recrystallization was carried out using MC and Hex to obtain compound 7-3 (13.6 g, 83.4%).

Preparation of compound 7-4

Compound 7-3 (13.6 g, 40.3 mmol), bromocarbazole (9.9 g, 40.3 mmol), Pd(PPh ₃ ) ₄ (2.3 g, 2.0 mmol), K ₂ CO ₃ (13.4 g, 96.7 mmol), 200 ml of toluene and 48 ml of distilled water were mixed, and stirred at 90° C. for 2 hours. The organic layer was distilled under reduced pressure and triturated with MeOH. The obtained solid was dissolved in MC, filtered on silica, and triturated with MC and hexane to obtain compound 7-4 (15 g, 81%).

Preparation of compound 37

Compound 1-1 (4 g, 16.6 mmol) and compound 7-4 (7.6 g, 16.6 mmol) were suspended in 80 ml of DMF, and 60% NaH (1.1 g, 28.2 mmol) was added at room temperature, The mixture was stirred for 12 hours. 1 liter of distilled water was added, and the mixture was filtered under reduced pressure. The resulting solid was triturated with MeOH/EA, dissolved in MC, filtered on silica, and triturated with MC/n-hexane to give compound 37 (2.4 g, 21.8%).

The measured value of MS/FAB is 662.78, and the theoretical value is 662.25

[Preparation Example 8] Preparation of Compound 116

Preparation of Compound 8-1

Compound 7-1 (10 g, 33.8 mmol), dibenzo[b,d]furan-4-ylboronic acid (8.6 g, 40.56 mmol), Pd(PPh ₃ ) ₄ (2 g, 1.7 mmol ), K ₂ CO ₃ (34 g, 321 mmol), 60 ml of toluene, 12 ml of EtOH and 12 ml of purified water were mixed and stirred at 120° C. for 15 hours. After the reaction was terminated, the resulting mixture was left standing, the aqueous layer was removed, and then the organic layer was concentrated. Silica gel column purification was then performed to obtain Compound 8-1 (10.2 g, 78%).

Preparation of compound 116

Compound 8-1 (3 g, 7.8 mmol) and compound 2-1 (2.1 g, 7.8 mmol) were suspended in 30 ml of DMF, and 60% NaH (376 mg, 9.4 mmol) was added at room temperature, The mixture was stirred for 12 hours. 500 ml of purified water was added, and the mixture was filtered under reduced pressure. The obtained solid was triturated sequentially with MeOH/EA, DMF and EA/THF. The obtained product was dissolved in MC, filtered on silica and triturated with MeOH/EA to give compound 116 (2.4 g, 46%).

The measured value of MS/FAB is 663.76, and the theoretical value is 663.23

[Preparation Example 9] Preparation of Compound 128

Preparation of compound 9-1

3-Bromo-9H-carbazole (5 g, 20.32 mmol), dibenzo[b,d]furan-4-ylboronic acid (4.7 g, 22.35 mmol), K ₂ CO ₃ (7 g, 50.79 mmol), Pd(PPh ₃ ) ₄ (1.17 g, 1.01 mmol), 100 mL of toluene, 25 mL of EtOH and 25 mL of purified water were mixed and stirred at 100°C for 3 hours. After the reaction was terminated, the mixture was cooled to room temperature, allowed to stand, and the water layer was removed. The organic layer was concentrated and purified using a silica gel column to obtain compound 9-1 (4.3 g, 64%).

Preparation of Compound 128

Compound 2-1 (3 g, 8.99 mmol) and compound 9-1 (3.14 g, 9.89 mmol) were suspended in 50 mL of anhydrous DMF, and 60% NaH (0.54 g, 13.5 mmol) was added at room temperature . The mixture was stirred at room temperature for 5 hours. After the reaction was terminated, 3 ml of MeOH was added dropwise, and a solid was obtained due to excess MeOH, which was purified on a silica gel column, suspended with EA, filtered, and crystallized with THF to obtain compound 128 (1 g, 18%).

The measured value of MS/FAB is 613.70, and the theoretical value is 613.22

[Example 1] Preparation of OLED devices using the organic electroluminescent compound of the present invention

OLED devices are fabricated using the inventive compounds of organic electronic materials. First, the transparent electrode ITO film (15Ω/□) for OLED made of glass (purchased from Samsung-Corning) was ultrasonically cleaned with trichlorethylene, acetone, ethanol and distilled water in sequence, before use Store in isopropanol. Then, the ITO substrate was placed in the substrate folder of the vacuum deposition equipment, and N ¹ , N ^1' -([1,1'-biphenyl]-4,4'-diyl)di( N ¹ -(naphthalene-1-yl)-N ⁴ , N ⁴ -diphenylbenzene-1,4-diamine is placed in the small chamber (cell) of the vacuum deposition equipment, and then exhausted to a maximum vacuum of 10 ^-6 torr.Then, apply electric current to described small chamber and make it evaporate, thereby on the ITO substrate, deposit the hole injection layer that thickness is 60 nanometers.Subsequently, N, N '-bis (4-biphenyl)-N , N'-bis(4-biphenyl)-4,4'-diaminobiphenyl is placed in another small chamber of the vacuum deposition equipment, and the NPB is evaporated by applying an electric current to the small chamber, so that in the air Deposition thickness is the hole transport layer of 20 nanometers on the hole injection layer.After forming hole injection layer and hole transport layer, form electroluminescent layer on it, specifically as follows.In vacuum vapor deposition equipment, will serve as substrate The compound 1 of is placed in a small chamber, and the compound D-11 as dopant is placed in another small chamber.These two kinds of materials are evaporated with different rates, so that 4% by weight of doping occurs, thus the thickness is 30 A nanometer electroluminescent layer is vapor deposited on the hole transport layer. Subsequently, 2-(4-(9,10-bis(naphthalene-2-yl)anthracen-2-yl)phenyl)-1-phenyl -1H-benzo[d]imidazole is placed in one chamber, quinolate is lithium-treated in another chamber, and then the two materials are evaporated at the same rate so that 50% by weight doping occurs, thereby in the On the electroluminescence layer, vapor deposition thickness is an electron transport layer of 30 nanometers. Then, vapor deposition thickness is 2 nanometers of Liq (quinoline alloy lithium) as electron injection layer, and then use another vacuum vapor deposition equipment to vapor deposition thickness of 150nm Al cathode to make an OLED.

Each compound used in OLED devices was purified by vacuum sublimation at 10 ⁻⁶ Torr before use.

As a result, it was confirmed that the current flow was 8.8 mA/cm ² at a voltage of 4.4 V, and red light of 900 cd/m ² was emitted.

[Example 2] Preparation of OLED devices using the organic electroluminescent compound of the present invention

An OLED device was fabricated using the same method as in Example 1, except that Compound 2 was used as a host material and D-7 was used as a dopant in the electroluminescent layer.

As a result, it was confirmed that a current of 22.9 mA/cm ² flowed at a voltage of 4.9 V, and red light of 2710 cd/m ² was emitted.

[Example 3] Preparation of OLED devices using the organic electroluminescent compound of the present invention

An OLED device was fabricated using the same method as in Example 1, except that Compound 25 was used as a host material in the electroluminescent layer.

As a result, it was confirmed that a current of 16.9 mA/cm ² flowed at a voltage of 4.8 V, and red light of 1780 cd/m ² was emitted.

[Example 4] Preparation of OLED devices using the organic electroluminescent compound of the present invention

An OLED device was fabricated using the same method as in Example 1, except that Compound 37 was used as a host material and D-7 was used as a dopant in the electroluminescent layer.

As a result, it was confirmed that a current of 41.2 mA/cm ² flowed at a voltage of 5.5 V, and red light of 4800 cd/m ² was emitted.

[Example 5] Preparation of OLED devices using the organic electroluminescent compound of the present invention

An OLED device was fabricated using the same method as in Example 1, except that Compound 128 was used as a host material and D-7 was used as a dopant in the electroluminescent layer.

As a result, it was confirmed that the current flow was 8.7 mA/cm ² at a voltage of 4.2 V, and red light of 900 cd/m ² was emitted.

[Example 6] Preparation of OLED devices using the organic electroluminescent compound of the present invention

An OLED device was fabricated using the same method as in Example 1, except that Compound 139 was used as a host material and D-7 was used as a dopant in the electroluminescent layer.

As a result, it was confirmed that the current flow was 3.2 mA/cm ² at a voltage of 4.1 V, and red light of 400 cd/m ² was emitted.

[Comparative Example 1] Electroluminescent properties of OLED devices using prior art electroluminescent materials

OLED devices were fabricated by the same method as in Example 1, except that 4,4'-N,N'-dicarbazole-biphenyl was used as a host and compound D-11 was used as a dopant by vapor deposition The electroluminescent layer was obtained, and a thickness of 10 nm hole blocking layer.

As a result, it was confirmed that a current flowed at 20.0 mA/cm ² at a voltage of 8.2 V, and red light of 1000 cd/m ² was emitted.

It was confirmed that the organic electroluminescent compound of the present invention exhibits excellent electroluminescent properties compared to conventional materials. A device using the organic electroluminescent compound of the present invention as a host material can exhibit excellent electroluminescent properties and can reduce operating voltage, thereby increasing power efficiency and further improving power consumption.

Although the preferred embodiment of the present invention has been described for illustrative purposes, those skilled in the art will appreciate that various improvements, additions and substitutions are possible without departing from the scope and scope of the present invention as defined by the appended claims. Spirit.

Industrial Applicability

According to the present invention, the organic electroluminescent compound can have high luminous efficiency and excellent material lifetime, and can be used to prepare OLED devices with extremely superior working lifetime.

Claims (10)

1. An organic electroluminescent compound represented by the following chemical formula 1: chemical formula 1

in: Ring A represents a monocyclic or polycyclic aromatic ring; X ₁ and X ₂ independently represent N or CR'; _L represents a single bond, a substituted or unsubstituted (C6-C30) arylene group, a substituted or unsubstituted (C2-C30) heteroarylene group or a substituted or unsubstituted (C3-C30) cycloalkylene group; Ar ₁ represents hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, or substituted or unsubstituted (C2-C30) heteroaryl; Z is independently selected from the following structures:

And when the ring A is a monocyclic aromatic ring, Z is only selected from the following structures:

Y represents -O-, -S-, -C(R ₁₁ R ₁₂ )-, -Si(R ₁₃ R ₁₄ )- or -N(R ₁₅ )-; R ₁ to R ₉ independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C2-C30) Heteroaryl, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl (C1-C30 ) alkyl, substituted or unsubstituted (C6-C30) aryl fused to one or more (C3-C30) cycloalkyl, 5- fused to one or more substituted or unsubstituted aromatic rings To 7-membered heterocycloalkyl, (C3-C30)cycloalkyl fused with one or more substituted or unsubstituted aromatic rings, -NR ₁₆ R ₁₇ , -SiR ₁₈ R ₁₉ R ₂₀ , -SR ₂₁ , -OR ₂₂ , cyano, nitro or hydroxyl; or R ₁ to R ₉ can be substituted or unsubstituted (C3-C30) alkenylene or substituted or unsubstituted (C3- C30) The alkylene group is connected with adjacent substituents to form an alicyclic ring and a monocyclic or polycyclic aromatic ring, and the carbon atoms of the alicyclic ring and a monocyclic or polycyclic aromatic ring can be replaced by one or more carbon atoms selected from N, O and S heteroatom substitution; R' and R ₁₁ to R ₂₂ independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C2 -C30)heteroaryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl or substituted or unsubstituted (C3-C30)cycloalkyl; or they may be substituted or unsubstituted with or without fused rings Unsubstituted (C3-C30) alkenylene or substituted or unsubstituted (C3-C30) alkylene is connected with adjacent substituents to form alicyclic and monocyclic or polycyclic aromatic rings, and the alicyclic and monocyclic The carbon atoms of the ring or polycyclic aromatic ring may be replaced by one or more heteroatoms selected from N, O and S; a, c, e and i independently represent an integer of 1 to 4, and when a, c, e and i are integers greater than or equal to 2, each of R ₁ , R ₃ , R ₅ and R ₉ may be the same or each other different; b, d and g independently represent an integer of 1 to 3, and when b, d and g are integers greater than or equal to 2, each of R ₂ , R ₄ and R ₇ may be the same or different from each other; f represents an integer from 1 to 6, and when f is an integer greater than or equal to 2, each R ₆ can be the same or different from each other; h represents an integer from 1 to 5, and when h is an integer greater than or equal to 2, each _R may be the same or different from each other; and The heteroaryl ring, heteroarylene, heterocycloalkyl, and heteroaryl include one or more heteroatoms selected from B, N, O, S, P(=O), Si, and P. 2. The organic electroluminescent compound according to claim 1, wherein each substituent L ₁ , Ar ₁ , R ₁ to R ₉ , R and R ₁₁ to R ₂₂ are further selected from one or more of the following groups: Multiple substituents: deuterium, halogen, halogen substituted or unsubstituted (C1-C30) alkyl, (C6-C30) aryl, (C6-C30) aryl substituted or unsubstituted (C2-C30) hetero Aryl, 5- to 7-membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl fused to one or more aromatic rings, (C3-C30)cycloalkyl, and one or more aromatic rings Ring-fused (C6-C30) cycloalkyl, R ^a R ^b R ^c Si-, (C2-C30) alkenyl, (C2-C30) alkynyl, cyano, carbazolyl, -NR ^d R ^e , -BR ^f R ^g , -PR ^h R ⁱ , -P(=O)R ^j R ^k , (C6-C30)aryl(C1-C30)alkyl, (C1-C30)alkyl(C6-C30 ) aryl, R ^l T-, R ^m C(=O)-, R ^m C(=O)O-, carboxyl, nitro and hydroxyl, wherein R ^a to R ^l independently represent (C1-C30) alkane Base, (C6-C30) aryl or (C2-C30) heteroaryl; T is S or O; R ^m represents (C1-C30) alkyl, (C1-C30) alkoxy, (C6-C30) Aryl or (C6-C30)aryloxy. 3. The organic electroluminescent compound according to claim 1, wherein the compound is selected from compounds represented by the following chemical formulas 2-9: chemical formula 2 chemical formula 3

chemical formula 4

chemical formula 5

chemical formula 6

chemical formula 7

chemical formula 8

chemical formula 9

In the formula, X ₂ is N or CH; Y is -O-, -S-, -C(R ₁₁ R ₁₂ )- or -N(R ₁₅ )-; L ₁ represents a single bond, substituted or unsubstituted ( C6-C30) arylene, or substituted or unsubstituted (C2-C30) heteroarylene; Ar ₁ represents hydrogen, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6- C30) aryl, or substituted or unsubstituted (C2-C30) heteroaryl; R ₁ to R ₉ independently represent hydrogen, deuterium, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C2-C30) Heteroaryl, NR ₁₆ R ₁₇ or SiR ₁₈ R ₁₉ R ₂₀ ; R ₁₁ , R ₁₂ , R ₁₅ and R ₁₆ to R ₂₀ independently represent hydrogen, deuterium, substituted or unsubstituted (C1- C30) alkyl, substituted or unsubstituted (C6-C30) aryl or substituted or unsubstituted (C2-C30) heteroaryl; or R ₁₆ and R ₁₇ can be substituted or unsubstituted with or without fused rings Substituted (C3-C30) alkenylene groups or substituted or unsubstituted (C3-C30) alkylene groups are connected to form alicyclic or monocyclic or polycyclic aromatic rings, and the alicyclic and monocyclic or polycyclic aromatic rings are Carbon atoms of the ring may be substituted with one or more heteroatoms selected from N, O and S. 4. The organic electroluminescent compound as claimed in claim ₃ , wherein X represents N or CH; Y represents -O-, -S-, -C(R ₁₁ R ₁₂ )- or -N(R ₁₅ )-; _L represents a single bond or is selected from the following structures of arylene:

R ₃₁ and R ₃₂ independently represent methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n- Octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl , phenyl, naphthyl, pyridyl or quinolinyl; Ar ₁ represents hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, 2-Ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, phenyl , biphenyl, terphenyl, naphthyl, 9,9-diphenylfluorenyl, 9,9-dimethylfluorenyl, fluoranthene, pyridyl, dibenzofuranyl, dibenzothienyl Or N-phenylcarbazolyl, and the phenyl, biphenyl, terphenyl, naphthyl and carbazolyl of Ar ₁ can also be substituted by one or more substituents selected from the group: deuterium, fluorine, Methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl , n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, triphenylsilyl, Trimethylsilyl, Dimethylphenylsilyl, Diphenylmethylsilyl, Phenyl, Naphthyl, 9,9-Diphenylfluorenyl, 9,9-Dimethylfluorenyl , phenylpyridyl, carbazolyl, fluoranthenyl, dibenzofuranyl and dibenzothienyl; and R ₁ to R ₉ independently represent hydrogen, deuterium, phenyl, pyridyl, dibenzofuryl, dibenzothienyl, amino or carbazolyl; R ₁₁ , R ₁₂ and R ₁₅ independently represent hydrogen, deuterium , methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethyl Hexyl, n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, phenyl, biphenyl , 9,9-diphenylfluorenyl, 9,9-dimethylfluorenyl, naphthyl, pyridyl, N-phenylcarbazolyl or quinolinyl, and the benzene of R ₁₁ , R ₁₂ and R ₁₅ The group can also be substituted by one or more substituents selected from the group consisting of deuterium, halogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl , isopentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, three Fluoroethyl, perfluoropropyl, perfluorobutyl, phenyl and naphthyl, and R ₁₁ and R ₁₂ may be connected to each other to form a ring. 5. The organic electroluminescent compound as claimed in claim 4, wherein the compound is selected from the following compounds:

6. An organic electroluminescent device comprising the organic electroluminescent compound according to any one of claims 1-5. 7. The organic electroluminescent device according to claim 6, wherein the device comprises a first electrode; a second electrode; one or more organic layers interposed between the first electrode and the second electrode. layer, wherein the organic layer comprises one or more organic electroluminescent compounds and one or more phosphorescent dopants represented by the following Chemical Formula 10, chemical formula 10 M ¹ L ¹⁰¹ L ¹⁰² L ¹⁰³ in: M ¹ is a metal selected from Group 7, Group 8, Group 9, Group 10, Group 11, Group 13, Group 14, Group 15 and Group 16 of the Periodic Table of the Elements, ligand L ¹⁰¹ , L ¹⁰² , and L ¹⁰³ are independently selected from the following structures:

R ₂₀₁ to R ₂₀₃ independently represent hydrogen, deuterium, halogen substituted or unsubstituted (C1-C30) alkyl, (C1-C30) alkyl substituted or unsubstituted (C6-C30) aryl or halogen; R ₂₀₄ to R ₂₁₉ independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) ring Alkyl, substituted or unsubstituted (C2-C30)alkenyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted mono-(C1-C30)alkylamino or substituted or unsubstituted Di-(C1-C30)alkylamino, substituted or unsubstituted mono-(C6-C30)arylamino or substituted or unsubstituted di-(C6-C30)arylamino, SF ₅ , substituted or unsubstituted Tri(C1-C30)alkylsilyl, substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, substituted or unsubstituted tri(C6-C30)aryl Silyl, cyano or halogen; R ₂₂₀ to R ₂₂₃ independently represent hydrogen, deuterium, halogen substituted or unsubstituted (C1-C30) alkyl or (C1-C30) alkyl substituted or unsubstituted (C6-C30) aryl; R ₂₂₄ and R ₂₂₅ independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or halogen, or R ₂₂₄ and R ₂₂₅ can be represented by having or A (C3-C12) alkenylene group or (C3-C12) alkylene group without a fused ring is connected to form an alicyclic ring and a monocyclic or polycyclic aromatic ring; R ₂₂₆ represents substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C2-C30) heteroaryl or halogen; R ₂₂₇ to R ₂₂₉ independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or halogen; and Q means

or

R ₂₃₁ to R ₂₄₂ independently represent hydrogen, deuterium, halogen substituted or unsubstituted (C1-C30) alkyl, (C1-C30) alkoxy, halogen, substituted or unsubstituted (C6-C30) aryl, A cyano group or a substituted or unsubstituted (C3-C30) cycloalkyl group, or they can be connected to adjacent substituents through an alkylene or alkenylene to form a spiro or fused ring, or they can be connected through an alkylene or alkenene The group is connected with _R207 or _R208 to form a saturated or unsaturated condensed ring. 8. The organic electroluminescent device according to claim 7, wherein the phosphorescent dopant is selected from the following compounds:

9. The organic electroluminescent device according to claim 7, wherein the organic layer comprises an electroluminescent layer and a charge generation layer. 10. The organic electroluminescent device according to claim 7, wherein the organic layer further comprises one or more organic electroluminescent layers emitting red light, green light and blue light to emit white light.