WO2012036482A1

WO2012036482A1 - Novel organic electroluminescent compounds and organic electroluminescent device using the same

Info

Publication number: WO2012036482A1
Application number: PCT/KR2011/006810
Authority: WO
Inventors: Hyo Nim Shin; Soo-Jin Hwang; Hee Sook Kim; Seok Keun Yoon; Mi Ja Lee; Nam Kyun Kim; Young Jun Cho; Hyuck Joo Kwon; Kyung Joo Lee; Bong Ok Kim
Original assignee: Rohm and Haas Electronic Materials Korea Ltd
Current assignee: DuPont Specialty Materials Korea Ltd
Priority date: 2010-09-17
Filing date: 2011-09-16
Publication date: 2012-03-22
Anticipated expiration: 2013-03-17
Also published as: CN109020960A; TW201224110A; TWI560258B; KR101477614B1; JP2019050382A; JP2013539750A; JP6672416B2; JP2017031167A; EP2616462A4; CN109020960B; KR20120030009A; CN103221406A; EP2616462A1

Abstract

Provided are novel organic electroluminescent compounds and an organic electroluminescent device using the same. Because the organic electroluminescent compound disclosed herein exhibits good luminous efficiency and an excellent life performance, it may be used to manufacture OLED devices very superior in terms of operating life and which consume less power due to improved power efficiency.

Description

NOVEL ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME

The present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device including the same.

Among display devices, electroluminescent (EL) devices, which are self-emissive display devices, are advantageous in that they provide wide viewing angle, superior contrast and a fast response rate. In 1987, Eastman Kodak first developed an organic EL device using a low-molecular-weight aromatic diamine and aluminum complex as a substance for forming an electroluminescent layer [Appl. Phys. Lett. 51, 913, 1987].

The most important factor to determine luminous efficiency in an organic light-emitting diode (OLED) is electroluminescent material. Though fluorescent materials have been widely used as electroluminescent material up to the present, development of phosphorescent materials is one of the best ways to improve the luminous efficiency theoretically up to four (4) times, in view of electroluminescent mechanism. Up to now, iridium (III) complexes have been widely known as phosphorescent material, including (acac)Ir(btp)₂, Ir(ppy)₃ and Firpic, as the red, green and blue one, respectively. In particular, a lot of phosphorescent materials have been recently investigated in Japan, Europe and America.

At present, CBP is most widely known as a host material for a phosphorescent material. High-efficiency OLEDs using a hole blocking layer comprising BCP, BAlq, etc. are reported. High-performance OLEDs using BAlq derivatives as a host were reported by Pioneer (Japan) and others.

Although these materials provide good electroluminescence characteristics, they are disadvantageous in that degradation may occur during the high-temperature deposition process in vacuum because of low glass transition temperature and poor thermal stability. Since the power efficiency of an OLED is given 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 an OLED. Actually, OLEDs using phosphorescent materials provide much better current efficiency (cd/A) than those using fluorescent materials. However, when the existing materials such as BAlq, CBP, etc. are used as a host of the phosphorescent material, there is no significant advantage in power efficiency (lm/W) over the OLEDs using fluorescent materials because of high driving voltage. Furthermore, the life of an OLED device using such a material is not satisfactory.

On the other hand, International Patent Publication No. WO 2006/049013 discloses a compound for an organic electroluminescent material the backbone of which has a fused bicyclic group. However, this literature does not specifically disclose a compound having both a carbazole backbone substituted with cycloalkyl or heterocycloalkyl that is fused with an aromatic ring and a nitrogen-containing fused bicyclic group.

Therefore, the present invention has been made keeping in mind the problems occurring in the related art and an object of the present invention is to provide organic electroluminescent compounds having the backbone to provide better luminous efficiency and device life with appropriate color coordinate as compared to conventional material.

Another object of the present invention is to provide an organic electroluminescent device having high efficiency and a long life using the organic electroluminescent compound as an electroluminescent material.

Provided are compounds for organic electroluminescent compound represented by Chemical Formula 1 below, and an organic electroluminescent device using the same. With superior luminescence efficiency and excellent life property, the organic electroluminescent compound according to the present invention may be used to manufacture an OLED device having very superior operation life and consuming less power due to improved power efficiency.

[Chemical Formula 1]

wherein,

ring A represents a monocyclic or polycyclic aromatic ring;

X₁ and X₂ independently represent N or CR';

L₁ represents a single bond, substituted or unsubstituted (C6-C30)arylene, substituted or unsubstituted (C2-C30)heteroarylene, or substituted or unsubstituted (C3-C30)cycloalkylene;

Ar₁ 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 following structures;

but Z is selected from following structures only when the ring A is a monocyclic aromatic ring;

Y represents -O-, -S-, -C(R₁₁R₁₂)-, -Si(R₁₃R₁₄)- or -N(R₁₅)-;

R₁ through R₉ 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)ar(C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl fused with one or more (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl fused with substituted or unsubstituted one or more aromatic rings, (C3-C30)cycloalkyl fused with substituted or unsubstituted one or more aromatic rings, -NR₁₆R₁₇, -SiR₁₈R₁₉R₂₀, -SR₂₁, -OR₂₂, cyano, nitro or hydroxyl, or R₁ through R₉ may be linked to an adjacent substituent via substituted or unsubstituted (C3-C30)alkylene or substituted or unsubstituted (C3-C30)alkenylene with or without a fused ring to form an alicyclic ring and a monocyclic or polycyclic aromatic ring, and a carbon atom of the alicyclic ring and the monocyclic or polycyclic aromatic ring may be substituted with one or more heteroatom(s) selected from the group consisting of N, O and S;

R' and R₁₁ through R₂₂ 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 linked to an adjacent substituent via substituted or unsubstituted (C3-C30)alkylene or substituted or unsubstituted (C3-C30)alkenylene with or without a fused ring to form an alicyclic ring and a monocyclic or polycyclic aromatic ring, and a carbon atom of the alicyclic ring and the monocyclic or polycyclic aromatic ring may be substituted with one or more heteroatom(s) selected from the group consisting of 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 an integer of 2 or greater, each of R₁, R₃, R₅ and R₉ may be identical or different from each other;

b, d, and g independently represent an integer of 1 to 3, and when b, d, and g are an integer of 2 or greater, each R₂, R₄ and R₇ may be identical or different from each other;

f represents an integer of 1 to 6, and when f is an integer of 2 or greater, each R₆ may be identical or different from each other;

h represents an integer of 1 to 5, and when h is an integer of 2 or greater, each R₈ may be identical or different from each other; and

the heteroaromatic ring, heteroarylene, heterocycloalkyl and heteroaryl include one or more heteroatom(s) selected from the group consisting of B, N, O, S, P(=O), Si and P.

As described herein, "alkyl", "alkoxy" and other substituents containing the "alkyl" moiety include both linear and branched species, and the "cycloalkyl" includes polycyclic hydrocarbon ring such as substituted or unsubstituted adamantyl or substituted or unsubstituted (C7-C30)bicycloalkyl as well as a monocyclic hydrocarbon ring. As described herein, "aryl" means an organic radical derived from an aromatic hydrocarbon by the removal of one hydrogen atom, and may include a 4- to 7-membered, particularly, 5- or 6-membered, single ring or fused ring, and even further includes a structure where a plurality of aryls are linked by single bond(s). Specific examples thereof include phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc., but are not limited thereto. The naphthyl includes 1-naphthyl and 2-naphthyl, the anthryl includes 1-anthryl, 2-anthryl and 9-anthryl, the phenanthryl includes 1-phenanthryl, 2-phenanthryl, 3-phenanthryl, 4-phenanthryl and 9-phenanthryl, and the naphthacenyl includes 1-naphthacenyl, 2-naphthacenyl and 9-naphthacenyl. The pyrenyl includes 1-pyrenyl, 2-pyrenyl and 4-pyrenyl, and the biphenyl includes 2-biphenyl, 3-biphenyl and 4-biphenyl, 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, and the fluorenyl includes 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl and 9-fluorenyl.

The "heteroaryl" described herein means an aryl group containing 1 to 4 heteroatom(s) selected from the group consisting of B, N, O, S, P(=O), Si and P as aromatic ring backbone atom(s) and the remaining aromatic ring backbone atom is carbon. It may be 5- or 6-membered monocyclic heteroaryl or polycyclic heteroaryl condensed with one or more benzene ring(s), and may be partially saturated. In the present invention, "heteroaryl" includes a structure where one or more heteroaryls are linked by single bonds. The heteroaryl includes a divalent aryl group wherein the heteroatom(s) in the ring may be oxidized or quaternized to form, for example, N- oxide or quaternary salt. Specific examples thereof include monocyclic heteroaryl such as furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, or the like, polycyclic heteroaryl such as benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, isobenzofuranyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenanthridinyl, benzodioxolyl, acridinyl, phenanthrolinyl, phenazinyl, phenothiazinyl, phenoxazinyl or the like, N-oxide thereof (e.g., pyridyl N-oxide, quinolyl N-oxide), quaternary salt thereof, and the like, but are not limited thereto.

The pyrrolyl includes 1-pyrrolyl, 2-pyrrolyl and 3-pyrrolyl; the pyridyl includes 2-pyridyl, 3-pyridyl and 4-pyridyl; the indolyl includes 1-indolyl, 2-indolyl, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl and 7-indolyl; the isoindolyl includes 1-isoindolyl, 2-isoindolyl, 3-isoindolyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl and 7-isoindolyl; the furyl includes 2-furyl and 3-furyl; the benzofuranyl includes 2-benzofuranyl, 3-benzofuranyl, 4-benzofuranyl, 5-benzofuranyl, 6-benzofuranyl and 7-benzofuranyl; the isobenzofuranyl includes 1-isobenzofuranyl, 3-isobenzofuranyl, 4-isobenzofuranyl, 5-isobenzofuranyl, 6-isobenzofuranyl and 7-isobenzofuranyl; the quinolyl includes 3-quinolyl, 4-quinolyl, 5-quinolyl, 6-quinolyl, 7-quinolyl and 8-quinolyl; the isoquinolyl includes 1-isoquinolyl, 3-isoquinolyl, 4-isoquinolyl, 5-isoquinolyl, 6-isoquinolyl, 7-isoquinolyl and 8-isoquinolyl; the quinoxalinyl includes 2-quinoxalinyl, 5-quinoxalinyl and 6-quinoxalinyl; the carbazolyl includes 1-carbazolyl, 2-carbazolyl, 3-carbazolyl, 4-carbazolyl and 9-carbazolyl; the phenanthridinyl includes 1-phenanthridinyl, 2-phenanthridinyl, 3-phenanthridinyl, 4-phenanthridinyl, 6-phenanthridinyl, 7-phenanthridinyl, 8-phenanthridinyl, 9-phenanthridinyl and 10-phenanthridinyl; the acridinyl includes 1-acridinyl, 2-acridinyl, 3-acridinyl, 4-acridinyl and 9-acridinyl; the phenanthrolinyl 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-phenanthrolin-6-yl, 1,8-phenanthrolin-7-yl, 1,8-phenanthrolin-9-yl, 1,8-phenanthrolin-10-yl, 1,9-phenanthrolin-2-yl, 1,9-phenanthrolin-3-yl, 1,9-phenanthrolin-4-yl, 1,9-phenanthrolin-5-yl, 1,9-phenanthrolin-6-yl, 1,9-phenanthrolin-7-yl, 1,9-phenanthrolin-8-yl, 1,9-phenanthrolin-10-yl, 1,10-phenanthrolin-2-yl,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-phenanthrolin-3-yl, 2,8-phenanthrolin-4-yl, 2,8-phenanthrolin-5-yl, 2,8-phenanthrolin-6-yl, 2,8-phenanthrolin-7-yl, 2,8-phenanthrolin-9-yl, 2,8-phenanthrolin-10-yl, 2,7-phenanthrolin-1-yl, 2,7-phenanthrolin-3-yl, 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; the phenazinyl includes 1-phenazinyl and 2-phenazinyl; the phenothiazinyl includes 1-phenothiazinyl, 2-phenothiazinyl, 3-phenothiazinyl, 4-phenothiazinyl and 10-phenothiazinyl; the phenoxazinyl includes 1-phenoxazinyl, 2-phenoxazinyl, 3-phenoxazinyl, 4-phenoxazinyl and 10-phenoxazinyl; the oxazolyl includes 2-oxazolyl, 4-oxazolyl and 5-oxazolyl; the oxadiazolyl includes 2-oxadiazolyl and 5-oxadiazolyl; the furazanyl includes 3-furazanyl; the dibenzofuranyl includes 1-dibenzofuranyl, 2-dibenzofuranyl, 3-dibenzofuranyl and 4-dibenzofuranyl; and the dibenzothiophenyl includes 1-dibenzothiophenyl, 2-dibenzothiophenyl, 3-dibenzothiophenyl and 4-dibenzothiophenyl.

As described herein, the term "(C1-C30)alkyl" 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 substitutent(s))" used herein, "with substituted(with substitutent(s))" means that the unsubstituted substituent is further substituted with substituent(s). The each substituent of the L₁, Ar₁, R₁ through R₉, R and R₁₁ through R₂₂ may be further substituted by one or more substituent(s) 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, 5- to 7-membered heterocycloalkyl fused with one or more aromatic rings, (C3-C30)cycloalkyl, (C6-C30)cycloalkyl fused with one or more aromatic rings, R^aR^bR^cSi-, (C2-C30)alkenyl, (C2-C30)alkynyl, cyano, carbazolyl, -NR^dR^e, -BR^fR^g, -PR^hRⁱ, -P(=O)R^jR^k, (C6-C30)ar(C1-C30)alkyl, (C1-C30)alkyl(C6-C30)aryl, R^lT-, R^mC(=O)-, R^mC(=O)O-, carboxyl, nitro and hydroxyl, wherein R^a through R^l independently represent (C1-C30)alkyl, (C6-C30)aryl or (C2-C30)heteroaryl; T is S or O; and R^m represents (C1-C30)alkyl, (C1-C30)alkoxy, (C6-C30)aryl, or (C6-C30)aryloxy.

The organic electroluminescent compound may be represented by Chemical Formulas 2 to 9 below.

[Chemical Formula 2]

[Chemical Formula 3]

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

[Chemical Formula 7]

[Chemical Formula 8]

[Chemical Formula 9]

wherein, X₂ is N or CH; Y is -O-, -S-, -C(R₁₁R₁₂)- or -N(R₁₅)-; L₁ represents a single bond, substituted or unsubstituted (C6-C30)arylene, or substituted or unsubstituted (C2-C30)heteroarylene; Ar₁ represents hydrogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (C2-C30)heteroaryl; R₁ through R₉ independently represent hydrogen, deuterium, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-C30)heteroaryl, NR₁₆R₁₇ or SiR₁₈R₁₉R₂₀; R₁₁, R₁₂, R₁₅ and R₁₆ through R₂₀ independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl or substituted or unsubstituted (C2-C30)heteroaryl, or R₁₆ and R₁₇ may be linked to via substituted or unsubstituted (C3-C30)alkylene or substituted or unsubstituted (C3-C30)alkenylene with or without a fused ring to form an alicyclic ring or a monocyclic or polycyclic aromatic ring, and the carbon atom of the alicyclic ring and the monocyclic or polycyclic aromatic ring may be substituted with one or more heteroatom(s) selected from the group consisting of N, O and S.

To be specific, X₂ represents N or CH; Y represents -O-, -S-, -C(R₁₁R₁₂)- or -N(R₁₅)-;

L₁ represents a single bond or arylene selected from the following structures:

;

R₃₁ and R₃₂ independently represent methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, phenyl, naphthyl, pyridyl or quinolyl;

Ar₁ represents hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, 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, fluoranthenyl, pyridyl, dibenzofuranyl, dibenzothiophenyl or N-phenylcarbazolyl, and the phenyl, biphenyl, terphenyl, naphthyl and carbazolyl of Ar₁ may be further substituted with one or more substituents selected from the group consisting of deuterium, fluorine, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, 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 dibenzothiophenyl; and

R₁ through R₉ independently represent hydrogen, deuterium, phenyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, amino or carbazolyl; R₁₁, R₁₂ and R₁₅ independently represent hydrogen, deuterium, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, phenyl, biphenyl, 9,9-diphenylfluorenyl, 9,9-dimethylfluorenyl, naphthyl, pyridyl, N-phenylcarbazolyl or quinolyl, and the phenyl of R₁₁, R₁₂ and R₁₅ may be further substituted with one or more substituents selected from the group consisting of deuterium, halogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, phenyl and naphthyl, and R₁₁ and R₁₂ may be linked to each other to form a ring.

The organic electroluminescent compound according to the present invention may be exemplified by the following compounds, which are not intended to limit the present invention.

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

[Scheme 1]

In Scheme 1, ring A, X₁, X₂, L₁, Ar₁, R₁, R₂, R₃, a, b, c and Z are the same as defined in Chemical Formula 1; and Hal represents halogen.

Provided is an organic electroluminescent device, which comprises a first electrode; a second electrode; and one or more organic layer(s) interposed between the first electrode and the second electrode, wherein the organic layer comprises one or more organic electroluminescent compounds represented by Chemical Formula 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 dopant(s) is included. The phosphorescent dopant applied to the organic electroluminescent device according to the present invention is not specifically limited, but may be selected from among compounds represented by Chemical Formula 10 below.

[Chemical Formula 10]

M¹L¹⁰¹L¹⁰²L¹⁰³

wherein,

M¹ is selected from the group consisting of metals of Groups 7, 8, 9, 10, 11, 13, 14, 15 and 16 of the Periodic table, and ligands L¹⁰¹, L¹⁰² and L¹⁰³ are independently selected from the following structures:

R₂₀₁ through R₂₀₃ independently represent hydrogen, deuterium, halogen-substituted or unsubstituted (C1-C30)alkyl, (C1-C30)alkyl-substituted or unsubstituted (C6-C30)aryl or halogen;

R₂₀₄ through R₂₁₉ independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C1-C30)alkoxy, substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted (C2-C30)alkenyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted mono- or di-(C1-C30)alkylamino, substituted or unsubstituted mono- or di-(C6-C30)arylamino, SF₅, substituted or unsubstituted tri(C1-C30)alkylsilyl, substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, substituted or unsubstituted tri(C6-C30)arylsilyl, cyano or halogen;

R₂₂₀ through R₂₂₃ independently represent hydrogen, deuterium, halogen-substituted or unsubstituted (C1-C30)alkyl, or (C1-C30)alkyl-substituted or unsubstituted (C6-C30)aryl;

R₂₂₄ and R₂₂₅ independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl or halogen, or R₂₂₄ and R₂₂₅ may be linked via (C3-C12)alkylene or (C3-C12)alkenylene with or without a fused ring to form an alicyclic ring and a monocyclic or polycyclic aromatic ring;

R₂₂₆ represents substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-C30)heteroaryl, or halogen;

R₂₂₇ through R₂₂₉ independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, or halogen; and

Q represents

,

or

;

R₂₃₁ through R₂₄₂ independently represent hydrogen, deuterium, halogen-substituted or unsubstituted (C1-C30)alkyl, (C1-C30)alkoxy, halogen, substituted or unsubstituted (C6-C30)aryl, cyano or substituted or unsubstituted (C3-C30)cycloalkyl, or they may be linked to an adjacent substituent via alkylene or alkenylene to form a spiro ring or a fused ring, or may be linked to R₂₀₇ or R₂₀₈ via alkylene or alkenylene to form a saturated or unsaturated fused ring.

The dopant compound of Chemical Formula 10 may be exemplified by the following compounds, but is not limited thereto.

In the organic electronic device of the present invention, the organic layer may further include, in addition to the organic electroluminescent compound represented by Chemical Formula 1, one or more compound(s) selected from the group consisting of arylamine compounds and styrylarylamine compounds, at the same time. The arylamine compounds or styrylarylamine compounds are exemplified in Korean Patent Application No. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but are not limited thereto.

Further, in the organic electroluminescent device of the present invention, the organic layer may further include, in addition to the organic electroluminescent compound represented by Chemical Formula 1, one or more metal(s) selected from the group consisting of organic metals of Group 1, Group 2, 4th period and 5th period transition metals, lanthanide metals and d-transition elements or complex compound(s). The organic layer may include an electroluminescent layer and a charge generating layer.

Further, the organic layer may include, in addition to the organic electroluminescent compound of Chemical Formula 1, one or more organic electroluminescent layer(s) emitting blue, green or red light at the same time in order to embody a white-emitting organic electroluminescent device. The compounds emitting blue, green or red light may be exemplified by the 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 electroluminescent device of the present invention, a layer (hereinafter referred to as "surface layer") selected from a chalcogenide layer, a metal halide layer and a metal oxide layer may be placed on the inner surface of one or both electrode(s) among the pair of electrodes. More specifically, a metal chalcogenide (including oxide) layer of silicon or aluminum may be placed on the anode surface of the electroluminescent medium layer, and a metal halide layer or metal oxide layer may be placed on the cathode surface of the electroluminescent medium layer. Operation stability may be attained therefrom. The chalcogenide may be, for example, SiO_x(1 ≤ x ≤ 2), AlO_x(1 ≤ x ≤ 1.5), SiON, SiAlON, etc. The metal halide may be, for example, LiF, MgF₂, CaF₂, a rare earth metal fluoride, etc. The metal oxide may be, for example, Cs₂O, Li₂O, MgO, SrO, BaO, CaO, etc.

In the organic electroluminescent device according to the present invention, it is also preferable to arrange on at least one surface of the pair of electrodes thus manufactured 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. In that case, since the electron transport compound is reduced to an anion, injection and transport of electrons from the mixed region to an electroluminescent medium are facilitated. In addition, since the hole transport compound is oxidized to a cation, injection and transport of holes from the mixed region to an electroluminescent medium are facilitated. Preferable oxidative dopants include various Lewis acids and acceptor compounds. Preferable reductive dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. Further, a white-emitting electroluminescent device having two or more electroluminescent layers may be manufactured by employing a reductive dopant layer as a charge generating layer.

According to the present invention, an organic electroluminescent compound can exhibit high luminous efficiency and can have excellent material life, and can be used to manufacture OLED devices having very superior operating life.

Hereinafter, the present invention is further described by taking representative compounds of the present invention as examples of the organic electroluminescent compounds according to the invention, a preparing method thereof, and electroluminescent properties of the devices. But, those examples are provided only for the sake of illustrating the embodiments, and are not intended to limit the scope of the invention.

[Preparation Example 1] Preparation of Compound 1

Preparation of Compound 1-1

2,4-dichloroquinazoline (8.1g, 40.6mmol), phenylboronic acid (5.0g, 40.6mmol), toluene 200mL, ethanol 50mL and water 50mL were mixed and then Pd(PPh₃)₄ (1.9g, 1.64mmol) and K₂CO₃ (12.9g, 122mmol) were added. The mixture was stirred at 120℃ for 5 hours and cooled to room temperature, after which the reaction was terminated with aqueous ammonium chloride 200mL. The mixture was extracted with ethyl acetate (EA) 500mL, and then washed with distilled water 50mL. The obtained organic layer was dried with anhydrous MgSO₄, and the organic solvent was removed under reduced pressure. Subsequently, silica gel filtration and recrystallization were performed, yielding Compound 1-1 (6.6g, 68%).

Preparation of Compound 1-2

7H-benzo[c]carbazole (8.9g, 41.10 mmol), Compound 1-1 (11.9g, 49.32mmol), Pd(OAc)₂ (0.46g, NaOt-bu 7.9g, 82.20mmol), toluene 100mL, and P(t-bu)₃ (2mL, 4.11mmol, 50% in toluene) were stirred under reflux. 10 hours later, the mixture was cooled to room temperature and distilled water was added. The resultant mixture was extracted with EA, dried with anhydrous MgSO₄, and further dried under reduced pressure. Subsequently column separation was performed, yielding Compound 1-2 (14.5g, 84%).

Preparation of Compound 1-3

Compound 1-2 (14.3g, 33.98mmol) was placed into a one-neck flask, and a vacuum atmosphere was created and then the flask was filled with argon. THF 500mL was added and the mixture was stirred at 0℃ for 10 minutes. NBS (7.35g, 40.78mmol) 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 MgSO₄, the solvent was removed using a rotary evaporator, and then column chromatography using hexane and EA as developers was performed, yielding Compound 1-3 (14.6g, 85%).

Preparation of Compound 1-4

Compound 1-3 (13.2g, 26.30mmol) was placed into a one-neck flask, and a vacuum atmosphere was created and then the flask was filled with argon. THF 500mL was added and the mixture was stirred at -78℃ for 10 minutes. n-BuLi (2.5M in hexane) (15.8mL, 39.45mmol) was added in droplets and the mixture was stirred at -78℃ for 1 hour 30 minutes. Trimethylborate (4.85mL, 39.45mmol) was added at -78℃. The mixture was stirred at -78℃ for 30 minutes and then at room temperature for 4 hours. The reaction was terminated, and the resultant mixture was extracted with distilled water and EA. The organic layer was dried with anhydrous MgSO₄, the solvent was removed using a rotary evaporator, and then column chromatography was conducted using hexane and EA as developers, yielding Compound 1-4 (6.9g, 18.05mmol, 65%).

Preparation of Compound 1

Compound 1-4 (8.1g, 17.4mmol), 3-bromo-9-phenyl-9H-carbazole (6.7g, 20.88mmol), Pd(PPh₃)₄ (0.8g, 0.7mmol), 2M K₂CO₃ aqueous solution 20mL, toluene 100mL, and ethanol 50mL were stirred under reflux for 12 hours. The mixture was washed with distilled water and extracted with EA. Drying with anhydrous MgSO₄, distillation under reduced pressure and column separation were performed, yielding Compound 1 (6.8g, 10.3mmol, 58%).

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

[Preparation Example 2] Preparation of Compound 2

Preparation of Compound 2-1

2,4-dichloroquinazoline (8.1g, 40.6mmol), biphenyl phenylboronic acid (8.0g, 40.6mmol), toluene 200mL, ethanol 50mL and water 50mL were mixed and Pd(PPh₃)₄ (1.9g, 1.64mmol) and K₂CO₃ (12.9g, 122mmol) were added. The mixture was stirred at 120℃ for 5 hours and cooled to room temperature, and the reaction was terminated with aqueous ammonium chloride 200mL. The mixture was extracted with EA 500mL, and washed with distilled water 50mL. The obtained organic layer was dried with anhydrous MgSO₄, and the organic solvent was removed under reduced pressure. Subsequently, silica gel filtration and then recrystallization were performed, yielding Compound 2-1 (8.2g, 25.9mmol, 64%).

Preparation of Compound 2-2

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

Preparation of Compound 2-3

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

Preparation of Compound 2-4

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

Preparation of Compound 2

Compound 2 (2.8g, 4.6mmol, 51%) was prepared from Compound 2-4 (4.0g, 7.4mmol) and 3-bromo-9-phenyl-9H-carbazole (6.7g, 20.88mmol) by the same method as in the preparation of Compound 1.

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

[Preparation Example 3] Preparation of Compound 7

Preparation of Compound 7

Compound 7 (2.8g, 4.6mmol, 51%) was prepared from Compound 2-4 (4.0g, 7.4mmol) and 2-bromodibenzo[b,d]thiophene (5.5g, 20.88mmol) by the same method as in the preparation of Compound 1.

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

[Preparation Example 4] Preparation of Compound 12

Preparation of Compound 12

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

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

[Preparation Example 5] Preparation of Compound 16

Preparation of Compound 16

Compound 16 (7.6g, 11.0mmol, 61%) was prepared from Compound 2-4 (9.8g, 18.05mmol) and 2-bromo-9,9-dimethyl-9H-fluorene (5.7g, 20.88mmol) by the same method as in the preparation of Compound 1.

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

[Preparation Example 6] Preparation of Compound 25

Preparation of Compound 6-1

7H-benzo[c]carbazole (20g, 92mmol) and 1-bromo-4-iodobenzene (43.5g, 184mmol) were dissolved in toluene 500mL, and CuI (8.8g, 46 mmol), diaminoethane (6.2mL, 92mmol) and K₃PO₄ (8.7g, 276mmol) were added, and the mixture was refluxed for 30 hours. The mixture was cooled to room temperature, and the reaction was terminated with 2.0M aqueous HCl 50mL. The resultant mixture was extracted with EA 1L and then washed with distilled water 200mL. The obtained organic layer was dried with anhydrous MgSO₄, and the organic solvent was removed under reduced pressure. Silica gel column chromatography was then conducted, yielding Compound 6-1 (19g, 56%).

Preparation of Compound 6-2

Compound 6-1 (19g, 51mmol) was dissolved in THF 250mL and then cooled to -78℃, and n-BuLi(2.5 M in hexane) (24.5mL) was added at -78℃. The mixture was stirred at -78℃ for 1 hour, and B(OMe)₃ (8.5mL) was added, after which the mixture was stirred for 2 hours, and the reaction was terminated with aqueous ammonium chloride 100mL. The resultant mixture was extracted with EA 500mL and then washed with distilled water 100mL. The obtained organic layer was dried with anhydrous MgSO₄, and the organic solvent was removed under reduced pressure. Recrystallization was then conducted, yielding Compound 6-2 (14g, 81%).

Preparation of Compound 6-3

Compound 1-1 (3.3g, 13.7mmol) and Compound 6-2 (5.5g, 16.4mmol) were mixed with toluene 100mL, ethanol 20mL and water 20mL, and Pd(PPh₃)₄ (1.6g, 1.4mmol) and K₂CO₃ (5.7g, 41.1mmol) were added. The mixture was stirred at 120℃ for 5 hours and cooled to room temperature, and the reaction was terminated with aqueous ammonium chloride 20mL. The mixture was extracted with EA 250mL and then washed with distilled water 30mL. The obtained organic layer was dried with anhydrous MgSO₄, and the organic solvent was removed under reduced pressure. Silica gel filtration and recrystallization were then performed, yielding Compound 6-3 (4.9g, 9.8mmol, 72%).

Preparation of Compound 6-4

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

Preparation of Compound 6-5

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

Preparation of Compound 25

Compound 25 (7.6g, 10.3mmol, 57%) was prepared from Compound 6-5 (9.8g, 18.05mmol) and 3-bromo-9-phenyl-9H-carbazole (6.7g, 20.88mmol) by the same method as in the preparation of Compound 1.

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

[Preparation Example 7] Preparation of Compound 37

Preparation of Compound 7-1

7H-benzo[c]carbazole (50g, 0.23mol) was dissolved in DMF 1.4L, and NBS (41g, 0.23mol) was added, after which the mixture was stirred at room temperature for 24 hours. After termination of the reaction, the resultant mixture was extracted with EA and the organic layer was distilled under reduced pressure. Silica column separation was then performed, yielding Compound 7-1 (53.2g, 78%).

Preparation of Compound 7-2

Compound 7-1 (30g, 0.10mol), iodobenzene (22.6mL, 0.20mmol), CuI (9.6g, 0.05mol), Cs₂CO₃ (99g, 0.030mol), and EDA (13.7mL, 0.20mol) were added to toluene 500mL and stirred under reflux for 24 hours. The mixture was extracted with EA, distilled under reduced pressure and column separated using MC/Hex, yielding Compound 7-2 (20g, 53%).

Preparation of Compound 7-3

Compound 7-2 (18g, 48.4mmol) was dissolved in THF 250mL, and 2.5M n-BuLi(in Hexane) (23.2mL, 58.0mmol) was added at -78℃ after which the mixture was stirred for 1 hour. B(Oi-Pr)₃ (16.7mL, 72.5mmol) was slowly added and the solution was stirred for 2 hours. 2M HCl was added and the mixture was quenched and extracted with distilled water and EA. Recrystallization using MC and Hex was then conducted, yielding Compound 7-3 (13.6g. 83.4%).

Preparation of Compound 7-4

Compound 7-3 (13.6g, 40.3mmol), bromocarbazole (9.9g, 40.3mmol), Pd(PPh₃)₄ (2.3g, 2.0mmol), K₂CO₃ (13.4g, 96.7mmol), toluene 200mL and distilled water 48mL were mixed and then stirred at 90℃ for 2 hours. The organic layer was distilled under reduced pressure and triturated with MeOH. The obtained solid was dissolved in MC, silica filtered and triturated with MC and hexane, yielding Compound 7-4 (15g, 81%).

Preparation of Compound 37

Compound 1-1 (4g, 16.6mmol) and Compound 7-4 (7.6g, 16.6mmol) were suspended in DMF 80mL, and 60% NaH (1.1g, 28.2mmol) was added at room temperature and the mixture was stirred for 12 hours. Distilled water 1L was added and the mixture was filtered under reduced pressure. The obtained solid was triturated with MeOH/EA, dissolved in MC, silica filtered and then triturated with MC/n-Hexane, yielding Compound 37 (2.4g, 21.8%).

MS/FAB found 662.78, calculated 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(PPh₃)₄ (2 g, 1.7mmol), K₂CO₃ (34 g, 321 mmol), toluene 60mL, EtOH 12mL and purified water 12mL were mixed and then stirred at 120℃ for 15 hours. After termination of the reaction, the resultant mixture was allowed to stand and the water layer was removed, after which the organic layer was concentrated. Silica column purification was then carried out, yielding Compound 8-1 (10.2 g, 78%).

Preparation of Compound 116

Compound 8-1 (3g, 7.8mmol) and Compound 2-1 (2.1g, 7.8mmol) were suspended in DMF 30mL, and 60% NaH (376mg, 9.4 mmol) was added at room temperature, and the mixture was stirred for 12 hours. Purified water 500mL was added and the mixture was filtered under reduced pressure. The obtained solid was triturated with MeOH/EA, DMF and then EA/THF in that order. The resultant product was dissolved in MC, silica filtered, and triturated with MeOH/EA, yielding Compound 116 (2.4g, 46%).

MS/FAB found 663.76, calculated 663.23

[Preparation Example 9] Preparation of Compound 128

Preparation of Compound 9-1

3-bromo-9H-carbazole (5g, 20.32mmol), dibenzo[b,d]furan-4-ylboronic acid (4.7g, 22.35mmol), K₂CO₃ (7g, 50.79mmol), Pd(PPh₃)₄ (1.17g, 1.01mmol), toluene 100mL, EtOH 25mL and purified water 25mL were mixed and then stirred at 100℃ for 3 hours. After termination of the reaction, the mixture was cooled to room temperature and allowed to stand and the water layer was removed. The organic layer was concentrated and then purified using a silica column, yielding Compound 9-1 (4.3g, 64%).

Preparation of Compound 128

Compound 2-1 (3g, 8.99mmol) and Compound 9-1 (3.14g, 9.89mmol) were suspended in anhydrous DMF 50mL, and 60% NaH (0.54g, 13.5mmol) was added at room temperature. The mixture was stirred at room temperature for 5 hours. After termination of the reaction, MeOH 3mL was added in droplets and the solid was obtained due to excessive MeOH, and silica column purification, suspending with EA, filtration and then crystallization with THF were performed, yielding Compound 128 (1g, 18%).

MS/FAB found 613.70, calculated 613.22

[Example 1] Manufacture of OLED device using the organic electroluminescent compound according to the present invention

An OLED device was manufactured using the compound for organic electronic materials according to the present invention. First, a transparent electrode ITO thin film (15 Ω/□) obtained from a glass for OLED (produced by Samsung Corning) was subjected to ultrasonic washing with trichloroethylene, acetone, ethanol and distilled water, sequentially, and stored in isopropanol before use. Then, an ITO substrate was equipped in a substrate folder of a vacuum deposition apparatus, and N¹,N^1'([1,1'-biphenyl]-4,4'-diyl)bis(N¹-(naphthalen-1-yl)-N⁴,N⁴-diphenylbenzene-1,4-diamine was placed in a cell of the vacuum deposition apparatus, which was then evacuated up to 10^-6 torr of vacuum in the chamber. Then, electric current was applied to the cell to evaporate it, thereby depositing a hole injection layer having a thickness of 60 nm on the ITO substrate. Subsequently, N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl was placed in another cell of the vacuum deposition apparatus, and electric current was applied to the cell to evaporate NPB, thereby depositing a hole transport layer having a thickness of 20 nm on the hole injection layer. After forming the hole injection layer and the hole transport layer, an electroluminescent layer was formed thereon as follows. Compound 1 as a host was placed in a cell, and Compound D-11 as a dopant was placed in another cell, within a vacuum vapor deposition apparatus. The two materials were evaporated at different rates such that 4 wt% doping taken place, and thereby the electroluminescent layer having a thickness of 30 nm was vapor-deposited on the hole transport layer. Subsequently, 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was placed in a cell and lithium quinolate was placed in another cell, after which the two materials were evaporated at the same rate such that 50 wt% doping taken place, and thereby an electron transport layer was vapor-deposited to a thickness of 30 nm on the electroluminescent layer. Subsequently, Liq (lithium quinolate) was vapor-deposited to a thickness of 2 nm as an electron injection layer, after which an Al cathode was vapor-deposited to a thickness of 150 nm using another vacuum vapor deposition apparatus to manufacture an OLED.

Each compound used in the OLED device was purified by vacuum sublimation at 10^-6 torr before use.

As a result, it was confirmed that current of 8.8 mA/cm² flows at voltage of 4.4 V and a red light of 900 cd/m² was emitted.

[Example 2] Manufacture of OLED device using the organic electroluminescent compound according to the present invention

An OLED device was manufactured by the same method as in Example 1, with the exception that Compound 2 was used as the host material, and D-7 was used as a dopant in the electroluminescent layer.

As a result, it was confirmed that current of 22.9 mA/cm² flows at voltage of 4.9 V and a red light of 2710 cd/m² was emitted.

[Example 3] Manufacture of OLED device using the organic electroluminescent compound according to the present invention

An OLED device was manufactured by the same method as in Example 1, with the exception that Compound 25 was used as the host material in the electroluminescent layer.

As a result, it was confirmed that current of 16.9 mA/cm² flows at voltage of 4.8 V and a red light of 1780 cd/m² was emitted.

[Example 4] Manufacture of OLED device using the organic electroluminescent compound according to the present invention

An OLED device was manufactured by the same method as in Example 1, with the exception that Compound 37 was used as the host material, and D-7 was used as a dopant in the electroluminescent layer.

As a result, it was confirmed that current of 41.2 mA/cm² flows at voltage of 5.5 V and a red light of 4800 cd/m² was emitted.

[Example 5] Manufacture of OLED device using the organic electroluminescent compound according to the present invention

An OLED device was manufactured by the same method as in Example 1, with the exception that Compound 128 was used as the host material, and D-7 was used as a dopant in the electroluminescent layer.

As a result, it was confirmed that current of 8.7 mA/cm² flows at voltage of 4.2 V and a red light of 900 cd/m² was emitted.

[Example 6] Manufacture of OLED device using the organic electroluminescent compound according to the present invention

An OLED device was manufactured by the same method as in Example 1, with the exception that Compound 139 was used as the host material, and D-7 was used as a dopant in the electroluminescent layer.

As a result, it was confirmed that current of 3.2 mA/cm² flows at voltage of 4.1 V and a red light of 400 cd/m² was emitted.

[Comparative Example 1] Electroluminescent properties of OLED device using an electroluminescent material of the prior art.

An OLED device was manufactured by the same method as in Example 1, with the exception that an electroluminescent layer was vapor-deposited using 4,4'-N,N'-dicarbazole-biphenyl used as a host and Compound D-11 as a dopant, and a hole blocking layer was vapor-deposited to a thickness of 10 nm using aluminum(III)bis(2-methyl-8-quinolinato)4-phenylphenolate between the electroluminescent layer and the electron transport layer.

As a result, it was confirmed that current of 20.0 mA/cm² flows at voltage of 8.2 V and a red light of 1000 cd/m² was emitted.

It was confirmed that the organic electroluminescent compounds developed in the present invention showed superior electroluminescent properties compared to the conventional material. The devices using the organic electroluminescent compounds of the present invention as a host material can exhibit superior electroluminescent properties and can reduce operating voltage to thus increase power efficiency, thereby improving power consumption.

Although the preferred embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that various modifications, additions, and substitutions are possible, without departing from the scope and spirit of the invention as disclosed in the accompanying claims.

Claims

An organic electroluminescent compound represented by Chemical Formula 1 below.

[Chemical Formula 1]

wherein,

ring A represents a monocyclic or polycyclic aromatic ring;

X₁ and X₂ independently represent N or CR';

L₁ represents a single bond, substituted or unsubstituted (C6-C30)arylene, substituted or unsubstituted (C2-C30)heteroarylene, or substituted or unsubstituted (C3-C30)cycloalkylene;

Ar₁ 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 following structures;

but Z is selected from following structures only when the ring A is a monocyclic aromatic ring;

Y represents -O-, -S-, -C(R₁₁R₁₂)-, -Si(R₁₃R₁₄)- or -N(R₁₅)-;

R₁ through R₉ 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)ar(C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl fused with one or more (C3-C30)cycloalkyl, 5- to 7-membered heterocycloalkyl fused with substituted or unsubstituted one or more aromatic rings, (C3-C30)cycloalkyl fused with substituted or unsubstituted one or more aromatic rings, -NR₁₆R₁₇, -SiR₁₈R₁₉R₂₀, -SR₂₁, -OR₂₂, cyano, nitro or hydroxyl, or R₁ through R₉ may be linked to an adjacent substituent via substituted or unsubstituted (C3-C30)alkylene or substituted or unsubstituted (C3-C30)alkenylene with or without a fused ring to form an alicyclic ring and a monocyclic or polycyclic aromatic ring, and a carbon atom of the alicyclic ring and the monocyclic or polycyclic aromatic ring may be substituted with one or more heteroatom(s) selected from the group consisting of N, O and S;

R' and R₁₁ through R₂₂ 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 linked to an adjacent substituent via substituted or unsubstituted (C3-C30)alkylene or substituted or unsubstituted (C3-C30)alkenylene with or without a fused ring to form an alicyclic ring and a monocyclic or polycyclic aromatic ring, and a carbon atom of the alicyclic ring and the monocyclic or polycyclic aromatic ring may be substituted with one or more heteroatom(s) selected from the group consisting of 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 an integer of 2 or greater, each of R₁, R₃, R₅ and R₉ may be identical or different from each other;

b, d, and g independently represent an integer of 1 to 3, and when b, d, and g are an integer of 2 or greater, each R₂, R₄ and R₇ may be identical or different from each other;

f represents an integer of 1 to 6, and when f is an integer of 2 or greater, each R₆ may be identical or different from each other;

h represents an integer of 1 to 5, and when h is an integer of 2 or greater, each R₈ may be identical or different from each other; and

the heteroaromatic ring, heteroarylene, heterocycloalkyl and heteroaryl include one or more heteroatom(s) selected from the group consisting of B, N, O, S, P(=O), Si and P.
The organic electroluminescent compound of claim 1, wherein each substituent of the L₁, Ar₁, R₁ through R₉, R and R₁₁ through R₂₂ is further substituted by one or more substituent(s) 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, 5- to 7-membered heterocycloalkyl fused with one or more aromatic rings, (C3-C30)cycloalkyl, (C6-C30)cycloalkyl fused with one or more aromatic rings, R^aR^bR^cSi-, (C2-C30)alkenyl, (C2-C30)alkynyl, cyano, carbazolyl, -NR^dR^e, -BR^fR^g, -PR^hRⁱ, -P(=O)R^jR^k, (C6-C30)ar(C1-C30)alkyl, (C1-C30)alkyl(C6-C30)aryl, R^lT-, R^mC(=O)-, R^mC(=O)O-, carboxyl, nitro and hydroxyl, wherein R^a through R^l independently represent (C1-C30)alkyl, (C6-C30)aryl or (C2-C30)heteroaryl; T is S or O; and R^m represents (C1-C30)alkyl, (C1-C30)alkoxy, (C6-C30)aryl, or (C6-C30)aryloxy.
The organic electroluminescent compound of claim 1, which is selected from the group consisting of compounds represented by Chemical Formulas 2 to 9 below.

[Chemical Formula 2]

[Chemical Formula 3]

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

[Chemical Formula 7]

[Chemical Formula 8]

[Chemical Formula 9]

wherein, X₂ is N or CH; Y is -O-, -S-, -C(R₁₁R₁₂)- or -N(R₁₅)-; L₁ represents a single bond, substituted or unsubstituted (C6-C30)arylene, or substituted or unsubstituted (C2-C30)heteroarylene; Ar₁ represents hydrogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (C2-C30)heteroaryl; R₁ through R₉ independently represent hydrogen, deuterium, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-C30)heteroaryl, NR₁₆R₁₇ or SiR₁₈R₁₉R₂₀; R₁₁, R₁₂, R₁₅ and R₁₆ through R₂₀ independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl or substituted or unsubstituted (C2-C30)heteroaryl, or R₁₆ and R₁₇ may be linked to via substituted or unsubstituted (C3-C30)alkylene or substituted or unsubstituted (C3-C30)alkenylene with or without a fused ring to form an alicyclic ring or a monocyclic or polycyclic aromatic ring, and the carbon atom of the alicyclic ring and the monocyclic or polycyclic aromatic ring may be substituted with one or more heteroatom(s) selected from the group consisting of N, O and S.
The organic electroluminescent compound of claim 3, wherein X₂ represents N or CH; Y represents -O-, -S-, -C(R₁₁R₁₂)- or -N(R₁₅)-;

L₁ represents a single bond or arylene selected from the following structures:

;

R₃₁ and R₃₂ independently represent methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, phenyl, naphthyl, pyridyl or quinolyl;

Ar₁ represents hydrogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, 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, fluoranthenyl, pyridyl, dibenzofuranyl, dibenzothiophenyl or N-phenylcarbazolyl, and the phenyl, biphenyl, terphenyl, naphthyl and carbazolyl of Ar₁ may be further substituted with one or more substituents selected from the group consisting of deuterium, fluorine, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, 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 dibenzothiophenyl; and

R₁ through R₉ independently represent hydrogen, deuterium, phenyl, pyridyl, dibenzofuranyl, dibenzothiophenyl, amino or carbazolyl; R₁₁, R₁₂ and R₁₅ independently represent hydrogen, deuterium, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, phenyl, biphenyl, 9,9-diphenylfluorenyl, 9,9-dimethylfluorenyl, naphthyl, pyridyl, N-phenylcarbazolyl or quinolyl, and the phenyl of R₁₁, R₁₂ and R₁₅ may be further substituted with one or more substituents selected from the group consisting of deuterium, halogen, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl, n-heptyl, n-octyl, 2-ethylhexyl, n-nonyl, decyl, dodecyl, hexadecyl, trifluoromethyl, perfluoroethyl, trifluoroethyl, perfluoropropyl, perfluorobutyl, phenyl and naphthyl, and R₁₁ and R₁₂ may be linked to each other to form a ring.
The organic electroluminescent compound of claim 4, which is selected from following compounds.
An organic electroluminescent device comprising the organic electroluminescent compound of any one of claims 1 to 5.
The organic electroluminescent device of claim 6, which comprises 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 one or more organic electroluminescent compounds and one or more phosphorescent dopants represented by Chemical Formula 10 below.

[Chemical Formula 10]

M¹L¹⁰¹L¹⁰²L¹⁰³

wherein,

M¹ is selected from the group consisting of metals of Groups 7, 8, 9, 10, 11, 13, 14, 15 and 16 of the Periodic table, and ligands L¹⁰¹, L¹⁰² and L¹⁰³ are independently selected from the following structures:

R₂₀₁ through R₂₀₃ independently represent hydrogen, deuterium, halogen-substituted or unsubstituted (C1-C30)alkyl, (C1-C30)alkyl-substituted or unsubstituted (C6-C30)aryl or halogen;

R₂₀₄ through R₂₁₉ independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C1-C30)alkoxy, substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted (C2-C30)alkenyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted mono- or di-(C1-C30)alkylamino, substituted or unsubstituted mono- or di-(C6-C30)arylamino, SF₅, substituted or unsubstituted tri(C1-C30)alkylsilyl, substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, substituted or unsubstituted tri(C6-C30)arylsilyl, cyano or halogen;

R₂₂₀ through R₂₂₃ independently represent hydrogen, deuterium, halogen-substituted or unsubstituted (C1-C30)alkyl, or (C1-C30)alkyl-substituted or unsubstituted (C6-C30)aryl;

R₂₂₄ and R₂₂₅ independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl or halogen, or R₂₂₄ and R₂₂₅ may be linked via (C3-C12)alkylene or (C3-C12)alkenylene with or without a fused ring to form an alicyclic ring and a monocyclic or polycyclic aromatic ring;

R₂₂₆ represents substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (C2-C30)heteroaryl, or halogen;

R₂₂₇ through R₂₂₉ independently represent hydrogen, deuterium, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, or halogen; and

Q represents
,
or
;

R₂₃₁ through R₂₄₂ independently represent hydrogen, deuterium, halogen-substituted or unsubstituted (C1-C30)alkyl, (C1-C30)alkoxy, halogen, substituted or unsubstituted (C6-C30)aryl, cyano or substituted or unsubstituted (C3-C30)cycloalkyl, or they may be linked to an adjacent substituent via alkylene or alkenylene to form a spiro ring or a fused ring, or may be linked to R₂₀₇ or R₂₀₈ via alkylene or alkenylene to form a saturated or unsaturated fused ring.
The organic electroluminescent device of claim 7, wherein the phosphorescent dopont is selected from following compounds:
The organic electroluminescent device of claim 7, wherein the organic layer comprises an electroluminescent layer and a charge generating layer.
The organic electroluminescent device of claim 7, wherein the organic layer further comprises one or more organic electroluminescent layers emitting red, green and blue light to emit white light.