KR20140141933A - An organic electroluminescent compound and an organic electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to an organic electroluminescent compound and an organic electroluminescent device including the same. If the organic electroluminescent compound of the present invention is used, an organic electroluminescent device having excellent current efficiency can be manufactured. The purpose of the present invention is providing an organic electroluminescent compound having excellent current efficiency. An organic electroluminescent compound represented by following chemical formula 1 achieves the purpose. The compound of the present invention represented by chemical formula 1 has an asymmetric structure having three different substituent on a benzene parent structure.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic electroluminescent compound and an organic electroluminescent device including the same. BACKGROUND ART < RTI ID = 0.0 >

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

Among display devices, an electroluminescent device (EL device) is a self-luminous display device having a wide viewing angle, an excellent contrast, and a high response speed. In 1987, Eastman Kodak Company developed an organic EL device using an aromatic diamine and an aluminum complex having low molecular weight as a light emitting layer forming material [Appl. Phys. Lett. 51, 913, 1987].

The most important factor determining the luminous efficiency in an organic electroluminescent device is a light emitting material. Fluorescent materials have been widely used as luminescent materials to date, but the development of phosphorescent materials has been widely studied in that phosphorescent materials can improve luminous efficiency up to 4 times the theoretical efficiency of phosphorescent materials in terms of the mechanism of electroluminescence . Until now, an iridium (III) complex series has been widely known as a phosphorescent material. Each RGB has bis (2- (2'-benzothienyl) -pyridinate-N, C-3 ') iridium (acetylacetonate ) [(acac) Ir (btp ) 2], tris (2-phenylpyridine) iridium [Ir (ppy) _3] and bis (4,6-difluorophenyl pyridinyl Nei Sat -N, C2) avoid collision Ney And materials such as tolidium (Firpic) are known.

In the prior art, 4,4'-N, N'-dicarbazole-biphenyl (CBP) is the most widely known phosphorescent host material. In recent years, Pioneer et al. Of Japan have been using bathocuproine (BCP) and aluminum (III) bis (2-methyl-8-quinolinate) (4-phenyl phenolate) Balq) as a host material and developed a high-performance organic electroluminescent device.

However, existing materials have advantages in terms of luminescence properties, but they have the following disadvantages: (1) They have a low glass transition temperature and a low thermal stability, which deteriorate during a high-temperature deposition process under vacuum, and the lifetime of the device deteriorates. (2) In the organic electroluminescent device, the power efficiency is in the relation of [(? / Voltage) x current efficiency], so that the power efficiency is inversely proportional to the voltage. In the organic electroluminescent device using the phosphorescent host material, The current efficiency (cd / A) is higher than that of the light emitting device, but the driving voltage is also very high, so there is no great advantage in terms of power efficiency (lm / w). (3) In addition, when used in an organic electroluminescent device, it is unsatisfactory in terms of operating life, and luminous efficiency is still required to be improved.

On the other hand, the organic electroluminescent device has a multi-layer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer in order to improve its efficiency and stability. At this time, the selection of a compound included in the hole transport layer or the like is recognized as a means for improving device characteristics such as hole transport efficiency, luminous efficiency, and lifetime of the light emitting layer.

(NPB), N, N (1-naphthyl) -NPhenylamino] biphenyl (NPB) as a hole injection and transport material in organic electroluminescent devices, (TPD), 4,4 ', 4 "-tris (3-methylphenyl) -4,4'-diamine Phenylamino) triphenylamine (MTDATA). However, when such a material is used, there is a problem that the quantum efficiency and lifetime of the organic electroluminescent device are lowered. This is because when the organic electroluminescent device is driven at a high current , Thermal stress is generated between the anode and the hole injection layer, and the lifetime of the device is rapidly lowered due to the thermal stress. The organic material used for the hole injection layer has a very high mobility Therefore, the hole-electron charge balance of holes and electrons is broken and the quantum efficiency (cd / A) is low It becomes.

Therefore, development of a hole transport layer for improving the durability of an organic electroluminescent device is still required.

International Publication WO 2013-011891A1 discloses a compound in which a heteroaryl group is directly bonded to a nitrogen atom of a carbazole skeleton fused with a benzene ring and a pentane ring via a linker such as an aryl or heteroaryl group to a compound for an organic electroluminescence device .

However, this document discloses that a benzene ring in which a diarylamine and aryl or the like is bonded is bonded to a nitrogen atom of a carbazole skeleton fused with a benzene ring and a pentane ring directly or via a linker such as an aryl or heteroaryl group Compounds and an organic electroluminescent device using the same as a hole transport layer are not specifically disclosed.

[ Patent Literature ]

(Patent Document 1) International Publication WO 2013-011891 A1 (published on March 21, 2014)

An object of the present invention is to provide an organic electroluminescent compound excellent in current efficiency.

As a result of intensive studies to solve the above technical problems, the present inventors have found that an organic electroluminescent compound represented by the following formula (1) achieves the above-mentioned object.

The compound of the present invention represented by the following formula (1) has an asymmetric structure having three different substituents on the benzene macronucleus and has a lower crystallinity than a symmetrical structure, which is advantageous for forming an amorphous thin film [Chem. Rev. 2007, 107, page 960, 4.1.2], the introduction of heteroaryl groups allows both host materials and hole transport layer materials to be used, and has a high glass transition temperature due to nitrogen-containing pentacyclic fusion residues.

[Chemical Formula 1]

In Formula 1,

이고;A ring

ego;

이며;The B ring

;

이고;The C ring

ego;

X ₁ and X ₂ are each independently CR ₄ or N;

Y is _{-O-, -S-, -C (R 5} ) (R 6) -, -Si (R 7) (R 8) - or -N (R ₉₎ - is;

L ₁ to L ₃ each independently represents a single bond, a substituted or unsubstituted (C 2 -C 30) alkylene, a substituted or unsubstituted (C 6 -C 30) arylene, or a substituted or unsubstituted (5-30 membered) Heteroarylene;

Ar ₁ to Ar ₃ are each independently substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, substituted or unsubstituted (5-30 membered) heteroaryl;

R ₁ to R ₄ each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, substituted or unsubstituted Substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) NR ₁₀ R ₁₁ , -SiR ₁₂ R ₁₃ R ₁₄ , -SR ₁₅ , -OR ₁₆ , cyano, nitro, or hydroxy, or connected to adjacent substituents (3-30 membered) to form a monocyclic or polycyclic alicyclic or aromatic May form a ring; The carbon atom of the alicyclic or aromatic ring formed may be replaced by one or more heteroatoms selected from nitrogen, oxygen and sulfur;

R ₅ to R ₁₆ each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, substituted or unsubstituted Substituted or unsubstituted (3- to 7-membered) heterocycloalkyl, or substituted or unsubstituted (C3-C30) cycloalkyl, or (3-30 membered) monocyclic or polycyclic alicyclic Group or an aromatic ring; The carbon atom of the alicyclic or aromatic ring formed may be replaced by one or more heteroatoms selected from nitrogen, oxygen and sulfur;

l, m and n are each independently an integer of 0 to 3, and when L is an integer of 2 or more, each of L ₁ to L ₃ may be the same or different;

a and c are each independently an integer of 1 to 4, and when R is an integer of 2 or more, each of R ₁ and R ₃ may be the same or different;

b is 1 or 2, and when R < 2 > is 2, each R < ₂ > may be the same or different;

The heterocycloalkyl and heteroaryl (Rhen) comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P.

The organic electroluminescent compound according to the present invention has an advantage that an organic electroluminescent device having excellent current efficiency can be produced.

The present invention will now be described in more detail, but this should not be construed as limiting the scope of the present invention.

The present invention relates to an organic electroluminescent compound represented by Formula 1, an organic electroluminescent material including the organic electroluminescent compound, and an organic electroluminescent device including the same.

The organic electroluminescent compound represented by Formula 1 will be described in more detail as follows.

The term "(C1-C30) alkyl (phenylene)" as used in the present invention means a linear or branched alkylene having 1 to 30 carbon atoms, wherein the number of carbon atoms is preferably 1 to 10, 6 is more preferable. Specific examples of the alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. As used herein, "(C2-C30) alkenyl" means straight or branched chain alkenyl having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms. Specific examples of the alkenyl include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl and the like. As used herein, "(C2-C30) alkynyl" means straight or branched chain alkynyl having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms. Examples of the alkynyl include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl and 1-methylpent-2-onyl. The term "(C3-C30) cycloalkyl" as used herein means a monocyclic or polycyclic hydrocarbon having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, more preferably 3 to 7 carbon atoms. Examples of the cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. The term " (3-7 member) heterocycloalkyl "as used herein refers to a heterocycloalkyl group having 3 to 7 ring skeletal atoms and at least one heteroatom selected from the group consisting of B, N, O, S, P (= O) Preferably one or more heteroatoms selected from O, S and N, and includes, for example, tetrahydrofuran, pyrrolidine, thiolane, tetrahydropyran and the like. The term "(C6-C30) aryl (phenylene)" as used herein refers to a single ring or fused ring radical derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, wherein the number of carbon atoms in the ring is 6 to 20, 15 < / RTI > Examples of the aryl include phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenan Naphthacenyl, fluoranthenyl, and the like can be given as examples of the aryl group, the arylthio group, the arylthio group, the arylthio group, and the arylthio group. As used herein, the term "(5-30) heteroaryl (phenylene)" refers to a heteroaryl group having 5 to 30 ring skeletal atoms and one or more heteroatoms selected from the group consisting of B, N, O, S, P Quot; means an aryl group containing an atom. The number of heteroatoms is preferably 1 to 4, and may be a monocyclic ring system or a fused ring system condensed with at least one benzene ring, and may be partially saturated. In addition, the heteroaryl (phenylene) also includes a heteroaryl group in which at least one heteroaryl or aryl group is linked to a heteroaryl group by a single bond. Examples of such heteroaryls include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl , Monocyclic heteroaryl such as triazolyl, tetrazolyl, furanzyl, pyridyl, pyrazinyl, pyrimidinyl and pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, di Benzoimidazolyl, benzothiazolyl, benzothiazolyl, benzoisothiazolyl, benzooxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, Fused heterocyclic heteroaryl such as norbornyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxaphyl, phenanthridinyl, benzodioxolyl and the like. As used herein, "halogen" includes F, Cl, Br, and I atoms.

은 하기 구조로부터 선택될 수 있다.According to one embodiment of the present invention,

Can be selected from the following structures.

Y, R ₁ to R ₃ , and a to c are the same as defined in formula (1).

Also, in the phrase "substituted or unsubstituted" described in the present invention, "substituted" means that a hydrogen atom is replaced with another atom or another functional group (ie, a substituent) in a certain functional group. Substituted by the L ₁ to L _3, Ar ₁ to Ar _3, R ₁ to R ₁₆ of said formula (1) alkyl (alkylene), substituted aryl (alkylene), substituted heteroaryl (alkylene), substituted cycloalkyl, substituted heterocycloalkyl (C1-C30) alkoxy, (C6-C30) aryl and (C6-C30) aryl, each of which is substituted with deuterium, halogen, halogen substituted or unsubstituted (C3-C30) cycloalkyl, (3-7 membered) heterocycloalkyl, tri (C1-C30) alkylsilyl, tri (C6-C30) arylsilyl, di (C2-C30) alkenyl, (C2-C30) alkynyl, cyano, carbazolyl (C1-C30) alkylsilyl, (C6-C30) arylamino, di (C6-C30) alkylamino, di (C6-C30) (C6-C30) aryl (C1-C30) alkyl, (C1-C30) alkylcarbonyl, ) Alkyl ( (C6-C30) aryl, carboxyl, nitro and hydroxy, each independently selected from the group consisting of (C6-C30) aryl and di Or more.

In Formula 1, X ₁ and X ₂ are each independently CR ₄ or N; Preferably CR < _{4 &} gt ;.

Wherein Y is _{-O-, -S-, -C (R 5} ) (R 6) -, -Si (R 7) (R 8) - or -N (R ₉₎ - a.

Each of L ₁ to L ₃ is independently a single bond, a substituted or unsubstituted (C 2 -C 30) alkylene, a substituted or unsubstituted (C 6 -C 30) arylene, or a substituted or unsubstituted ) Heteroarylene; Preferably a single bond or unsubstituted (C6-C20) arylene; More preferably a single bond or unsubstituted (C6-C15) arylene.

Wherein Ar ₁ to Ar ₃ are each independently substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, or substituted or unsubstituted (5-30 membered) heteroaryl; Preferably substituted or unsubstituted (C6-C20) aryl, or substituted or unsubstituted (5-20 membered) heteroaryl; (5 to 15 membered) heteroaryl which is unsubstituted or substituted by (C6-C15) aryl or (C6-C15) aryl which is substituted by di (C6-C15) arylamino.

Each of R ₁ to R ₄ is independently hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, substituted or unsubstituted Substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) _{-NR 10 R 11, -SiR 12 R} 13 R 14, -SR 15, -OR 16, cyano, nitro or hydroxy, or, is connected to an adjacent substituent via (3-30 W) or a monocyclic or polycyclic alicyclic or May form an aromatic ring; The carbon atom of the alicyclic or aromatic ring formed may be replaced by one or more heteroatoms selected from nitrogen, oxygen and sulfur; Preferably hydrogen or may be connected to adjacent substituents to form a (3-20 membered) monovalent aromatic ring; More preferably hydrogen or may be connected to adjacent substituents to form a (3- to 15-membered) monocyclic aromatic ring.

Wherein R ₅ to R ₁₆ are each independently selected from the group consisting of hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, Substituted or unsubstituted (3- to 7-membered) heterocycloalkyl, or substituted or unsubstituted (C3-C30) cycloalkyl, or (3-30 membered) monocyclic or polycyclic Lt; / RTI > may form an alicyclic or aromatic ring; The carbon atom of the alicyclic or aromatic ring formed may be replaced by one or more heteroatoms selected from nitrogen, oxygen and sulfur; Preferably unsubstituted (C1-C10) alkyl or unsubstituted (C6-C20) aryl; More preferably unsubstituted (C1-C6) alkyl or unsubstituted (C6-C15) aryl.

Each of l, m and n is independently an integer of 0 to 3, and when L is an integer of 2 or more, each of L ₁ to L ₃ may be the same or different; Preferably, each independently is 0 or 1.

Each of a and c is independently an integer of 1 to 4, and when it is an integer of 2 or more, each of R ₁ and R ₃ may be the same or different; Preferably 4, and each of R ₁ and R ₃ is the same.

B is 1 or 2, and when R is 2, each R < ₂ > may be the same or different; Preferably 2, and each R ₂ is the same.

According to an embodiment of the present invention, in Formula 1, X ₁ and X ₂ are each independently CR ₄ ; Y is _{-O-, -S-, -C (R 5} ) (R 6) -, -Si (R 7) (R 8) - or -N (R ₉₎ - is; L ₁ to L ₃ are each independently a single bond or unsubstituted (C 6 -C 20) arylene; Ar ₁ to Ar ₃ are each independently substituted or unsubstituted (C6-C20) aryl, or substituted or unsubstituted (5-20 membered heteroaryl); R ₁ to R ₄ are each independently hydrogen or may be connected to adjacent substituents to form a (3-20 membered) monovalent aromatic ring; R ₅ to R ₁₆ are each independently unsubstituted (C 1 -C 10) alkyl or unsubstituted (C 6 -C 20) aryl; l, m and n are each independently 0 or 1; a and c are each independently 4 and each R ₁ and R ₃ is the same; b is 2, and each R ₂ is the same.

According to another embodiment of the present invention, in Formula 1, X ₁ and X ₂ are each independently CR ₄ ; Y is _{-O-, -S-, -C (R 5} ) (R 6) -, -Si (R 7) (R 8) - or -N (R ₉₎ - is; L ₁ to L ₃ are each independently a single bond or unsubstituted (C 6 -C 15) arylene; Ar ₁ to Ar ₃ are each independently (C6-C20) aryl substituted or unsubstituted with di (C6-C15) arylamino or (5-15) hetero substituted or unsubstituted Aryl; R ₁ to R ₄ are each independently hydrogen or may be connected with adjacent substituents to form a (3 to 15 membered) monovalent aromatic ring; R ₅ to R ₁₆ are each independently unsubstituted (C 1 -C 6) alkyl or unsubstituted (C 6 -C 15) aryl; l, m and n are each independently 0 or 1; a and c are each independently 4 and each R ₁ and R ₃ is the same; b is 2, and each R ₂ is the same.

The organic electroluminescent compound of Formula 1 may be more specifically exemplified by the following compounds, but is not limited thereto.

The organic electroluminescent compound according to the present invention can be prepared by a synthesis method known to a person skilled in the art and can be prepared, for example, as shown in the following reaction formula.

[Reaction Scheme 1]

[Reaction Scheme 2]

In Formulas 1 and 2, A ring to C ring, L ₁ to L ₃ , R ₁ , Ar ₁ to Ar ₃ , a, l, m and n are the same as defined in formula (1), and Hal is halogen.

In the Suzuki reaction of Reaction Formulas 1 and 2, the arylboronic acid and the aryl halide are reacted under basic conditions such as potassium carbonate and potassium phosphate to form a carbon-carbon bond. The above reaction is mainly carried out in a mixed solvent of toluene and ethanol, and tetrakistriphenylphosphine palladium, palladium acetate and s-force (for example, S-force (2-dicyclophosphino-2 ', 6'- Dimethoxyphenyl)) in the presence of a palladium catalyst.

The Buchwald-Hartwig reaction of Schemes 1 and 2 reacts the arylamine and the aryl halide under basic conditions such as sodium t-butoxide to form a carbon-nitrogen bond. The reaction is carried out in an aromatic organic solvent such as toluene or xylene, and the combination of palladium acetate and s-force (e.g., S-force (2-dicyclophosphino-2 ', 6'-dimethoxyphenyl) And proceeds under reflux using the same palladium complex system as a catalyst.

The present invention also provides an organic electroluminescent material comprising an organic electroluminescent compound of Formula 1 and an organic electroluminescent device comprising the same.

The material may be made of the organic electroluminescent compound of the present invention alone, and may further include common materials included in the organic electroluminescent material.

An organic electroluminescent device according to the present invention includes a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, and the organic material layer may include at least one organic electroluminescent compound represented by Formula 1.

One of the first electrode and the second electrode may be an anode and the other may be a cathode. The organic material layer may further include one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.

The organic electroluminescent compound of the present invention may be included in at least one of the light emitting layer and the hole transporting layer. When used in the hole transporting layer, the organic electroluminescent compound of the present invention can be included as a hole transporting material. When used in the light emitting layer, the organic electroluminescent compound of the present invention can be included as a host material.

The organic electroluminescent device comprising the organic electroluminescent compound of the present invention may further include at least one other compound other than the organic electroluminescent compound of the present invention as a host material, and may further include at least one dopant.

When the organic electroluminescent compound of the present invention is contained as the host material (first host material) of the light emitting layer, other compounds may be included as the second host material. Here, the weight ratio of the first host material to the second host material ranges from 1:99 to 99: 1.

The host material of the compound other than the organic electroluminescent compound of the present invention may be any phosphorescent host known in the art, but is preferably selected from the group consisting of compounds represented by the following formulas (2) to (4) desirable.

(2)

(3)

[Chemical Formula 4]

In the above Chemical Formulas 2 to 4,

Cz has the following structure,

R ₂₁ to R ₂₄ each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, substituted or unsubstituted Heteroaryl or R ₂₅ R ₂₆ R ₂₇ Si-, R ₂₅ to R ₂₇ are each independently substituted or unsubstituted (C 1 -C 30) alkyl, or substituted or unsubstituted (C 6 -C 30) aryl; L ₄ is a single bond, substituted or unsubstituted (C6-C30) arylene, or substituted or unsubstituted (5-30 membered) heteroarylene; M is a substituted or unsubstituted (C6-C30) aryl, or a substituted or unsubstituted (5-30 membered) heteroaryl; Y ₁ and Y ₂ are -O-, -S-, -N (R ₃₁ ) -, -C (R ₃₂ ) (R ₃₃ ) -, and Y ₁ and Y ₂ are not simultaneously present; R ₃₁ to R ₃₃ each independently represent a substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (5-30 W) heteroaryl ring, R ₃₂ And R ₃₃ may be the same or different; each of h and i is independently an integer of 1 to 3, j, k, o and r are each independently an integer of 0 to 4, and when h, i, j, k, o or r is an integer of 2 or more, (Cz-L ₄ ), each (Cz), each R ₂₁ , each R ₂₂ , each R _23, or each R ₂₄ may be the same or different.

Specifically, preferred examples of the host material are as follows.

The dopant included in the organic electroluminescent device of the present invention is preferably at least one phosphorescent dopant. The phosphorescent dopant material to be applied to the organic electroluminescent device of the present invention is not particularly limited, but a complex compound of a metal atom selected from iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt) And more preferably an ortho-metallated complex compound of a metal atom selected from iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt), and still more preferably an orthometallated iridium complex compound.

The phosphorescent dopant is preferably selected from the group consisting of compounds represented by the following Chemical Formulas (5) to (7).

In Formulas 5 to 7, L is selected from the following structures;

R ₁₀₀ is hydrogen or substituted or unsubstituted (C 1 -C 30) alkyl; R ₁₀₁ to R ₁₀₉ and R ₁₁₁ to R ₁₂₃ are each independently selected from the group consisting of hydrogen, deuterium, halogen, (C 1 -C 30) alkyl, cyano, substituted or unsubstituted (C 1 -C 30) alkoxy, Or substituted or unsubstituted (C3-C30) cycloalkyl; R ₁₂₀ to R ₁₂₃ may be connected to adjacent substituents to form a (3-30 membered) monocyclic or polycyclic alicyclic or aromatic ring (e.g., quinoline); The carbon atom of the alicyclic or aromatic ring formed may be replaced by one or more heteroatoms selected from nitrogen, oxygen and sulfur; R ₁₂₄ to R ₁₂₇ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, or substituted or unsubstituted (C 6 -C 30) aryl; When R ₁₂₄ to R ₁₂₇ are aryl groups, they may be connected to adjacent groups to form (3-30 membered) monocyclic or polycyclic alicyclic or aromatic rings (for example, fluorene); The carbon atom of the alicyclic or aromatic ring formed may be replaced by one or more heteroatoms selected from nitrogen, oxygen and sulfur; R ₂₀₁ to R ₂₁₁ are each independently hydrogen, deuterium, halogen, or (C1-C30) alkyl in which the halogen is substituted or unsubstituted; o and p are each independently an integer of 1 to 3, and when o or p is an integer of 2 or more, each R ₁₀₀ may be the same or different from each other; q is an integer of 1 to 3;

Specific examples of the phosphorescent dopant material are as follows.

The present invention provides a composition for preparing an organic electroluminescent device in a further aspect. The composition includes a compound of the present invention as a hole transport layer material.

Further, the organic electroluminescent device of the present invention includes a first electrode; A second electrode; And at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer includes a light emitting layer, and the light emitting layer may include the composition for an organic electroluminescent device of the present invention.

The organic electroluminescent device of the present invention includes the organic electroluminescent compound of Formula 1, and at the same time, may include at least one compound selected from the group consisting of an arylamine-based compound and a styrylarylamine-based compound.

Further, in the organic electroluminescent device of the present invention, in addition to the organic electroluminescent compound of Formula 1, an organic electroluminescent compound of the group 1, 2, 4, 5 period transition metal, lanthanide series and d- The organic compound layer may further include at least one metal or complex compound selected from the group consisting of a light emitting layer and a charge generating layer.

In addition, the organic electroluminescent device of the present invention may emit white light by further including at least one light emitting layer containing a blue, red or green light emitting compound known in the art, in addition to the compound of the present invention. Further, if necessary, it may further include a yellow or orange light emitting layer.

In the organic electroluminescent device of the present invention, one layer selected from a chalcogenide layer, a metal halide layer and a metal oxide layer (hereinafter referred to as " surface layer ") is formed on the inner surface of at least one of the pair of electrodes, Or more. Concretely, it is preferable to dispose a halogenated metal layer or a metal oxide layer on the surface of the anode on the side of the light emitting medium layer and on the surface of the cathode on the side of the light emitting medium layer, with a chalcogenide (including oxide) layer of a metal of silicon and aluminum Do. Thus, stabilization of the drive can be obtained. Preferable examples of the chalcogenide include SiO _X (1? _X ? 2), AlO _x (1? _X ? 1.5), SiON or SiAlON. Preferred examples of the halogenated metal include LiF, MgF ₂ , CaF ₂ , Rare-earth metals, etc. Preferred examples of the metal oxides include Cs ₂ O, Li ₂ O, MgO, SrO, BaO, CaO and the like.

In addition, in the organic electroluminescent device of the present invention, a mixed region of the electron transfer compound and the reducing dopant or a mixed region of the hole transport compound and the oxidative dopant is disposed on at least one surface of the pair of electrodes thus fabricated desirable. In this way, since the electron transfer compound is reduced to an anion, it becomes easy to inject and transfer electrons from the mixed region to the light emitting medium. Further, since the hole transport compound is oxidized and becomes a cation, it becomes easy to inject and transport holes from the mixed region into the light emitting medium. Preferred oxidizing dopants include various Lewis acids and acceptor compounds, and preferred reducing dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals, and mixtures thereof. Also, a white organic light emitting device having two or more light emitting layers can be manufactured using a reducing dopant layer as a charge generating layer.

The formation of each layer of the organic electroluminescent device of the present invention may be performed by a dry film formation method such as vacuum deposition, sputtering, plasma or ion plating, or a wet film formation method such as spin coating, dip coating or flow coating Can be applied.

In the case of the wet film formation method, a thin film is formed by dissolving or dispersing a material forming each layer in an appropriate solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc., And it may be any thing that does not have a problem in the tabernacle.

Hereinafter, the organic electroluminescent compound according to the present invention, the method for producing the same, and the luminescent characteristics of the device will be described with reference to the representative compound of the present invention for a detailed understanding of the present invention.

[Example 1] Preparation of Compound C-1

Synthesis of Compound 1-1

The reaction vessel was charged with 5H-benzofuro [3,2-c] carbazole (30 g, 117 mmol), 4-bromo-1-fluoro-2-nitrobenzene (26 g, 117 mmol), cesium carbonate g, 140 mmol) and dimethylsulfoxide (300 mL) were added, and the mixture was stirred at room temperature overnight. The reaction solution was diluted with ethyl acetate and washed several times with water. Water was removed with anhydrous magnesium sulfate. The mixture was distilled under reduced pressure and purified by column chromatography to obtain Compound 1-1 (45 g, 85%).

Synthesis of Compound 1-2

Compound 1-1 (30 g, 66 mmol), hydrated tin (II) chloride (44.4 g, 200 mmol) and ethyl acetate (700 mL) were added to the reaction vessel and refluxed for 2 hours. The reaction solution cooled to room temperature was diluted with ethyl acetate and washed several times with water. Water was removed with anhydrous magnesium sulfate. The mixture was distilled under reduced pressure and purified by column chromatography to obtain Compound 1-2 (25 g, 83%)

Synthesis of Compound 1-3

(23 g, 54 mmol), 4-dibenzothiophene boronic acid (15 g, 65 mmol), palladium (0) tetrakis (triphenylphosphine) (2.5 g, 2.2 mmol) , Potassium carbonate (15 g, 108 mmol), toluene (150 mL), ethanol (50 mL), and distilled water (50 mL) were added, and the mixture was refluxed for 2 hours. After the reaction was completed, the reaction solution was washed with distilled water. Extracted with ethyl acetate and dried over magnesium sulfate. The solvent was removed by a rotary evaporator and then purified by column chromatography to obtain Compound 1-3 (29.5 g, calculated as a product).

Synthesis of Compound C-1

To the reaction vessel was added compound 1-3 (15.5 g, 29.2 mmol), iodobenzene (10 mL, 88 mmol, d = 1.823), palladium (II) acetate (1 g, 4.4 mmol), tri- (4 mL, 50%, 8.8 mmol), sodium tert-butoxide (8.5 g, 88 mmol) and o-xylene (150 mL) were added and refluxed for 48 hours. The reaction mixture was cooled to room temperature and the solid was then filtered and washed with methylene chloride (MC). The filtrate was distilled under reduced pressure and purified by column chromatography to obtain Compound C-1 (6.4 g, 32%).

Property data: melting point 284 ° C, UV 352 nm (in toluene), PL 407 nm (in toluene), molecular weight 683.54 [M + 1]

[Example 2] Preparation of Compound C-4

Synthesis of Compound 2-1

(30 g, 117 mmol), 1-bromo-3,5-dichlorobenzene (40 g, 176 mmol), copper iodine (I) (11 g, 59 mmol), ethylenediamine (15 mL, 234 mmol), potassium phosphate (50 g, 234 mmol) and 600 mL of toluene were added thereto and refluxed overnight. The reaction solution was diluted with ethyl acetate and washed several times with water. Water was removed with anhydrous magnesium sulfate. The mixture was distilled under reduced pressure and purified by column chromatography to obtain Compound 2-1 (28 g, 60%).

Synthesis of Compound 2-2

To the reaction vessel was added compound 2-1 (14.3 g, 35.5 mmol), diphenylamine (6 g, 35.5 mmol), palladium (II) acetate (0.16 g, 0.71 mmol), S- Dimethoxyphenyl) (0.58 g, 1.42 mmol), sodium t-butoxide (4 g, 43 mmol), and o-xylene (350 mL). The reaction solution cooled to room temperature was diluted with ethyl acetate and washed several times with water. Water was removed with anhydrous magnesium sulfate. The mixture was distilled under reduced pressure and purified by column chromatography to obtain Compound 2-2 (12.5 g, 66%).

Synthesis of Compound C-4

The reaction vessel was charged with compound 2-2 (12 g, 22.4 mmol), 4-dibenzothiophene boronic acid (7.2 g, 27 mmol), palladium (II) acetate (0.25 g, 0.9 mmol), S- Dimethoxyphenyl) (0.55 g, 1.3 mmol), potassium carbonate (12 g, 56 mmol), toluene 75 mL, 25 mL of 1,4-dioxane and 25 mL of distilled water And the mixture was refluxed overnight. After the reaction was completed, the reaction solution was washed with distilled water. Extracted with ethyl acetate and dried over magnesium sulfate. The solvent was removed using a rotary evaporator and then purified by column chromatography to obtain the compound C-4 (10 g, 67%).

Property data: melting point 238 캜, UV 342 nm (in toluene), PL 400 nm (in toluene), molecular weight 683.54 [M + 1]

[Example 3] Preparation of Compound C-12

Synthesis of Compound C-12

To the reaction vessel were added compound 2-1 (7.5 g, 18.5 mmol), 4- (diphenylamino) phenylboronic acid (12.3 g, 42.5 mmol), palladium (II) acetate (0.35 g, 1.5 mmol) (0.9 g, 2.2 mmol), potassium phosphate (12 g, 55.5 mmol), 100 mL of toluene, 25 mL of 1,4-dioxane, and distilled water 25 mL was added, and the mixture was refluxed overnight. After the reaction was completed, the reaction solution was washed with distilled water. Extracted with ethyl acetate and dried over magnesium sulfate. The solvent was removed using a rotary evaporator and then purified by column chromatography to obtain the compound C-12 (9.4 g, 62%).

Property data: melting point 178 캜, UV 354 nm (in toluene), PL 396 nm (in toluene), molecular weight 821.59 [M + 1]

[Example 4] Preparation of Compound C-11

Synthesis of Compound C-11

To the reaction vessel was added compound 2-2 (12 g, 22.4 mmol), 4- (diphenylamino) phenylboronic acid (7.8 g, 26.9 mmol), palladium (II) acetate (0.20 g, 0.90 mmol) (0.5 g, 1.34 mmol), potassium phosphate (12 g, 55.5 mmol), toluene 120 mL, 1,4-dioxane 30 mL, and distilled water 30 mL was added, and the mixture was refluxed overnight. After the reaction was completed, the reaction solution was washed with distilled water. Extracted with ethyl acetate and dried over magnesium sulfate. The solvent was removed using a rotary evaporator and then purified by column chromatography to obtain the compound C-11 (11.8 g, 71%).

Property data: melting point 160 캜, UV 312 nm (in toluene), PL 396 nm (in toluene), molecular weight 821.59 [M + 1]

[Example 5] Preparation of Compound C-3

Synthesis of Compound C-3

The reaction vessel was charged with compound 2-2 (11.2 g, 20.9 mmol), 4-dibenzofuranboronic acid (6.2 g, 29.3 mmol), palladium (II) acetate (0.23 g, 1.0 mmol), S- (0.60 g, 1.04 mmol), potassium carbonate (11.1 g, 52.3 mmol), 70 mL of toluene, 25 mL of 1,4-dioxane and 25 mL of distilled water And then refluxed overnight. After the reaction was completed, the reaction solution was washed with distilled water. Extracted with ethyl acetate and dried over magnesium sulfate. The solvent was removed by a rotary evaporator and then purified by column chromatography to obtain the compound C-3 (4.2 g, 30%).

Property data: melting point 243 ° C, UV 362 nm (in toluene), PL 415 nm (in toluene), molecular weight 667.76 [M + 1]

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

An OLED device having a structure using the light emitting material of the present invention was fabricated. First, a transparent electrode ITO thin film (15? /?) Obtained from a glass for OLED (manufactured by Samsung Corning) was ultrasonically cleaned using trichlorethylene, acetone, ethanol and distilled water sequentially and stored in isopropanol Respectively. Next, an ITO substrate was mounted on a substrate holder of a vacuum deposition apparatus, and N ¹ , N ^{1 '} - ([1,1'-biphenyl] -4,4'-diyl) bis ¹ - (naphthalene- ¹ -yl) -N ⁴ , N ⁴ -diphenylbenzene-1,4-diamine) was added and the chamber was evacuated until the degree of vacuum reached 10 ^-6 torr. And evaporated to deposit a 60 nm thick hole injection layer on the ITO substrate. Compound C-1 of the present invention was added to another cell in a vacuum deposition apparatus, and a current was applied to the cell to evaporate it, thereby depositing a hole transport layer having a thickness of 20 nm on the hole injection layer. A hole injecting layer and a hole transporting layer were formed, and then a light emitting layer was deposited thereon as follows. 9 - (4 - ([1,1 ': 3', 1 "-terphenyl] -4-yl) pyrimidin-2-yl) -9'-phenyl-9H , 9'H-3,3'-bicarbazole, D-1 as a dopant in another cell, and then evaporating the two materials at different rates to obtain a dopant of 15 The light emitting layer having a thickness of 30 nm was deposited on the hole transporting layer by doping with a weight%. Then, on one side of the luminescent layer, an electron transport layer was formed by adding a solution of 2- (4- (9,10-di (naphthalen-2-yl) anthracen- And Lithium quinolate was added to another cell. Then, the two materials were evaporated at the same rate and doped with 50 wt% each, thereby depositing a 30 nm electron transport layer. Next, lithium quinolate was deposited to a thickness of 2 nm as an electron injecting layer, and an Al cathode was deposited to a thickness of 150 nm using another vacuum vapor deposition apparatus to fabricate an OLED device. Each compound was purified by vacuum sublimation under 10 ^-6 torr.

As a result, a current of 2.8 mA / cm < ² > flowed and a green emission of 1300 cd / m < ² > was confirmed.

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

An OLED device was fabricated in the same manner as in Device Manufacturing Example 1 except that Compound C-4 was deposited to a thickness of 20 nm as a hole transporting layer.

As a result, a current of 11.0 mA / cm < ² > flowed and green emission of 5100 cd / m < ² > was confirmed.

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

An OLED device was fabricated in the same manner as in the Device Production Example 1 except that the compound C-12 was deposited to a thickness of 20 nm as the hole transport layer.

As a result, a current of 3.2 mA / cm < ² > flowed and green luminescence of 1500 cd / m < ² > was confirmed.

[Device preparation example 4] Production of OLED device using organic electroluminescence compound according to the present invention

An OLED device was fabricated in the same manner as in Device Manufacturing Example 1 except that Compound C-11 was deposited as a hole transporting layer to a thickness of 20 nm.

As a result, a current of 15.5 mA / cm < ² > flowed and a green emission of 7600 cd / m < ² > was confirmed.

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

An OLED device was fabricated in the same manner as in Device Manufacturing Example 1 except that Compound C-3 was deposited as a hole transporting layer to a thickness of 20 nm.

As a result, a current of 9.8 mA / cm < ² > flowed and a green emission of 4700 cd / m < ² > was confirmed.

[Comparative Example] OLED element fabrication using a conventional organic electroluminescent compound

Except that N, N'-di (4-biphenyl) -N, N'-di (4-biphenyl) -4,4'- diaminobiphenyl was deposited to a thickness of 20 nm as a hole transporting layer OLED devices were fabricated in the same manner as in Example 1.

As a result, a current of 27.0 mA / cm < ² > flowed and green emission of 10730 cd / m < ² > was confirmed.

It was confirmed that the organic electroluminescent compounds developed in the present invention exhibited excellent luminescent properties compared to the conventional materials. Further, the device using the organic electroluminescent compound according to the present invention is excellent in luminescence characteristics, particularly current efficiency.

Claims (8)

An organic electroluminescent compound represented by the following formula (1).
[Chemical Formula 1]

In Formula 1,
A ring

ego;
The B ring

;
The C ring

ego;
X ₁ and X ₂ are each independently CR ₄ or N;
Y is _{-O-, -S-, -C (R 5} ) (R 6) -, -Si (R 7) (R 8) - or -N (R ₉₎ - is;
L ₁ to L ₃ each independently represents a single bond, a substituted or unsubstituted (C 2 -C 30) alkylene, a substituted or unsubstituted (C 6 -C 30) arylene, or a substituted or unsubstituted (5-30 membered) Heteroarylene;
Ar ₁ to Ar ₃ are each independently substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, substituted or unsubstituted (5-30 membered) heteroaryl;
R ₁ to R ₄ each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, substituted or unsubstituted Substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) NR ₁₀ R ₁₁ , -SiR ₁₂ R ₁₃ R ₁₄ , -SR ₁₅ , -OR ₁₆ , cyano, nitro, or hydroxy, or connected to adjacent substituents (3-30 membered) to form a monocyclic or polycyclic alicyclic or aromatic May form a ring; The carbon atom of the alicyclic or aromatic ring formed may be replaced by one or more heteroatoms selected from nitrogen, oxygen and sulfur;
R ₅ to R ₁₆ each independently represent hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, substituted or unsubstituted Substituted or unsubstituted (3- to 7-membered) heterocycloalkyl, or substituted or unsubstituted (C3-C30) cycloalkyl, or (3-30 membered) monocyclic or polycyclic alicyclic Group or an aromatic ring; The carbon atom of the alicyclic or aromatic ring formed may be replaced by one or more heteroatoms selected from nitrogen, oxygen and sulfur;
l, m and n are each independently an integer of 0 to 3, and when L is an integer of 2 or more, each of L ₁ to L ₃ may be the same or different;
a and c are each independently an integer of 1 to 4, and when R is an integer of 2 or more, each of R ₁ and R ₃ may be the same or different;
b is 1 or 2, and when R < 2 > is 2, each R < ₂ > may be the same or different;
The heterocycloalkyl and heteroaryl (Rhen) comprise at least one heteroatom selected from B, N, O, S, P (= O), Si and P. 2. The method of claim 1, wherein L ₁ to L _3, Ar ₁ to Ar _3, and R ₁ substituted alkyl (alkylene), in the through R _16, optionally substituted aryl (alkylene), substituted heteroaryl (alkylene), substituted cycloalkyl, substituted (C6-C30) aryl, (C6-C30) alkoxy, (C6-C30) aryl and (C6-C30) heteroaryl each independently substituted with deuterium, halogen, (C3-C30) cycloalkyl, (3-7 membered) heterocycloalkyl, tri (C1-C30) alkylsilyl, tri (C6-C30) aryl (C1-C30) alkylsilyl, (C2-C30) alkenyl, (C2-C30) alkynyl, cyano (C6-C30) arylamino, di (C6-C30) arylamino, di (C6-C30) arylamino substituted with (C6-C30) aryl (C1-C30) alkylcarbonyl, (C6-C30) arylcarbonyl, C1-C30) al (C6-C30) aryl, carboxyl, nitro, and hydroxy. The compound according to claim 1, wherein in Formula 1,

Lt; / RTI > is selected from the following structures.

Wherein Y, R ₁ to R ₃ , and a to c are the same as defined in claim 1. The compound according to claim 1, wherein X ₁ and X ₂ are each independently CR ₄ ; Y is _{-O-, -S-, -C (R 5} ) (R 6) -, -Si (R 7) (R 8) - or -N (R ₉₎ - is; L ₁ to L ₃ are each independently a single bond or unsubstituted (C 6 -C 20) arylene; Ar ₁ to Ar ₃ are each independently substituted or unsubstituted (C6-C20) aryl, or substituted or unsubstituted (5-20 membered heteroaryl); R ₁ to R ₄ are each independently hydrogen or may be connected to adjacent substituents to form a (3-20 membered) monovalent aromatic ring; R ₅ to R ₁₆ are each independently unsubstituted (C 1 -C 10) alkyl or unsubstituted (C 6 -C 20) aryl; l, m and n are each independently 0 or 1; a and c are each independently 4 and each R ₁ and R ₃ is the same; b is 2, and each R ₂ is the same. The compound according to claim 1, wherein X ₁ and X ₂ are each independently CR ₄ ; Y is _{-O-, -S-, -C (R 5} ) (R 6) -, -Si (R 7) (R 8) - or -N (R ₉₎ - is; L ₁ to L ₃ are each independently a single bond or unsubstituted (C 6 -C 15) arylene; Ar ₁ to Ar ₃ are each independently (C6-C20) aryl substituted or unsubstituted with di (C6-C15) arylamino or (5-15) hetero substituted or unsubstituted Aryl; R ₁ to R ₄ are each independently hydrogen or may be connected with adjacent substituents to form a (3- to 15-membered) monovalent aromatic ring; R ₅ to R ₁₆ are each independently unsubstituted (C 1 -C 6) alkyl or unsubstituted (C 6 -C 15) aryl; l, m and n are each independently 0 or 1; a and c are each independently 4 and each R ₁ and R ₃ is the same; b is 2, and each R ₂ is the same. Wherein said heteroaryl is selected from the group consisting of pyrrolyl, imidazolyl, triazinyl, tetrazinyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, dibenzofuranyl, dibenzothiophenyl, A benzothiazolyl group, a benzothiazolyl group, a benzothiazolyl group, a benzoxazolyl group, an isoindolyl group, an indolyl group, an indazolyl group, a benzothiadiazolyl group, a quinolyl group, an isoquinolyl group, a quinazolinyl group, a quinoxalinyl group, Or an organic electroluminescent compound, wherein R < 1 > The organic electroluminescent compound according to claim 1, wherein the compound is selected from the group consisting of the following compounds.

An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.