KR20150141179A - Novel organic electroluminescent compounds and organic electroluminescent device using the same - Google Patents

Abstract

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device adopting the same, and more specifically, to an organic electroluminescent compound represented by chemical formula 1 below. In the chemical formula 1, ring A and ring B are independently a monocyclic or polycyclic aromatic ring, a monocyclic or polycyclic heteroaromatic ring, a five- or six-membered heteroaromatic ring fused with an aromatic ring, or a monocyclic or polycyclic aromatic ring fused with a five- or six-membered heteroaromatic ring, where the ring A and ring B cannot both be a monocyclic aromatic ring. The organic electroluminescent compound according to the present invention shows good luminous efficiency, and superior material color purity and lifetime characteristics, thereby enabling manufacture of an OLED device with excellent driving time.

Description

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

TECHNICAL FIELD The present invention relates to a novel organic light emitting compound and an organic electroluminescent device including the same. In particular, the organic light emitting compound according to the present invention is represented by the following general formula (1).

[Chemical Formula 1]

Wherein A ring and B ring are independently a monocyclic or polycyclic aromatic ring, a monocyclic or polycyclic heteroaromatic ring, a 5- to 6-membered heteroaromatic ring fused with an aromatic ring, a 5-membered or 6-membered heteroaromatic ring fused with an aromatic ring, A 6-membered heteroaromatic ring is fused to a single ring or a polycyclic aromatic ring except when the rings A and B are simultaneously a single aromatic ring.

Among the display elements, an electroluminescence device (EL device) is a self-luminous display device having a wide viewing angle, excellent contrast, and fast response speed. In 1987, Eastman Kodak Company An organic EL device using an aromatic diamine and an aluminum complex having a low molecular weight as a material for forming a light emitting layer has been developed for the first time [Appl. Phys. Lett. 51, 913, 1987].

When an electric charge is injected into an organic film formed between an electron injection electrode (cathode) and a hole injection electrode (anode), the organic EL element forms excitons by paired electrons and holes. Light is emitted by using luminescence (phosphorescence or fluorescence) when excitons are inactive. The organic EL device emits a polarized light with a voltage of about 10 V and a high luminance of about 100 to 10,000 cd / m 2, and is characterized in that light is emitted from blue to red by simply selecting a fluorescent material. It is possible to form a device on a flexible transparent substrate such as a plastic substrate. Further, the device can be driven at a lower voltage (10 V or less) than a plasma display panel or an inorganic EL display, It has the advantage of being excellent in color.

The most important factors for determining the performance such as luminous efficiency and lifetime in an organic EL device are the luminescent material. Some characteristics required for such a luminescent material are that the fluorescent quantum yield in a solid state must be large, and the mobility of electrons and holes And should not be easily decomposed during vacuum deposition, and a uniform thin film should be formed and stabilized.

Organic light emitting materials can be roughly divided into polymer materials and low molecular materials. In the molecular structure, there are pure organic light emitting materials which do not contain metal complex compounds and metals. As such light emitting materials, there are known light emitting materials such as chelate complexing agents such as tris (8-quinolinolato) aluminum complexing agent, coumarin derivatives, tetraphenylbutadiene derivatives, bisstyrylarylene derivatives and oxadiazole derivatives. It is reported that visible light emission from blue to red can be obtained.

In order to realize a full-color OLED display, three kinds of light emitting materials for RGB are used. Development of a high-efficiency, long-life RGB light emitting material is an important task to improve the characteristics of the entire organic EL. The luminescent material can be divided into a host material and a dopant material in terms of function. Generally, it is known that an EL material has the best EL structure to form a light emitting layer by doping a host with a dopant. In recent years, development of high-efficiency, long-life organic EL devices has become an urgent task. In particular, considering the level of EL characteristics required for medium to large-sized OLED panels, it is urgent to develop materials that are superior to conventional light emitting materials. In this respect, the development of host materials is one of the most important factors to be solved. At this time, the desirable characteristics of the host material serving as a solid state solvent and energy transfer agent should be high purity and have a proper molecular weight to enable vacuum deposition. In addition, the glass transition temperature and thermal decomposition temperature must be high to ensure thermal stability, high electrochemical stability is required for longevity improvement, amorphous thin film must be easy to form, and adhesion to other adjacent layers is good, You should not.

When the organic EL device is manufactured using the doping technique, the energy transfer from the host molecule to the dopant in the excited state is not 100%, and the dopant as well as the host material emits light. Particularly, in the case of a red light emitting device, the color purity is deteriorated by the cloudy light emission of the host material because the host material emits light in a wavelength range with greater visibility than the dopant. When actually applied, it is necessary to improve the luminescence lifetime and the sustainability.

Meanwhile, CBP is the most widely known host material for a phosphorescent light emitting material, and a high efficiency OLED using a hole blocking layer such as BCP and BAlq is known. In Pioneer, Japan, a high performance OLED using a BAlq derivative as a host Is known.

However, existing materials have advantages in terms of luminescence properties, but they have disadvantages such as low glass transition temperature and very poor thermal stability, such as material changes when subjected to a high temperature deposition process under vacuum. Since the power efficiency in OLED = (π / voltage) × current efficiency, the power efficiency is inversely proportional to the voltage, and the power efficiency of the OLED should be high if the power consumption is low. OLEDs using real phosphorescent materials have significantly higher current efficiency (cd / A) than OLEDs using fluorescent materials. However, when conventional materials such as BAlq and CBP are used as hosts for phosphorescent materials, OLEDs using fluorescent materials (Lm / w) because the driving voltage is higher than that of the conventional device.

In addition, since the lifetime of the OLED device is never satisfactory, development of a more stable and more excellent host material is required.

Accordingly, an object of the present invention is to provide an organic luminescent compound having a superior skeleton having a suitable color coordinate and a luminescent efficiency and a device lifetime better than conventional materials in order to solve the above problems, and secondly, And to provide an organic electroluminescent device with high efficiency and long life, which is employed as a light emitting material.

The present invention relates to an organic electroluminescent compound represented by the following general formula (1) and an organic electroluminescent device including the same, wherein the organic electroluminescent compound according to the present invention has excellent luminescent efficiency, excellent color purity and lifetime characteristics of a material, There is an advantage that a device can be manufactured.

[Chemical Formula 1]

Wherein A ring and B ring are independently a monocyclic or polycyclic aromatic ring, a monocyclic or polycyclic heteroaromatic ring, a 5- to 6-membered heteroaromatic ring fused with an aromatic ring, a 5-membered or 6-membered heteroaromatic ring fused with an aromatic ring, A 6-membered heteroaromatic ring is a fused single- or multi-ring aromatic ring, except that the rings A and B are simultaneously a single aromatic ring;

R ₁ , R ₂ and R ₃ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) C30) heteroaryl, substituted or unsubstituted 5- to 7-membered heterocycloalkyl, 5- to 7-membered heterocycloalkyl in which one or more substituted or unsubstituted aromatic rings are fused, substituted or unsubstituted (C3- C30) cycloalkyl, (C3-C30) cycloalkyl substituted or unsubstituted with at least one aromatic ring, substituted or unsubstituted adamantyl, substituted or unsubstituted (C7-C30) bicycloalkyl, cyano _{, NR 11 R 12, BR 13} R 14, PR 15 R 16, P (= O) R 17 R 18 [R 11 to R ₁₈ are each independently a substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted Substituted or unsubstituted di (C1-C30) alkylsilyl, substituted or unsubstituted di (C1-C30) aryl or substituted or unsubstituted (C3-C30) heteroaryl, Substituted or unsubstituted (C6-C30) arylsilyl, substituted or unsubstituted tri (C6-C30) arylsilyl, substituted or unsubstituted (C6- Substituted or unsubstituted (C6-C30) arylthio, substituted or unsubstituted (C1-C30) alkylthio, substituted or unsubstituted Substituted or unsubstituted (C 1 -C 30) alkoxycarbonyl, substituted or unsubstituted (C 1 -C 30) alkylcarbonyl, substituted or unsubstituted (C 6 -C 30) arylcarbonyl, substituted or unsubstituted Substituted or unsubstituted (C 1 -C 30) alkoxycarbonyloxy, substituted or unsubstituted (C 1 -C 30) alkynyl, substituted or unsubstituted (C 1 -C 30) aryloxycarbonyl, substituted or unsubstituted C30) alkylcarbonyloxy, substituted or unsubstituted (C6-C30) arylcarbonyloxy, substituted or unsubstituted (C6-C30) aryloxycarbonyloxy, carboxyl, nitro, And fused rings Does not (C3-C30) alkylene or (C3-C30) alkenylene with an alicyclic ring, or a monocyclic or polycyclic, and may form a ring;

The hydrogen atoms of ring A and ring B may be further substituted with deuterium.

Substituents comprising " alkyl ", " alkoxy " and other " alkyl " moieties described in the present invention include both straight chain and branched forms.

&Quot; Aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination and is a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, And includes a form in which a plurality of aryls are connected by a single bond. Specific examples include phenyl, naphthyl, biphenyl, anthryl, indenyl, fluorenyl, phenanthryl, triphenylenyl, pyrenyl, perylenyl, crycenyl, naphthacenyl, fluoranthenyl, But is not limited thereto. The naphthyl includes 1-naphthyl and 2-naphthyl, anthryl includes 1-anthryl, 2-anthryl and 9-anthryl, and fluorenyl includes 1-fluorenyl, 2- Fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl. "Heteroaryl" in the present invention includes 1 to 4 heteroatoms selected from B, N, O, S, P (= O), Si and P as aromatic ring skeletal atoms and the remaining aromatic ring skeletal atoms are carbon Means a 5 to 6 membered monocyclic heteroaryl and a polycyclic heteroaryl condensed with at least one benzene ring and may be partially saturated. The heteroaryl in the present invention also includes a form in which at least one heteroaryl is linked by a single bond. The heteroaryl groups include divalent aryl groups in which the heteroatoms in the ring are oxidized or trisubstituted to form, for example, an N-oxide or a quaternary salt. Specific examples include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetra Monocyclic heteroaryl such as pyrrolyl, pyrrolyl, pyrrolyl, pyrrolyl, pyrrolyl, pyrrolyl, pyrrolyl, pyrazinyl, pyrrolyl, pyrrolyl, pyrazinyl, pyrimidinyl, pyridazinyl, Benzyloxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenanthridinyl (Such as pyridyl N-oxide, quinolyl N-oxide), quaternary salts thereof, and the like, and the like, but are not limited thereto .

(C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) arylsilyl, (C6- (C1-C30) alkyloxycarbonyl, (C1-C30) alkyloxycarbonyl, (C1-C30) alkylthio, C1-C30) alkylcarbonyloxy "and the like may be limited to a carbon number of 1 to 20, and may be limited to a carbon number of 1 to 10. (C6-C30) aryl, di (C1-C30) alkyl (C6-C30) arylsilyl, tri (C6-C30) aryloxycarbonyloxy, (C6-C30) arylthio, (C6-C30) arylcarbonyl, Quot; and the like can be limited to 6 to 20 carbon atoms, and may be limited to 6 to 12 carbon atoms. The heteroaryl of "(C3-C30) heteroaryl" may be limited to from 4 to 20 carbon atoms and may be limited to from 4 to 12 carbon atoms. The heteroaryl of the "(C3-C30) cycloalkyl" may be limited to 3 to 20 carbon atoms and may be limited to 3 to 7 carbon atoms. The alkenyl or alkynyl of "(C2-C30) alkenyl or alkynyl" may be limited to from 2 to 20 carbon atoms and may be limited to from 2 to 10 carbon atoms.

The term "substituted or unsubstituted" in the present invention means that the substituents of R ₁ to R ₃ and R ₁₁ to R ₁₈ are each independently a substituted or unsubstituted (C1-C30 (C6-C30) aryl, (C6-C30) aryl, (C3-C30) heteroaryl, 5 to 7 membered heterocycloalkyl, (C6-C30) cycloalkyl, tri (C1-C30) alkylsilyl, di (C1-C30) alkyl (C6-C30) cycloalkyl substituted with one or more aromatic rings, (C2-C30) alkenyl, (C2-C30) alkynyl, cyano, carbazolyl, NR < ₂₁ > R _22, BR ₂₃ R a _{24, PR 25 R 26, P} (= O) R 27 R 28 [R 21 to R ₂₈ independently represent a substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted with each other ring ( C6-C30) aryl or substituted or unsubstituted (C3-C30) hetero (C1-C30) alkyl, (C6-C30) aryl, (C1-C30) alkyloxy, (C6-C30) aryloxycarbonyl, (C1-C30) alkylcarbonyl, (C6-C30) arylcarbonyl, (C6-C30) aryloxycarbonyl, (C6-C30) alkoxycarbonyloxy, (C1-C30) alkylcarbonyloxy, (C6-C30) arylcarbonyloxy, (C6-C30) aryloxycarbonyloxy, carboxyl, nitro or hydroxy Quot; means that one or more substituents selected from the group consisting of the substituents are adjacent to each other, or adjacent substituents are connected to form a ring.

The organic electroluminescent compound of Formula 1 according to the present invention includes organic electroluminescent compounds represented by Formulas 2 to 6 below.

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

[Wherein B ring, R ₁ and R ₃ are the same as defined in Formula 1 above;

R ₄₁ to R ₄₄ each independently represent (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) heteroaryl, substituted or unsubstituted 5-membered To 7-membered heterocycloalkyl, a 5- to 7-membered heterocycloalkyl in which one or more substituted or unsubstituted aromatic rings are fused, a substituted or unsubstituted (C3-C30) cycloalkyl, a substituted or unsubstituted aromatic ring the fused one or more (C3-C30) cycloalkyl, substituted or unsubstituted adamantyl, substituted or unsubstituted alkyl, cyano (C7-C30) bicycloalkyl, NR ₂₁ R _22, BR ₂₃ R _24, PR _{25 R 26, P (= O} ) R 27 R 28 [R 21 to R ₂₈ independently represent a substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or substituted or unsubstituted Substituted or unsubstituted di (C1-C30) heteroaryl, substituted or unsubstituted tri (C1-C30) alkylsilyl, substituted or unsubstituted di Substituted or unsubstituted (C6-C30) arylsilyl, substituted or unsubstituted (C6-C30) aryl (C1-C30) alkyl, substituted or unsubstituted Substituted or unsubstituted (C6-C30) arylthio, substituted or unsubstituted (C1-C30) alkoxycarbonyl, substituted or unsubstituted Substituted or unsubstituted (C 1 -C 30) alkylcarbonyl, substituted or unsubstituted (C 6 -C 30) arylcarbonyl, substituted or unsubstituted (C 2 -C 30) alkenyl, Substituted or unsubstituted (C1-C30) alkylcarbonyloxy, substituted or unsubstituted (C6-C30) aryloxycarbonyl, substituted or unsubstituted (C1-C30) alkoxycarbonyloxy, substituted or unsubstituted (C3-C30) arylcarbonyloxy, substituted or unsubstituted (C6-C30) aryloxycarbonyloxy, carboxyl, nitro, hydroxy, C30) alkylene or (C 3-C30) alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring.

는

,

,

또는

이고; 상기 B₁ 내지 B₆는 서로 독립적으로 CR₃ 또는 N이고, 서로 인접한 B₁ 내지 B₆가 CR₃인 경우 각각의 R₃가 융합고리를 포함하거나 포함하지 않는 (C3-C30)알킬렌 또는 (C3-C30)알케닐렌으로 연결되어 지환족 고리 및 단일환 또는 다환의 방향족 고리를 형성할 수 있으며; R₃는 상기 화학식 1에서의 정의와 동일하다. remind

The

,

,

or

ego; Wherein B ₁ to B ₆ are independently of each other CR ₃ or N, and when adjacent B ₁ to B ₆ are CR ₃ , each R ₃ is a (C3-C30) alkylene or a C3-C30) alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring; R ₃ is the same as defined in the above formula (1).

The organic electroluminescent compound according to the present invention is selected from the following compounds, but is not limited thereto.

[Wherein R ₁ is the same as defined in the formula (1), R ₄₁ to R ₄₄ are the same as defined in the formulas (2) to (6);

R ₄₅ to R ₆₆ are each independently (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) heteroaryl, substituted or unsubstituted 5-membered To 7-membered heterocycloalkyl, a 5- to 7-membered heterocycloalkyl in which one or more substituted or unsubstituted aromatic rings are fused, a substituted or unsubstituted (C3-C30) cycloalkyl, a substituted or unsubstituted aromatic ring the fused one or more (C3-C30) cycloalkyl, substituted or unsubstituted adamantyl, substituted or unsubstituted alkyl, cyano (C7-C30) bicycloalkyl, NR ₂₁ R _22, BR ₂₃ R _24, PR _{25 R 26, P (= O} ) R 27 R 28 [R 21 to R ₂₈ independently represent a substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or substituted or unsubstituted Substituted or unsubstituted di (C1-C30) heteroaryl, substituted or unsubstituted tri (C1-C30) alkylsilyl, substituted or unsubstituted di Substituted or unsubstituted (C6-C30) arylsilyl, substituted or unsubstituted (C6-C30) aryl (C1-C30) alkyl, substituted or unsubstituted Substituted or unsubstituted (C6-C30) arylthio, substituted or unsubstituted (C1-C30) alkoxycarbonyl, substituted or unsubstituted Substituted or unsubstituted (C 1 -C 30) alkylcarbonyl, substituted or unsubstituted (C 6 -C 30) arylcarbonyl, substituted or unsubstituted (C 2 -C 30) alkenyl, Substituted or unsubstituted (C1-C30) alkylcarbonyloxy, substituted or unsubstituted (C6-C30) aryloxycarbonyl, substituted or unsubstituted (C1-C30) alkoxycarbonyloxy, substituted or unsubstituted (C6-C30) arylcarbonyloxy, substituted or unsubstituted (C6-C30) aryloxycarbonyloxy, carboxyl, nitro, hydroxy, or a substituent with or without a fused ring ) Alkylene or (C3 -C30) alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring.

The organic luminescent compound according to the present invention may be more specifically exemplified as the following compounds, but the following compounds are not intended to limit the present invention.

The organic luminescent compound according to the present invention can be prepared as shown in the following Reaction Schemes 1 to 3.

[Reaction Scheme 1]

[Reaction Scheme 2]

[Reaction Scheme 3]

[A rings, B rings and R ₁ to R ₃ in the above Reaction Schemes 1 to 3 are the same as defined in the above Chemical Formula 1].

The present invention provides an organic electroluminescent device, wherein the organic electroluminescent device according to the present invention comprises 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 comprises at least one organic light emitting compound of Formula 1.

The organic layer includes a light emitting layer, and the light emitting layer further includes at least one dopant in addition to one or more organic light emitting compounds of Formula 1, and the dopant applied to the organic light emitting device of the present invention is not particularly limited .

The dopant applied to the organic electroluminescent device of the present invention is preferably selected from compounds represented by the following general formula (7).

(7)

M ^One L ¹⁰¹ L ¹⁰² L ¹⁰³

Wherein M ¹ is selected from the group consisting of metals of Groups 7, 8, 9, 10, 11, 13, 14, 15 and 16, and the ligands L ¹⁰¹ , L ¹⁰² and L ¹⁰³ Are independently selected from the following structures.

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

R ₂₀₄ to R ₂₁₉ independently represent hydrogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 1 -C 30) alkoxy, substituted or unsubstituted (C 3 -C 30) Substituted or unsubstituted (C2-C30) alkenyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted mono- or substituted or unsubstituted di- mono- or di - (C6-C30) arylamino, SF _5, a substituted or unsubstituted tree (C1-C30) alkylsilyl, substituted or unsubstituted di (C1-C30) alkyl (C6-C30) arylsilyl, substituted Or unsubstituted tri (C6-C30) arylsilyl, cyano or halogen,

R ₂₂₀ to R ₂₂₃ are each independently hydrogen, (C 1 -C 30) alkyl in which halogen is substituted or unsubstituted, or (C 6 -C 30) aryl in which (C 1 -C 30) alkyl is unsubstituted or substituted;

R ₂₂₄ and R ₂₂₅ independently of one another are hydrogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl or halogen, or R ₂₂₄ and R ₂₂₅ comprise or consist of a fused ring (C3-C12) alkylene or (C3-C12) alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring;

R ₂₂₆ is substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl, substituted or unsubstituted (C 5 -C 30) heteroaryl or halogen;

R ₂₂₇ to R ₂₂₉ are independently of each other hydrogen, substituted or unsubstituted (C 1 -C 30) alkyl, substituted or unsubstituted (C 6 -C 30) aryl or halogen;

,

또는

이며, R₂₃₁ 내지 R₂₄₂는 서로 독립적으로 수소, 할로겐이 치환되거나 치환되지 않은 (C1-C30)알킬, (C1-C30)알콕시, 할로겐, 치환 또는 비치환된 (C6-C30)아릴, 시아노, 치환 또는 비치환된 (C5-C30)시클로알킬이거나, 인접한 치환체와 알킬렌 또는 알케닐렌으로 연결되어 스피로 고리 또는 융합고리를 형성할 수 있거나, R₂₀₇ 또는 R₂₀₈과 알킬렌 또는 알케닐렌으로 연결되어 포화 또는 불포화의 융합고리를 형성할 수 있다.]
Q is

,

or

R ₂₃₁ to R ₂₄₂ are independently selected from the group consisting of hydrogen, (C 1 -C 30) alkyl, (C 1 -C 30) alkoxy, halogen, substituted or unsubstituted (C 6 -C 30) aryl, , substituted or unsubstituted (C5-C30) or cycloalkyl, are connected to an adjacent substituent via alkylene or alkenylene may form a spiro ring or a fused ring, linked to R ₂₀₇ or R ₂₀₈ and alkylene or alkenylene To form a saturated or unsaturated fused ring.

The dopant compound of formula (7) may be exemplified by the following compounds, but is not limited thereto.

In the organic electroluminescent device of the present invention, the organic electroluminescent device may include at least one compound selected from the group consisting of an arylamine compound and a styrylarylamine compound. The arylamine-based compound or styrylarylamine-based compound is exemplified in Application Nos. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but is not limited thereto.

In addition, in the organic electroluminescent device of the present invention, in addition to the organic luminescent compound of Formula 1, an organic electroluminescent compound of group 1, group 2, group 4, periodic transition metal, group of lanthanide metal and group of d- , And the organic layer may include a light emitting layer and a charge generating layer.

Further, a white organic electroluminescent device can be formed by simultaneously including at least one organic luminescent layer emitting red, green or blue light in addition to the organic luminescent compound in the organic material layer. The compounds emitting blue, green or red light are exemplified in Application Nos. 10-2008-0123276, 10-2008-0107606 or 10-2008-0118428, but are not limited thereto.

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. Examples of the chalcogenide include SiO _x (1? _X ? 2), AlO _x (1? _X ? 1.5), SiON and SiAlON. Examples of the halogenated metal include LiF, MgF ₂ , CaF ₂ , Rare-earth metals and the like. Preferable 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 the 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. Preferred reducing dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals, and mixtures thereof. The reducing dopant layer A white organic electroluminescent device having two or more light emitting layers can also be manufactured by using it as a charge generation layer.

The organic electroluminescent compound according to the present invention has an advantage of being able to produce an OLED device having excellent luminous efficiency, excellent color purity and life characteristics of the material, and excellent driving life of the device.

Hereinafter, the organic luminescent compound according to the present invention, the method for producing the same, and the luminescent characteristics of the device will be described in order to facilitate a detailed understanding of the present invention, but the present invention is not limited thereto. And are not intended to limit the scope of the invention.

[Preparation Example 1] Preparation of Compound 1

compound 1-1 Manufacturing

1-naphthalene boronic acid _{10.2 g (59.4 mmol), 4} 1.7 g (1.4 mmol), 2M K 2 CO 3 aqueous solution of 70 mL 1-bromo-2-benzene 10.0 g (49.5 mmol) nitro, Pd (PPh ₃₎ , 200 mL of toluene and 100 mL of ethanol were added, and the mixture was refluxed and stirred for 12 hours. Washed with distilled water, extracted with EA, dried over anhydrous MgSO ₄ , distilled under reduced pressure, and the obtained residue was subjected to column separation to obtain Compound 1-1 (9.0 g, 36.1 mmol, 73.7%).

compound 1-2 Manufacturing

9.0 g (36.1 mmol) of Compound 1-1 and 7.6 g (43.3 mmol) of N-bromosugatimide were dissolved in 300 mL of dichloromethane and stirred at room temperature for 12 hours. After distilling off under reduced pressure, the obtained solid was washed with distilled water, methanol and hexane in order to obtain 9.6 g (29.3 mmol, 81.3%) of Compound 1-2 .

compound 1-3 Manufacturing

9.6 g (29.3 mmol) of compound 1-2 and 72.2 g (175.5 mmol) of iron oxalate dihydrate were mixed, heated at 205 ° C for 30 minutes, cooled to room temperature, extracted with EA and washed with distilled water. And recrystallized with toluene to obtain 5.2 g (17.6 mmol, 60.5%) of Compound 1-3 .

compound 1-4 Manufacturing

Compound 1-3 5.2 g (17.6 mmol), copper 0.6 g (8.8 mmol), 18- crown -6 0.2 g (0.9 mmol), K 2 CO 3 4.8 g (35.1 mmol) and 100 mL 1,2- dichloro-benzene And the mixture was stirred at reflux for 12 hours at 180 ° C. Cooled to room temperature, distilled under reduced pressure, extracted with MC and washed with distilled water. Dried over anhydrous MgSO ₄ and distilled under reduced pressure. The resulting residue was subjected to column separation to obtain 5.0 g (13.4 mmol, 76.5%) of Compound 1-4 .

compound One Manufacturing

Compound 1-4 5.0 g (13.4 mmol), 9- phenyl-anthracene-10-boronic acid 4.8 g (16.1 mmol), Pd (PPh 3) 4 0.8 g (0.7 mmol), 2M K 2 CO 3 aqueous solution of 20 mL, 100 mL of toluene and 50 mL of ethanol were added, and the mixture was refluxed and stirred for 12 hours. Washed with distilled water, extracted with EA, dried over anhydrous MgSO ₄ , distilled under reduced pressure, and the obtained residue was subjected to column separation to obtain 4.3 g (7.9 mmol, 58.8%) of Compound 1 .

[Preparation Example 2] Preparation of Compound 13

compound 2-1 Manufacturing

10.0 g (54.22 mmol) of cyanuric chloride is dissolved in 35 mL of THF and cooled to 0 ° C. 45.1 mL (135.56 mmol) of phenylmagnesium bromide (3.0M in diethylether) is added slowly and stirred at room temperature for 3 hours. The resulting solid is filtered under reduced pressure and washed with methanol and hexane. 9g (62%) of Compound 2-1 was obtained.

compound 2-2 Manufacturing

1-naphthalene boronic acid _{10.2 g (59.4 mmol), 4} 1.7 g (1.4 mmol), 2M K 2 CO 3 aqueous solution of 70 mL 1-bromo-2-benzene 10.0 g (49.5 mmol) nitro, Pd (PPh ₃₎ , 200 mL of toluene and 100 mL of ethanol were added, and the mixture was refluxed and stirred for 12 hours. Washed with distilled water, extracted with EA, dried over anhydrous MgSO ₄ , distilled under reduced pressure, and the obtained residue was subjected to column separation to obtain 9.0 g (36.1 mmol, 73.7%) of Compound 2-2 .

compound 2-3 Manufacturing

9.6 g (29.3 mmol) of compound 2-2 and 72.2 g (175.5 mmol) of iron oxalate dihydrate were mixed, heated at 205 ° C for 30 minutes, cooled to room temperature, extracted with EA and washed with distilled water. And recrystallized with toluene to obtain 5.2 g (17.6 mmol, 60.5%) of the compound 2-3 .

compound 13 Manufacturing

Dilute 575 mg (14.38 mmol) of NaH (60% in mineral oil) in 30 mL of DMF. 2.5 g (11.50 mmol) of Compound 13 is dissolved in 20 mL of DMF and added to the solution. After stirring for one hour at room temperature, 3.0 g (11.50 mmol) of compound 2-1 is dissolved in 20 mL of DMF and added to the solution. After stirring at room temperature for 3 hours, add 50 mL of water and filter the resulting solid under reduced pressure. The resulting solid is recrystallized from DMF and EA. 2.8 g (54%) of Compound 13 was obtained.

[Preparation Example 3] Preparation of Compound 33

compound 3-1 Manufacturing

4-Fluorophenylhydrazine hydrochloride (10.0 g, 61.5 mmol) was added to methanol (143 mL) and water (47 mL), and the mixture was stirred for 5 minutes. 8.7 mL (65.8 mmol) of b-tetralone was added and stirred vigorously at room temperature for one hour. The organic layer is extracted with MC. Dried over anhydrous MgSO ₄ and distilled under reduced pressure. Column separation was conducted to obtain 9.7 g (66%) of the compound 3-1 .

compound 3-2 Manufacturing

9.7 g (40.53 mmol) of the compound 3-1 , 11.6 g of Pd / C (10%) and 135 mL of xylene were charged and the mixture was refluxed at 150 ° C for 12 hours. After cooling to room temperature, the organic layer is extracted with MC. Dried over anhydrous MgSO ₄ and distilled under reduced pressure. Column separation afforded 8.3 g (87%) of compound 3-2 .

compound 33 Manufacturing

Dilute 531 mg (13.28 mmol) of NaH (60% in mineral oil) in 20 mL of DMF. 2.5 g (10.6 mmol) of the compound 3-2 was dissolved in 20 mL of DMF and added to the solution. After stirring for one hour at room temperature, 2.8 g (10.6 mmol) of the compound 2-1 is dissolved in 30 mL of DMF and added to the solution. After stirring at room temperature for 3 hours, add 50 mL of water and filter the resulting solid under reduced pressure. The resulting solid is recrystallized from DMF and EA. 2.8 g (56%) of Compound 33 was obtained.

[Preparation Example 4] Preparation of Compound 124

compound 4-1 Manufacturing

2-chloro-3-nitropyridine 25 g (157.6 mmol), phenylboronic acid 24.9 g (204.9 mmol), Pd (PPh 3) 4 5.4 g (4.73 mmol), K 2 CO 3 54.48 g (394.2 mmol), distilled water 150 mL of toluene, 300 mL of toluene and 100 mL of ethanol were added, and the mixture was stirred under reflux. After 12 hours, cool to room temperature and add distilled water. Extracted with MC and dried over anhydrous MgSO ₄ . After distillation under reduced pressure, the column is separated. 30 g (149.85 mmol, 95.45%) of Compound 4-1 was obtained.

compound 4-2 Manufacturing

30 g (149.85 mmol) of the compound 4-1 was added to 150 mL of triethyl phosphite, and the mixture was stirred at 180 占 폚 for 4 hours. After cooling to room temperature, it is distilled under reduced pressure. Column separation afforded 2.1 g (12.48 mmol, 8.37%) of the compound 4-2 .

compound 124 Manufacturing

Add 0.45 g (18.72 mmol, 60% in mineral oil) of NaH and 12 mL of DMF and dissolve 2.1 g (12.48 mmol) of compound 4- 2 in 20 mL of DMF. After stirring for 30 minutes, 3.6 g (13.73 mmol) of the compound 2-1 is dissolved in 25 mL of DMF. After stirring for 12 hours, distilled water is added and the resulting solid is filtered under reduced pressure. EA to obtain 2.6 g of compound 124 (6.50 mmol, 54.24%).

[Preparation Example 5] Preparation of Compound 125

compound 5-1 Manufacturing

2-chloropyridine 10 g (74.87 mmol), 2- chloroaniline 11.4 g (89.85 mmol), Pd 2 (dba) 3 4.0 g (4.40 mmol), tree -tert- butylphosphine (P (t-Bu) ₃ ) 11.7 mL (17.61 mmol) of 50% in xylene, 69 g (616.46 mmol) of KOt-Bu and 50 mL of 1,4-dioxane are placed in a pressurized flask and heated at 120 DEG C for 20 hours. The organic layer is extracted with MC. Dried over anhydrous MgSO ₄ and distilled under reduced pressure. The column was separated to obtain 1.3 g (10%) of the compound 5-1 .

compound 125 Manufacturing

Dilute 594 mg (14.86 mmol) of NaH (60% in mineral oil) in 20 mL of DMF. 2.0 g (11.89 mmol) of the compound 5-1 was dissolved in 20 mL of DMF and added to the solution. After stirring for one hour at room temperature, 3.1 g (11.89 mmol) of the compound 2-1 is dissolved in 30 mL of DMF and added to the solution. After stirring at room temperature for 3 hours, add 50 mL of water and filter the resulting solid under reduced pressure. The obtained solid was recrystallized from DMF and EA to obtain 3.7 g (77%) of the compound 125 .

Organic luminescent compounds 1 to 128 were prepared using the method of Preparation Example 1, and ¹ H NMR and MS / FAB of the organic luminescent compounds prepared in Table 1 were shown.

[Table 1]

[Example 1] Fabrication of an OLED device using an organic light emitting 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 Ω / □) obtained from a glass for OLED (manufactured by Samsung Corning) was subjected to ultrasonic cleaning using trichlorethylene, acetone, ethanol and distilled water sequentially and then stored in isopropanol Respectively.

Next, an ITO substrate was placed in a substrate folder of a vacuum deposition apparatus, and 4,4 ', 4 "-tris (N, N- (2-naphthyl) -phenylamino) triphenylamine -TNATA) was added and the chamber was evacuated until the degree of vacuum reached 10 ^-6 torr. Then, a current was applied to the cell to evaporate 2-TNATA to deposit a 60 nm thick hole injection layer on the ITO substrate.

The NPB -diphenyl-4,4'-diamine into the (NPB), by applying a current to the cell - Then, to another cell of the vacuum vapor-deposit device structure, N, N 'N, N -bis (α-naphthyl)' And evaporated to deposit 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. Compound 13 according to the present invention was added as a host to one cell in a vacuum evaporation apparatus and compound (piq) ₂ Ir (acac) having the following structure was added as a dopant to another cell, and then the two cells were heated ) ₂ Ir (acac) was deposited at a deposition rate of 4 to 10% by weight to deposit a light emitting layer with a thickness of 30 nm on the hole transport layer.

Then (p -phenylphenolato) Bis (2- methyl-8-quinolinato) as a hole blocking layer on the light emitting layer to aluminum (III) (BAlq) was vapor-deposited to a thickness of 5 nm, of the following structure as an electron transport layer tris (8- hydroxyquinoline-aluminum (III) (Alq) was deposited to a thickness of 20 nm, and lithium quinolate (Liq) having the following structure was deposited as an electron injecting layer to a thickness of 1 to 2 nm, Al cathode was deposited to a thickness of 150 nm to fabricate an OLED.

Each compound was purified by vacuum sublimation under 10 ^-6 torr and used as an OLED light emitting material.

[Example 2] Fabrication of an OLED device using an organic light emitting compound according to the present invention

The OLED was fabricated in the same manner as in Example 1 except for the hole blocking layer.

[Comparative Example 1] Luminescence characteristics of OLED device using conventional light emitting material

After the hole injection layer and the hole transport layer were formed in the same manner as in Example 1, CBP was added as another light emitting host material to another cell in the vacuum vapor deposition equipment, and (piq) ₂ Ir (acac) , And the two cells were heated together to deposit a light emitting layer with a thickness of 30 nm on the hole transport layer by depositing a deposition rate ratio of (piq) ₂ Ir (acac) at 4 to 10 wt%.

Then (p -phenylphenolato) Bis (2- methyl-8-quinolinato) as a hole blocking layer on the light emitting layer to aluminum (III) (BAlq) was vapor-deposited to a thickness of 5 nm, of the following structure as an electron transport layer tris (8- hydroxyquinoline-aluminum (III) (Alq) was deposited to a thickness of 20 nm, and lithium quinolate (Liq) having the following structure was deposited as an electron injecting layer to a thickness of 1 to 2 nm, Al cathode was deposited to a thickness of 150 nm to fabricate an OLED.

The luminous efficiencies of the organic light emitting compounds prepared in Examples 1 and 2 and Comparative Example 1 and OLED devices containing the conventional light emitting compounds were measured at 1,000 cd / m ² , respectively, and are shown in Table 2 below.

[Table 2]

From Table 2, it can be seen that the luminescent properties of the organic luminescent compounds developed in the present invention are superior to those of conventional materials. In addition, the device using the organic luminescent compound according to the present invention as a host material not only excels in luminescence characteristics but also can lower the driving voltage, thereby inducing an increase in power efficiency of 1.7 to 3.2 lm / W, thereby improving power consumption.

Claims (1)

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

Wherein A ring and B ring are independently a monocyclic or polycyclic aromatic ring, a monocyclic or polycyclic heteroaromatic ring, a 5- to 6-membered heteroaromatic ring fused with an aromatic ring, a 5-membered or 6-membered heteroaromatic ring fused with an aromatic ring, A 6-membered heteroaromatic ring is a fused single- or multi-ring aromatic ring, except that the rings A and B are simultaneously a single aromatic ring;
R ₁ , R ₂ and R ₃ are Independently of each other (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (C3-C30) heteroaryl, substituted or unsubstituted 5-membered To 7-membered heterocycloalkyl, a 5- to 7-membered heterocycloalkyl in which one or more substituted or unsubstituted aromatic rings are fused, a substituted or unsubstituted (C3-C30) cycloalkyl, a substituted or unsubstituted aromatic ring It is a fused (C3-C30) cycloalkyl, substituted or unsubstituted adamantyl, substituted or unsubstituted (C7-C30) alkyl, bicycloalkyl, cyano, NR ₁₁ R _12, one or BR ₁₃ R _14, PR _{15 R 16, P (= O} ) R 17 R 18 [R 11 to R ₁₈ independently represent a substituted or unsubstituted (C1-C30) alkyl, substituted or unsubstituted (C6-C30) aryl or substituted or unsubstituted Substituted or unsubstituted di (C1-C30) heteroaryl, substituted or unsubstituted tri (C1-C30) alkylsilyl, substituted or unsubstituted di Substituted or unsubstituted (C6-C30) arylsilyl, substituted or unsubstituted (C6-C30) aryl (C1-C30) alkyl, substituted or unsubstituted Substituted or unsubstituted (C6-C30) arylthio, substituted or unsubstituted (C1-C30) alkoxycarbonyl, substituted or unsubstituted Substituted or unsubstituted (C 1 -C 30) alkylcarbonyl, substituted or unsubstituted (C 6 -C 30) arylcarbonyl, substituted or unsubstituted (C 2 -C 30) alkenyl, Substituted or unsubstituted (C1-C30) alkylcarbonyloxy, substituted or unsubstituted (C6-C30) aryloxycarbonyl, substituted or unsubstituted (C1-C30) alkoxycarbonyloxy, substituted or unsubstituted (C3-C30) arylcarbonyloxy, substituted or unsubstituted (C6-C30) aryloxycarbonyloxy, carboxyl, nitro, hydroxy, C30) alkylene or (C 3-C30) alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring;
The hydrogen atoms of ring A and ring B may be further substituted with deuterium.