KR20170086277A - Organic light-emitting compounds and Organic light-emitting device comprising the same - Google Patents

Abstract

[화학식 2]

The present invention relates to an organic electroluminescent device comprising a first compound represented by the following formula (1) and a second compound represented by the following formula (2) in an organic layer interposed between a first electrode and a second electrode opposite to each other, The organic light emitting device according to the present invention can be advantageously used in various display and lighting industries because it has low driving voltage, excellent efficiency, and long life characteristics.
[Chemical Formula 1]

(2)

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic light-emitting compound and an organic light-

The present invention relates to an organic light emitting device capable of realizing excellent driving voltage, efficiency and long life characteristics.

The organic light emitting diode is a self light emitting type device having a wide viewing angle, excellent contrast, fast response time, excellent luminance, driving voltage and response speed characteristics, and multi-coloring.

In the case of using only one material as the light emitting material, the light emitting layer is most important factor for determining the light emitting property such as efficiency in the organic light emitting device, and the maximum light emitting wavelength shifts to a long wavelength due to intermolecular interaction, In order to increase the color purity and increase the luminous efficiency through energy transfer, a host / dopant system is used as a light emitting material to co-deposit the two materials. If necessary, two or more substances may be notarized.

In addition, although fluorescent materials are widely used up to now, the development of phosphorescent materials has been widely carried out because phosphorescent materials can improve the luminous efficiency up to 4 times theoretically as compared with fluorescent luminous materials in terms of mechanism of organic luminescence .

However, in the case of phosphorescence, it is difficult to synthesize stable host and dopant compounds despite high efficiency, and there are many problems to be applied due to instability due to high energy barrier at the interface of the light emitting layer. Particularly, the current efficiency is high, but the driving voltage is high, the power efficiency is low, and the device life is remarkably low. Therefore, a solution thereof is urgently needed.

Accordingly, it is an object of the present invention to provide an organic light-emitting compound and an organic light-emitting device including the organic light-emitting compound, which are excellent in efficiency of the organic light-emitting device, have a low driving voltage, and can improve lifetime characteristics.

The present invention provides an organic electroluminescent device comprising a first compound represented by the following formula (1) and a second compound represented by the following formula (2) in an organic layer interposed between a first electrode and a second electrode opposite to each other, to provide.

[Chemical Formula 1]

(2)

Specific structures of the first compound and the second compound represented by the formulas (1) and (2) will be described later.

INDUSTRIAL APPLICABILITY The organic light emitting diode according to the present invention can be utilized in various display and lighting industries because it has low driving voltage, excellent efficiency, and long life characteristics.

Hereinafter, the present invention will be described in more detail.

The organic light emitting device according to the present invention is characterized in that the first compound represented by the following formula (1) and the second compound represented by the following formula (2) in the organic layer between the first electrode and the second electrode facing each other, Or a compound thereof.

[Chemical Formula 1]

In the above formula (1)

Y ₁ , Y ₂ and Y ₃ are the same or different and each independently selected from N, O, S, CRR ', SiRR', GeRR ', Se, PR, BR and P At least one of Y ₁ , Y ₂ and Y ₃ is N.

B ₁ and B _{2 each} represent a hydrogen atom, a heavy hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, An alkylsilyl group having 3 to 50 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 50 carbon atoms, a substituted or unsubstituted ring-forming aromatic hydrocarbon group having 6 to 30 carbon atoms, and a substituted or unsubstituted ring- Lt; / RTI >

B ₁ and B ₂ may combine with each other to form a ring selected from a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms and a substituted or unsubstituted heterocyclic group having 5 to 30 ring carbon atoms .

R, R ', and R ₁ to R ₁₀ each independently represent hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms An arylamine group, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom, a substituted or unsubstituted silyl group, ratio A nitro group, a halogen group, a selenium group, a tellurium group, an amide group and an ester group, which are substituted or unsubstituted, or a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, N1 is 1, and n2 is an integer of 1 to 3, provided that at least one of R < 1 > and R < 2 >

(2)

In the above formula (2)

HAr is selected from a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms and a heterocyclic group having 5 to 30 ring carbon atoms substituted or unsubstituted.

L is a linking group which is a single bond or a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 60 carbon atoms, Or a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, and a substituted or unsubstituted C2 to C60 substituted or unsubstituted cycloalkylene group having 3 to 60 carbon atoms, Lt; / RTI >

n3, n4 and m1 are each independently an integer of 1 to 4, and a plurality of HAr and a plurality of L are the same or different from each other.

Az is a nitrogen-containing heterocycle represented by the following structural formula 1.

[Structural formula 1]

X ₁ to X ₆ are the same or different and each independently N or CR ₁₁ ; X ₁ to X ₆ Is at least one of N, and at least one of R ₁₁ is CR ₁₁ , and at least one of R ₁₁ is linked to L of the formula (2).

Wherein the one or more R < ₁₁ > s are the same or different from each other and each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms An arylamine group, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having a hetero atom O, N or S, A substituted or unsubstituted aryl group, a substituted silyl group, a substituted or unsubstituted germanium group, a substituted or unsubstituted boron group, a substituted or unsubstituted aluminum group, a carbonyl group, a phosphoryl group, an amino group, a nitrile group, a hydroxy group, a nitro group, , A tellurium group, an amide group, and an ester group, and may form a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero with groups adjacent to each other.

In addition, the L, HAr, B _1, B _2, R, R 'and R ₁ to R ₁₁ each may be further substituted with one or more substituents, wherein at least one substituent is an alkyl group having 1 to 60 carbon atoms, A cycloalkyl group having 3 to 60 carbon atoms, an aryl group having 6 to 60 carbon atoms, an alkoxy group having 1 to 60 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, An alkylsilyl group having 1 to 20 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, an arylalkylamino group having 1 to 50 carbon atoms, an alkenyl group having 2 to 60 carbon atoms, a cyano group, a halogen group and deuterium.

The carbon number range of the alkyl group or aryl group in the above "substituted or unsubstituted C1-C30 alkyl group" or "substituted or unsubstituted C5-C50 aryl group"Quot; means the total number of carbon atoms constituting the alkyl moiety or the aryl moiety when considered as unsubstituted without consideration.

Specific examples of the alkyl group used in the present invention include a methyl group, ethyl group, propyl group, isopropyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isoamyl group, hexyl group, , An octyl group, a stearyl group, a trichloromethyl group, and a trifluoromethyl group, and at least one hydrogen atom of the alkyl group may be substituted with a substituent selected from the group consisting of a deuterium atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a trifluoromethyl group, (in this case, "alkylsilyl group" hereinafter), a substituted or unsubstituted amino group (-NH _2, -NH (R), -N (R ') (R "), where R, R' and R" are each A hydrazine group, a hydrazone group, a carboxyl group, a sulfonic acid group, a phosphoric acid group, an alkyl group having 1 to 24 carbon atoms, an alkyl group having 1 to 24 carbon atoms (preferably an alkyl group having 1 to 24 carbon atoms) A halogenated alkyl group, an alkenyl group having 2 to 24 carbon atoms, an alkynyl group having 2 to 24 carbon atoms , Which it may be substituted with a heteroarylalkyl group having 1 to 24 carbon atoms heteroaryl group, having 5 to 24 aryl group, C 6 -C 24 aryl group, a C 3 -C 24 heteroaryl group, or having from 3 to 24 of the.

Specific examples of the alkoxy group used in the present invention include a methoxy group, an ethoxy group, a propoxy group, an isobutyloxy group, a sec-butyloxy group, a pentyloxy group, an isoamyloxy group and a hexyloxy group , The same substituent as in the case of the above-mentioned alkyl group can be substituted.

Specific examples of the halogen group used in the present invention include fluorine (F), chlorine (Cl), bromine (Br), iodine (I) and the like.

The aryloxy group used in the present invention means an -O-aryl radical, wherein the aryl group is as defined above, and specific examples include phenoxy, naphthoxy, anthracenyloxy, phenanthrenyloxy, fluorenyloxy, Indenyloxy and the like, and at least one hydrogen atom contained in the aryloxy group may be further substituted.

Specific examples of the silyl group used in the present invention include trimethylsilyl, triethylsilyl, triphenylsilyl, trimethoxysilyl, dimethoxyphenylsilyl, diphenylmethylsilyl, diphenylvinylsilyl, methylcyclobutylsilyl, dimethylpurylsilyl And the like.

The aryl group used in the present invention is an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination, and includes a single or fused ring system containing 5 to 7, preferably 5 or 6, Where a substituent is present, it can be fused with neighboring substituents to further form a ring.

Specific examples of the aryl group include a phenyl group, o-biphenyl group, m-biphenyl group, p-biphenyl group, o-terphenyl group, m-terphenyl group, p-terphenyl group, naphthyl group, anthryl group, , Aromatic groups such as a pyrenyl group, an indenyl group, a fluorenyl group, a tetrahydronaphthyl group, a perylene group, a crycenyl group, a naphthacenyl group and a fluoranthenyl group.

More specifically, at least one hydrogen atom of the aryl group may be substituted with at least one substituent selected from the group consisting of a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a silyl group, an amino group (-NH ₂ , -NH (R), -N (R ') (R "), R' and R" are independently of each other an alkyl group having 1 to 10 carbon atoms and in this case an "alkylamino group"), an amidino group, An alkyl group having 1 to 24 carbon atoms, a halogenated alkyl group having 1 to 24 carbon atoms, an alkenyl group having 1 to 24 carbon atoms, an alkynyl group having 1 to 24 carbon atoms, a heteroatom having 1 to 24 carbon atoms, An alkyl group having 6 to 24 carbon atoms, an aryl group having 6 to 24 carbon atoms, an arylalkyl group having 6 to 24 carbon atoms, a heteroaryl group having 2 to 24 carbon atoms, a heteroarylalkyl group having 2 to 24 carbon atoms,

The heteroaryl group used in the present invention may be any one selected from the following Structural Formulas 1 to 14:

In the above Structural Formulas 1 to 10,

T ₁ to T ₁₂ are the same or different and are each independently any one selected from C (R ₁₀₁ ), C (R ₁₀₂ ) (R ₁₀₃ ), N, N (R ₁₀₄ ) and, T ₁ to not is if the T ₁₂ at the same time all the carbon atoms, the R ₁₀₁ to R ₁₀₄ are the same or different and each independently represent hydrogen, deuterium, an alkyl group, a substituted or unsubstituted 1 to 30 carbon atoms with each other, optionally substituted Or a substituted or unsubstituted aryl group having 5 to 30 carbon atoms and a heteroaryl group having 2 to 30 carbon atoms having a substituted or unsubstituted heteroatom, O, N, S, or P, Is selected.

The above-mentioned [formula 3] may include a compound represented by the following formula [3] by a resonance structure according to the movement of electrons.

[Structural Formula 3-1]

In the above structural formula 3-1, T ₁ to T ₇ are the same as defined in [Structural formulas 1] to [Structural formula 10].

According to a preferred embodiment of the present invention, the above Structural Formulas 1 to 10 can be selected from the following Structural Formula 11.

[Structural Formula 11]

In the above structural formula 11,

X is the same as defined for R ₁ to R ₇ in the above formula (1), m is an integer of 1 to 11, and when m is 2 or more, plural Xs may be the same as or different from each other.

The first compound represented by formula (1) according to the present invention may be any one selected from the following formulas (H-1) to (H-108) It is not.

The second compound represented by formula (2) according to the present invention may be any one selected from the following formulas (E-1) to (E-100) It is not.

According to another aspect of the present invention, there is provided an organic light emitting diode comprising an organic layer between a first electrode and a second electrode facing each other, the organic layer including a light emitting layer, and a hole transport layer between the light emitting layer and the first electrode, And an electron transport layer between the light emitting layer and the second electrode.

According to an embodiment of the present invention, the light emitting layer includes a first compound represented by Formula 1 according to the present invention and a second compound represented by Formula 2, wherein the light emitting layer includes a dopant compound As shown in FIG.

According to an embodiment of the present invention, the mixing weight ratio of the first compound, the second compound, and the dopant compound may be 1: 0.01 to 99: 0.01 to 15. When the weight ratio of the first compound, the second compound and the dopant is in the above range, satisfactory energy transfer and luminescence can occur.

The light emitting layer of the organic light emitting device according to the present invention may further include a phosphorescent dopant in addition to the first and second compounds. The phosphorescent dopant is not particularly limited, May be at least one compound selected from compounds represented by the formula (J-1).

[General Formula A-1]

Wherein M is selected from the group consisting of metals of Groups 7, 8, 9, 10, 11, 13, 14, 15 and 16, preferably Ir, Pt, Pd, Rh, Re , Os, Tl, Pb, Bi, In, Sn, Sb, Te, Au and Ag. L ₁ , L ₂ and L ₃ are the same or different from each other as ligands, and each independently selected from the following structural formula [D], but are not limited thereto. In the following [Structural Formula D], * represents a site binding to the metal ion M.

[Structural formula D]

In the above structural formula D,

A substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C6-C50 aryl group, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C1- A substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 heteroaryl group, A substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, an unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms and a substituted or unsubstituted arylsilyl And the like.

Each R is independently selected from an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 40 carbon atoms, a heteroaryl group having 3 to 20 carbon atoms, a cyano group, a halogen group, deuterium and hydrogen And may be further substituted with one or more substituents.

Further, the R may be connected to each adjacent substituent by alkylene or alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring.

The L may be connected to an adjacent substituent by alkylene or alkenylene to form a spiro ring or a fused ring.

As one example, the dopant represented by the above-mentioned [formula A-1] may be any one selected from the following compounds, but is not limited thereto.

[Formula B-1]

In the above general formula B-1,

M ^A1 represents the same metal ion as defined in [formula A-1], and Y ^A11 , Y ^A14 , Y ^A15 and Y ^A18 Y ^A13 , Y ^A16 and Y ^A17 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom or a sulfur atom, and Y ^A12 , Y ^A13 , Y ^A16 and Y ^A17 each independently represent a substituted or unsubstituted carbon atom, L ^A11 , L ^A12 , L ^A13 and L ^A14 each represent a linking group as defined above, and Q ^A11 and Q ^A12 represent a partial structure containing an atom bonding to M ^A1 .

Exemplary structures of the compound represented by the above-mentioned general formula B-1 are shown below, but the present invention is not limited thereto.

[Formula C-1]

In the above general formula (C-1)

M ^B1 represents the same metal ion as defined from the following formula ^{A-1], Y B11,} Y B14, Y B15 and Y ^B18 each independently represents a carbon atom or a nitrogen ^{atom, Y B12, Y B13, Y} B16 And Y ^B17 each independently represent a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom or a sulfur atom, L ^B11 , L ^B12 , L ^B13 and L ^B14 represent a linking group, Q ^B11 and Q ^B12 represent ^Represents a partial structure containing an atom bonding to M ^B1 .

Exemplary structures of the compound represented by the above-mentioned general formula C-1 are shown below, but the present invention is not limited thereto.

[Formula D-1]

In the above general formula (D-1)

M ^C1 represents a metal ion as defined in [formula A-1], R ^C11 and R ^C12 each independently represent a hydrogen atom, a substituent which is connected to each other to form a 5-membered ring, Each of R ^C13 and R ^C14 independently represents a hydrogen atom, a substituent which is connected to each other to form a 5-membered ring, or a substituent which does not have any one to be connected to each other, and G ^C11 and G ^C12 each independently represent a nitrogen atom, a substituent Or an unsubstituted carbon atom, L ^C11 and L ^C12 represent a linking group, and Q ^C11 and Q ^C12 represent a partial structure containing an atom bonding to M ^C1 .

Exemplary structures of the compound represented by the above-mentioned general formula (D-1) are shown below, but the present invention is not limited thereto.

[Formula E-1]

In the above general formula E-1,

M ^D1 represents the same metal ion as defined from the following formula A-1], G ^D11, G ^D12 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom, J ^D11, J ^D12, J ^D13 and J ^D14 each independently represents an atomic group necessary for forming a five-membered ring, and L ^D11 and L ^D12 represent a linking group.

Exemplary structures of the compound represented by the above-mentioned formula (E-1) are as follows, but are not limited thereto.

[Formula F-1]

In the above general formula F-1,

M ^E1 represents the same metal ion as defined in [Formula A-1], J ^E11 and J ^E12 each independently represent an atom group necessary for forming a 5-membered ring, and G ^E11 , G ^E12 , G ^E13 and G ^E14 each independently represents a nitrogen atom, a substituted or unsubstituted carbon atom, and Y ^E11 , Y ^E12 , Y ^E13 and Y ^E14 each independently represent a nitrogen atom, a substituted or unsubstituted carbon atom.

Exemplary structures of the compound represented by the above-mentioned general formula F-1 are shown below, but are not limited thereto.

[Formula G-1]

In the above general formula G-1,

M ^F1 represents the same metal ion as defined in [formula A-1].

L ^F11 , L ^F12 and L ^F13 represent a linking group, R ^F11 , R ^F12 , R ^F13 and R ^F14 represent substituents, R ^F11 and R ^F12 , R ^F12 And R ^F13 , R ^F13 and R ^F14 may be connected to form a ring, wherein the ring formed by R ^F1 and R ^F12 , R ^F13 and R ^F14 is a 5-membered ring. And Q ^F11 and Q ^F12 represent a partial structure containing an atom bonding to M ^F1 .

Exemplary structures of the compound represented by the above-mentioned general formula G-1 are shown below, but the present invention is not limited thereto.

[Formula H-1] [Formula H-2] [Formula H-3]

In the above formulas H-1 to H-3,

R ¹¹ and R ¹² are substituents of alkyl, aryl or heteroaryl; And q11 and q12 may be an integer of 0 to 4, preferably 0 to 2, and may form a fused ring with substituents adjacent to each other.

When q11 and q12 are 2 to 4, a plurality of R11 and R12 may be the same or different.

L ¹ is a ligand which binds to platinum and is preferably a ligand capable of forming an ortho metal platinum complex, a nitrogen-containing heterocyclic ligand, a diketone ligand, or a halogen ligand, more preferably an ortho metal ) Ligand, a bipyridyl ligand or a phenanthroline ligand, which form a platinum complex.

n ¹ is an integer of 0 to 3, preferably 0, m ¹ is 1 or 2, and preferably 2.

It is preferable that n ¹ and m ¹ denote the metal complex represented by the general formula H-1 as a neutral complex.

In the above-mentioned general formula H-2,

R ²¹ , R ²² , n ² , m ² , q ²² and L ² are respectively the same as R ¹¹ , R ¹² , n ¹ , m ¹ , q ¹² and L ¹ , q ²¹ is an integer of 0 to 2 , 0 is preferable.

In the above-mentioned general formula H-3,

R ³¹ , n ³ , m ³ and L ³ are the same as R ¹¹ , n ¹ , m ¹ and L ¹ , q ³¹ is an integer of 0 to 8, preferably 0 to 2, desirable.

Examples of the specific compounds of the above-mentioned general formulas H-1 to H-3 are shown below, but the present invention is not limited thereto.

[Formula I-1]

In the above general formula I-1,

Ring A, ring B, ring C and ring D represents a nitrogen-containing heterocyclic ring which may have a substituent, and the remaining two rings may be substituted with an aryl ring or a hetero ring which may have a substituent And may form a condensed ring with ring A and ring B, ring A and ring C and / or ring B and ring D, respectively. X ¹ , X ² , X ³ and X ⁴ represent a nitrogen atom in which two of them coordinate to a platinum atom, and the remaining two represent a carbon atom or a nitrogen atom. Q ¹ , Q ² and Q ³ each independently represent a divalent atom (or a bond), but Q ¹ , Q ² and Q ³ do not simultaneously represent a bond. ^{Two of} Z ¹ , Z ² , Z ³ and Z ⁴ represent coordinate bond, and the remaining two represent a covalent bond, an oxygen atom or a sulfur atom.

Examples of the specific compounds of the above-mentioned general formula I-1 include, but are not limited to, the following.

[Formula J-1]

In the above general formula J-1,

M represents the same metal ion as defined in [formula A-1], Ar1 represents a substituted or unsubstituted cyclic structure, and two azomethine bonds (-C = N-) , The nitrogen atom (N) binds to the M, respectively, and forms a three-terminal ligand which is bonded to the M at the 3-position as a whole.

Further, in Ar 1, C represents a carbon atom constituting a ring structure represented by Ar 1. R 1 and R 2 may be the same or different and each represents a substituted or unsubstituted alkyl or aryl group, and L represents a one-dimensional ligand.

In the above general formula J-1, it is preferable that M is Pt. The above-mentioned Ar1 is preferably selected from a 5-membered ring, a 6-membered ring and condensed ring group thereof.

Examples of the specific compounds of the above-mentioned general formula J-1 include, but are not limited to, the following.

Hereinafter, the organic light emitting device according to the present invention will be described in more detail.

The organic light emitting device according to the present invention may include an anode, a hole transporting layer, a light emitting layer, an electron transporting layer, and a cathode, and may further include a hole injection layer and an electron injection layer, Further, a hole blocking layer or an electron blocking layer may be further formed, or an organic layer having various functions may be further included depending on the characteristics of the device.

An organic light emitting device and a method of manufacturing the same according to the present invention will be described. First, an anode electrode material is coated on a substrate to form an anode. As the substrate, a substrate used in a conventional organic light emitting device is used, and an organic substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling, and waterproofness is preferable. As the material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO) and the like which are transparent and excellent in conductivity are used.

A hole injecting layer material is formed on the anode by vacuum thermal deposition or spin coating. Subsequently, a hole transport layer is formed on the hole injection layer by vacuum thermal deposition or spin coating.

The material for the hole injection layer is not particularly limited as long as it is commonly used in the art. Specific examples thereof include 2-TNATA [4,4 ', 4 "-tris (2-naphthylphenyl-phenylamino) -triphenylamine] , NPD [N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'- biphenyl-4,4'-diamine], DNTPD [N, N'-diphenyl-N, N'-bis- [4- ] Can be used.

The material for the hole transport layer is not particularly limited as long as it is commonly used in the art and includes, for example, N, N'-bis (3-methylphenyl) -N, N'- -Biphenyl] -4,4'-diamine (TPD) or N, N'-di (naphthalene-1-yl) -N, N'-diphenylbenzidine (? -NPD).

Then, a light emitting layer may be laminated on the hole transport layer, and a hole blocking layer may be selectively formed on the light emitting layer by a vacuum deposition method or a spin coating method. In the case where holes are injected into the cathode through the organic light-emitting layer, the lifetime and the efficiency of the device are reduced, and thus the hole blocking layer plays a role of preventing such a problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level . In this case, the hole blocking material to be used is not particularly limited, but it is required to have an ionization potential higher than that of the light emitting compound while having electron transporting ability. Typically, BAlq, BCP, TPBI and the like can be used.

An electron transport layer is deposited on the hole blocking layer through a vacuum deposition method or a spin coating method, and then an electron injection layer is formed. A metal for cathode formation is vacuum deposited on the electron injection layer to form a cathode electrode, The device is completed. Here, as the metal for forming the cathode, lithium, magnesium, aluminum, aluminum-lithium, calcium, magnesium-magnesium, Mg-Ag), and a transmissive cathode using ITO or IZO can be used to obtain a top light-emitting device.

As the electron transporting layer material, a known electron transporting material can be used as a material that stably transports electrons injected from an electron injection electrode (cathode). Examples of known electron transporting materials include quinoline derivatives, especially tris (8-quinolinolate) aluminum (Alq3), TAZ, Balq, beryllium bis (benzoquinolin-10- olate: Bebq2), ADN, oxadiazole derivative PBD, BMD, BND, and the like.

At least one layer selected from the hole injecting layer, the hole transporting layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transporting layer and the electron injecting layer may be formed by a single molecular deposition method or a solution process, Means a method of forming a thin film by evaporating a material used as a material for forming each of the layers by heating or the like under a vacuum or a low pressure state and the solution process is used as a material for forming each of the layers Means a method of forming a thin film by a method such as ink jet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating and the like.

Further, the organic light emitting device according to the present invention can be used in a device selected from a flat panel display device, a flexible display device, a monochromatic or white flat panel illumination device, and a monochromatic or white flexible illumination device.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

Synthetic example  1: Synthesis of formula H-4

Synthetic example  1- (1): Synthesis of Intermediate 1-a

Intermediate 1-a was synthesized according to Reaction Scheme 1 below.

<Intermediate 1-a>

To a 500 mL round bottom flask was added 1- bromo-2-nitrobenzene (20 g, 99 mmol), 9,9'-dimethylfluorene-2-boronic acid (25.95 g, 109 mmol), tetrakis (2.3 g, 2 mmol) and potassium carbonate (27.4 g, 198 mmol), and add 140 mL of toluene, 100 mL of ethanol and 60 mL of water. The temperature of the reactor was raised to 80 캜 and stirred overnight. When the reaction is completed, the temperature of the reactor is lowered to room temperature, extracted with ethyl acetate, and the organic layer is separated. The organic layer was concentrated under reduced pressure and then separated by column chromatography to obtain <Intermediate 1-a>. (27.4 g, 87.8%).

Synthetic example  1- (2): Synthesis of Intermediate 1-b

Intermediate 1-b was synthesized according to Reaction Scheme 2 below.

<Reaction Scheme 2>

<Intermediate 1-a> <Intermediate 1-b>

<Intermediate 1-a> (27.4 g, 87 mmol) and triphenylphosphine (45.6 g, 174 mmol) were placed in a 500 mL reactor and 220 mL of 1,2-dichlorobenzene was added. The temperature of the reactor was raised and stirred overnight at 120 ° C. After completion of the reaction, the reaction solution was concentrated by heating, and then separated and purified by column chromatography to obtain <Intermediate 1-b>. (5.8 g, 23.6%).

Synthetic example  1- (3): Synthesis of intermediate 1-c

Intermediate 1-c was synthesized according to Reaction Scheme 3 below.

<Reaction Scheme 3>

<Intermediate 1-b> <Intermediate 1-c>

(17.2 g, 61 mmol), iodobenzene (14.9 g, 73 mmol) and bis (dibenzylideneacetone) palladium (0) (0.7 g, 1 mmol) were added to a 500 mL round bottom flask reactor. , Tri-tertiary butylphosphine tetrahydroborate (1.8 g, 6 mmol), sodium tertiary butoxide (11.7 g, 121 mmol) and 180 mL of xylene. The temperature of the reactor was raised and stirred at reflux overnight. The reaction solution was filtered and concentrated under reduced pressure. Separation and purification were conducted by column chromatography to obtain < Intermediate 1-c &gt;. (15.8 g, 72.4%).

Synthetic example  1- (4): Synthesis of Intermediate 1-d

Intermediate 1-d &gt; was synthesized according to Reaction Scheme 4 below.

<Reaction Scheme 4>

<Intermediate 1-c> <Intermediate 1-d>

<Intermediate 1-c> (15.8 g, 44 mmol) was added to a 250 mL round-bottomed flask reactor and dissolved in 130 mL of dimethylformamide. After the reaction solution was cooled to 0 ° C, N-bromosuccinimide (9.4 g, 53 mmol) was dissolved in 20 mL of dimethylformamide and added dropwise to the reaction solution. After completion of dropwise addition, the mixture was stirred overnight at room temperature. After completion of the reaction, the reaction mixture was extracted with ethyl acetate, heptane and water. The organic layer was concentrated under reduced pressure and then purified by column chromatography to obtain <Intermediate 1-d>. (14.7 g, 76.3%).

Synthetic example  1- (5): Synthesis of formula H-4

<Formula H-4> was synthesized according to Reaction Scheme 5 below.

<Reaction Scheme 5>

<Intermediate 1-d> <Formula H-4>

Intermediate 1-d was used in place of 1-bromo-2-nitrobenzene in Synthesis Example 1- (1), N-phenylcarbazole-3- (Formula H-4) was obtained by using the same method except that boronic acid was used. (7.6 g, 37.7%)

MS (MALDI-TOF): m / z 600.26 [M ^&lt; ⁺ &^gt;].

Synthetic example  2: Synthesis of formula H-17

Synthetic example  2- (1): Synthesis of intermediate 2-a

Intermediate 2-a was synthesized according to Scheme 6 below.

<Reaction Scheme 6>

<Intermediate 2-a>

Except that 2-bromoaniline was used in place of <Intermediate 1-b> in Synthesis Example 1- (3), and 4-iododibenzofurane was used in place of iodobenzene, <Intermediate 2-a >. (29.4 g, 85.2%).

Synthetic example  2- (2): Synthesis of intermediate 2-b

Intermediate 2-b was synthesized according to Scheme 7 below.

<Reaction Scheme 7>

<Intermediate 2-a> <Intermediate 2-b>

(29.4 g, 87 mmol), potassium carbonate (24 g, 174 mol), bis (dibenzylideneacetone) palladium (0) (5 g, 9 mmol) Add 300 mL of dimethylformamide and stir at 130 ° C. After completion of the reaction, the reaction mixture was cooled to room temperature and extracted with ethyl acetate, heptane and water. The organic layer was concentrated under reduced pressure and then purified by column chromatography to obtain <Intermediate 2-b>. (10.3 g, 46.1%).

Synthetic example  2- (3): Synthesis of intermediate 2-c

Intermediate 2-c was synthesized according to Scheme 8 below.

<Reaction Scheme 8>

<Intermediate 2-b> <Intermediate 2-c>

<Intermediate 2-c> was obtained using the same method except that <Intermediate 2-b> was used in place of <Intermediate 1-b> in Synthesis Example 1- (3). (11.8 g, 88.4%).

Synthetic example  2- (4): Synthesis of intermediate 2-d

<Intermediate 2-d> was synthesized according to the following Reaction Scheme 9.

<Reaction Scheme 9>

<Intermediate 2-c> <Intermediate 2-d>

<Intermediate 2-d> was obtained using the same method except that <Intermediate 2-c> was used in place of <Intermediate 1-c> in Synthesis Example 1- (4). (10.9 g, 74.7%).

Synthetic example  2- (5): Synthesis of formula H-17

<Formula H-17> was synthesized according to Reaction Scheme 10 below.

<Reaction formula 10>

<Intermediate 2-d> <Formula H-17>

Intermediate 2-d was used in place of 1-bromo-2-nitrobenzene in Synthesis Example 1- (1), and N-phenylcarbazole-3- (Formula H-17) was obtained using the same method except that boronic acid was used. (6.9 g, 45.4%).

MS (MALDI-TOF): m / z 574.20 [M ^&lt; ⁺ &^gt;

Synthetic example  3: Synthesis of formula H-26

Synthetic example  3- (1): Synthesis of intermediate 3-a

Intermediate 3-a was synthesized according to Scheme 11 below.

<Reaction Scheme 11>

<Intermediate 3-a>

Except that 4-iododibenzothiophene was used instead of 2-bromoaniline and iodobenzene in place of < Intermediate 1-b > in Synthesis Example 1- (3) a>. (19.1 g, 83.6%)

Synthetic example  3- (2): Synthesis of intermediate 3-b

Intermediate 3-b was synthesized according to Scheme 12 below.

<Reaction Scheme 12>

<Intermediate 3-a> <Intermediate 3-b>

<Intermediate 3-b> was obtained using the same method except that <Intermediate 3-a> was used in place of <Intermediate 2-a> in the above Synthesis Example 2- (2). (7.2 g, 48.9%).

Synthetic example  3- (3): Synthesis of intermediate 3-c

Intermediate 3-c was synthesized according to Scheme 13 below.

<Reaction Scheme 13>

<Intermediate 3-b> <Intermediate 3-c>

<Intermediate 3-c> was obtained using the same method except that Intermediate 3-b was used instead of Intermediate 1-b in Synthesis Example 1- (3). (8.1 g, 88%).

Synthetic example  3- (4): Synthesis of intermediate 3-d

Intermediate 3-d &gt; was synthesized according to the following Reaction Scheme 14.

<Reaction Scheme 14>

<Intermediate 3-c> <Intermediate 3-d>

<Intermediate 3-d> was obtained using the same method except that <Intermediate 3-c> was used in place of <Intermediate 1-c> in Synthesis Example 1- (4). (8.4 g, 84.6%).

Synthetic example  3- (5): Synthesis of formula H-26

<Formula H-26> was synthesized according to Reaction Scheme 15 below.

<Reaction Scheme 15>

<Intermediate 3-d> <Formula H-26>

Intermediate 3-d &gt; was obtained in the same manner as in Synthesis Example 1- (1), except that 1-bromo-2-nitrobenzene was used instead of N-phenylcarbazole- <Formula H-26> was obtained by the same method except that boronic acid was used. (3.8 g, 32.8%)

MS (MALDI-TOF): m / z 590.18 [M ^&lt; ⁺ &^gt;

Synthetic example  4: Synthesis of formula H-44

Synthetic example  4- (1): Synthesis of intermediate 4-a

Intermediate 4-a was synthesized according to Scheme 16 below.

<Reaction Scheme 16>

<Intermediate 4-a>

<Intermediate 4-a> was obtained in the same manner as in Synthesis Example 1- (3) except that 3-bromodibenzothiophene was used instead of 2-chloroaniline and iodobenzene in place of Intermediate 1-b. . (20.2 g, 85.8%)

Synthetic example  4- (2): Synthesis of intermediate 4-b

Intermediate 4-b was synthesized according to Scheme 17 below.

<Reaction Scheme 17>

<Intermediate 4-a> <Intermediate 4-b>

<Intermediate 4-b> was obtained using the same method except that <Intermediate 4-a> was used in place of <Intermediate 2-a> in the above Synthesis Example 2- (2). (8.4 g, 47.1%).

Synthetic example  4- (3): Synthesis of intermediate 4-c

Intermediate 4-c was synthesized according to Scheme 18 below.

<Reaction Scheme 18>

<Intermediate 4-b> <Intermediate 4-c>

<Intermediate 4-c> was obtained using the same method except that Intermediate 4-b was used instead of Intermediate 1-b in Synthesis Example 1- (3). (8.3 g, 77.3%).

Synthetic example  4- (4): Synthesis of intermediate 4-d

<Intermediate 4-d> was synthesized according to the following Reaction Scheme 19.

<Reaction Scheme 19>

<Intermediate 4-c> <Intermediate 4-d>

<Intermediate 4-c> (8.3 g, 24 mmol) was added to a 250 mL round bottom flask reactor and 90 mL of tetrahydrofuran was added to dissolve. The reaction solution was cooled to -78 deg. C under a nitrogen atmosphere. N-butyllithium (16 mL, 26 mmol) was slowly added dropwise to the cooled solution for 30 minutes, stirred at room temperature overnight, cooled again to -78 ° C, trimethylborate (3.2 g, 31 mmol) was added dropwise, Respectively. The reaction mixture was acidified by adding 2N hydrochloric acid dropwise, and the mixture was extracted with ethyl acetate. The organic layer was separated and concentrated under reduced pressure. N-hexane was added thereto to crystallize <Intermediate 4-d>. (6.1 g, 65.3%).

Synthetic example  4- (5): Synthesis of formula H-44

<Formula H-44> was synthesized according to Reaction Scheme 20 below.

<Reaction Scheme 20>

<Intermediate 4-d> <Formula H-44>

Instead of 3-bromo-N-phenylcarbazole and 9,9'-dimethylfluorene-2-boronic acid in place of 1-bromo-2-nitrobenzene in Synthesis Example 1- (1) d &gt; was used, the same method was used to obtain &lt; Formula H-44 &gt;. (2.9 g, 31.6%).

MS (MALDI-TOF): m / z 590.18 [M ^&lt; ⁺ &^gt;

Synthetic example  5: Synthesis of formula H-55

Synthetic example  5- (1): Synthesis of intermediate 5-a

Intermediate 5-a was synthesized according to Scheme 21 below.

<Reaction Scheme 21>

<Intermediate 5-a>

To a 1 L round bottom flask reactor were added 1-bromo-2-nitrobenzene (50 g, 248 mmol), bis (pinacolato) diboron (81.7 g, 322 mmol) (4.03 g, 5 mmol), potassium acetate (48.6 g, 495 mmol), and toluene (500 mL) were added, and the mixture was refluxed overnight. After completion of the reaction, the solution was passed through a celite pad, and the filtrate was concentrated under reduced pressure. Separation and purification were conducted by column chromatography to obtain &lt; Intermediate 5-a &gt;. (46.8 g, 75.9%)

Synthetic example  5- (2): Synthesis of intermediate 5-b

<Intermediate 5-b> was synthesized according to the following Reaction Scheme 22.

<Reaction Formula 22>

<Intermediate 5-b>

1-Hydroxydibenzofuran (30 g, 163 mmol) and pyridine (25.8 g, 3264 mmol) were placed in a 1 L round bottom flask reactor and 300 mL of chloroform was added to dissolve. The reaction solution was cooled to 0 ° C under a nitrogen atmosphere. Trifluoromethanesulfonic acid hydride (32.1 g, 196 mmol) was slowly added dropwise over 20 minutes to the cooled solution, which was warmed to room temperature and stirred overnight. To the reaction solution, 2N hydrochloric acid was added dropwise to acidify, and the mixture was stirred for 1 hour. The reaction mixture was extracted with ethyl acetate, and the organic layer was separated and concentrated under reduced pressure. Separation and purification were conducted by column chromatography to obtain Intermediate 5-b. (46.8 g, 90.9%)

Synthetic example  5- (3): Synthesis of intermediate 5-c

<Intermediate 5-c> was synthesized according to the following Reaction Scheme 23.

<Reaction Scheme 23>

<Intermediate 5-b> <Intermediate 5-a> <Intermediate 5-c>

<Intermediate 5-b> was used in place of 1-bromo-2-nitrobenzene in Synthesis Example 1- (1), and <Intermediate 5-a> was used in place of 9,9'-dimethylfluorene- <Intermediate 5-c> was obtained using the same method, except that (16.3 g, 89.1%).

Synthetic example  5- (4): Synthesis of intermediate 5-d

Intermediate 5-d was synthesized according to Scheme 24 below.

<Reaction Scheme 24>

<Intermediate 5-c> <Intermediate 5-d>

<Intermediate 5-d> was obtained using the same method except that Intermediate 5-c was used instead of Intermediate 1-a in Synthesis Example 1- (2). (9.4 g, 64.8%).

Synthetic example  5- (5): Synthesis of intermediate 5-e

Intermediate 5-e was synthesized according to Scheme 25 below.

<Reaction Scheme 25>

<Intermediate 5-d> <Intermediate 5-e>

<Intermediate 5-e> was obtained using the same method except that <Intermediate 5-d> was used instead of <Intermediate 1-b> in Synthesis Example 1- (3). (10.5 g, 86.2%).

Synthetic example  5- (6): Synthesis of intermediate 5-f

<Intermediate 5-f> was synthesized according to the following Reaction Scheme 26.

<Reaction Scheme 26>

<Intermediate 5-e> <Intermediate 5-f>

<Intermediate 5-f> was obtained using the same method except that <Intermediate 5-e> was used in place of <Intermediate 4-c> in the above Synthesis Example 4- (4). (7.9 g, 66.5%).

Synthetic example  5- (7): Synthesis of formula H-55

<Formula H-55> was synthesized according to Reaction Scheme 27 below.

<Reaction Scheme 27>

<Intermediate 5-f> <Formula H-55>

Instead of 3-bromo-N-phenylcarbazole and 9,9'-dimethylfluorene-2-boronic acid in place of 1-bromo-2-nitrobenzene in Synthesis Example 1- (1) f &gt; was used, the same method was used to obtain &lt; Formula H-55 &gt;. (5.1 g, 42.4%).

MS (MALDI-TOF): m / z 574.20 [M ^&lt; ⁺ &^gt;

Synthetic example  6: Synthesis of formula H-75

Synthetic example  6- (1): Synthesis of intermediate 6-a

Intermediate 6-a was synthesized according to Reaction Scheme 28 below.

<Reaction Scheme 28>

<Intermediate 6-a>

In the same manner as in Synthesis Example 1- (1), except that methyl 2-bromobenzoate instead of 1-bromo-2-nitrobenzene and dibenzothiophene-4- <Intermediate 6-a> was obtained using the same method except that boronic acid was used. (23.8 g, 85.2%).

Synthetic example  6- (2): Synthesis of intermediate 6-b

Intermediate 6-b was synthesized according to Scheme 29 below.

<Reaction Scheme 29>

<Intermediate 6-a> <Intermediate 6-b>

<Intermediate 6-a> (23.8 g, 75 mmol) was added to a 500 mL round bottom flask reactor and dissolved in 190 mL of tetrahydrofuran. The reaction solution was cooled to 0 占 폚 in a nitrogen atmosphere. To the cooled solution was added methyl magnesium bromide (87.2 mL, 262 mmol) slowly dropwise over 30 minutes and warmed to room temperature. After 1 hour, the reaction solution was heated to 60 DEG C and stirred overnight. To the reaction solution, 2N hydrochloric acid was added dropwise to acidify, and the mixture was stirred for 1 hour. The reaction mixture was extracted with ethyl acetate, and the organic layer was separated and concentrated under reduced pressure. The residue was purified by column chromatography to obtain Intermediate 6-b. (20.4 g, 85.7%).

Synthetic example  6- (3): Synthesis of intermediate 6-c

Intermediate 6-c was synthesized according to Reaction Scheme 30 below.

<Reaction Scheme 30>

<Intermediate 6-b> <Intermediate 6-c>

<Intermediate 6-b> (20.4 g, 64 mmol), 2 mL of hydrochloric acid and 140 mL of acetic acid were placed in a 250 mL round bottom flask reactor, and the temperature of the reactor was raised and stirred at reflux overnight. The resulting crystals were filtered and recrystallized from toluene and acetone to obtain Intermediate 6-c &gt;. (13.7 g, 71.2%).

Synthetic example  6- (4): Synthesis of intermediate 6-d

Intermediate 6-d &gt; was synthesized according to Reaction Scheme 31 below.

<Reaction Scheme 31>

<Intermediate 6-c> <Intermediate 6-d>

<Intermediate 6-d> was obtained using the same method except that <Intermediate 6-c> was used in place of <Intermediate 1-c> in Synthesis Example 1- (4). (14.9 g, 86.1%).

Synthetic example  6- (5): Synthesis of intermediate 6-e

Intermediate 6-e was synthesized according to Scheme 32 below.

<Reaction equation 32>

<Intermediate 6-d> <Intermediate 6-e>

Intermediate 6-d was used in place of 1-bromo-2-nitrobenzene in Synthesis Example 1- (1), N-phenylcarbazole-3- (Intermediate 6-e) was obtained by using the same method except that boronic acid was used. (15.8 g, 74.3%).

Synthetic example  6- (6): Synthesis of intermediate 6-f

<Intermediate 6-f> was synthesized according to the following Reaction Scheme 33.

<Reaction Scheme 33>

<Intermediate 6-e> <Intermediate 6-f>

<Intermediate 6-f> was obtained using the same method except that <Intermediate 6-e> was used in place of <Intermediate 4-c> in Synthesis Example 4- (4). (13.2 g, 77.3%).

Synthetic example  6- (7): Synthesis of formula H-75

<Formula H-75> was synthesized according to Reaction Scheme 34 below.

<Reaction formula 34>

<Intermediate 6-f> <Formula H-75>

Intermediate 6-f> was used instead of 3-bromobiphenyl and 9,9'-dimethylfluorene-2-boronic acid instead of 1-bromo-2-nitrobenzene in Synthesis Example 1- (1) &Lt; Formula H-75 &gt; was obtained by using the same method. (5.1 g, 32.6%).

MS (MALDI-TOF): m / z 693.25 [M ⁺ ] &^lt;

Synthetic example  7: Synthesis of formula E-19

Synthetic example  7- (1): Synthesis of Intermediate 7-a

Intermediate 7-a was synthesized according to Reaction Scheme 35 below.

<Reaction Scheme 35>

<Intermediate 7-a>

<Intermediate 7-a> was obtained using the same method except that methyl 2-bromobenzoate was used in place of 1-bromo-2-nitrobenzene in Synthesis Example 5- (1). (48.7 g, 79.9%).

Synthetic example  7- (2): Synthesis of Intermediate 7-b

Intermediate 7-b was synthesized according to Scheme 36 below.

<Reaction Formula 36>

<Intermediate 7-a> <Intermediate 7-b>

Instead of 2,2'-dibromodibenzothiophene and 9,9'-dimethylfluorene-2-boronic acid instead of 1-bromo-2-nitrobenzene in Synthesis Example 1- (1) -a> was used in place of Intermediate 7-b, the procedure of Intermediate 7-b was obtained. (24.9 g, 82.1%).

Synthetic example  7- (3): Synthesis of Intermediate 7-c

Intermediate 7-c was synthesized according to Scheme 37 below.

(Reaction Scheme 37)

<Intermediate 7-b <Intermediate 7-c>

<Intermediate 7-c> was obtained using the same method except that Intermediate 7-b was used instead of Intermediate 6-a in Synthesis Example 6- (2). (17.6 g, 70.7%)

Synthetic example  7- (4): Synthesis of intermediate 7-d

Intermediate 7-d was synthesized according to Scheme 38 below.

<Reaction Formula 38>

<Intermediate 7-c> <Intermediate 7-d>

<Intermediate 7-d> was obtained using the same method except that Intermediate 7-c was used instead of Intermediate 6-b in Synthesis Example 6- (3). (15.2 g, 90.5%).

Synthetic example  7- (5): Synthesis of Intermediate 7-e

Intermediate 7-e was synthesized according to Scheme 39 below.

<Reaction Scheme 39>

<Intermediate 7-d> <Intermediate 7-e>

<Intermediate 7-e> was obtained by using the same method except that <Intermediate 7-d> was used instead of <Intermediate 4-c> in the above Synthesis Example 4- (4). (9.4 g, 68.1%).

Synthetic example  7- (6): Synthesis of compound of formula E-19

E-19 was synthesized according to Scheme 40 below.

<Reaction formula 40>

<Intermediate 7-e> &Lt; Formula (E-19)

(3-bromophenyl) -4,6-diphenyl-1,3,5-triazine instead of 1-bromo-2-nitrobenzene in Synthesis Example 1- (1) (E-19) was obtained in the same manner as in Example 1, except that <Intermediate 7-e> was used instead of dimethylfluorene-2-boronic acid. (8.2 g, 49.4%)

MS (MALDI-TOF): m / z 607.21 [M ⁺ ] &^lt;

Synthetic example  8: Synthesis of formula E-60

Synthetic example  8- (1): Synthesis of intermediate 8-a

Intermediate 8-a was synthesized according to Reaction Scheme 41 below.

<Reaction Scheme 41>

<Intermediate 8-a>

Except that 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine was used instead of 1-bromo-2-nitrobenzene in Synthesis Example 5- (1) , <Intermediate 8-a> was obtained using the same method. (15.9 g, 70.9%).

Synthetic example  8- (2): Synthesis of the compound of the formula E-60

<Formula E-60> was synthesized according to Reaction Scheme 42 below.

<Reaction Scheme 42>

<Intermediate 8-a> <Intermediate 3-d> <E-60>

<Intermediate 3-d> was used in place of 1-bromo-2-nitrobenzene in Synthesis Example 1- (1), and <Intermediate 8-a> was used in place of 9,9'-dimethylfluorene- <Formula (E-60)> was obtained using the same method, except that (4.6 g, 30.5%).

MS (MALDI-TOF): m / z 656.20 [M ⁺ ] &^lt;

Example  1: Fabrication of organic light emitting device

The ITO glass was patterned to have a light emitting area of 2 mm x 2 mm and then cleaned. After the substrate was mounted in a vacuum chamber, the substrate pressure was adjusted to 1 x 10 &lt; ^-6 &gt; torr. Then, the organic material was coated on the ITO with HATCN (50 ANGSTROM), NPD (900 ANGSTROM) The weight ratio of H-4 and E-19 of the second compound was 5: 5, and GD was doped with 7% to form a 400 Å thick light emitting layer. The films were deposited in the order of ET: Liq = 1: 1 (300 Å), Liq (10 Å), and Al (1,000 Å).

[HATCN]  [NPD]

[ET] [Liq] [GD]

Example  2

An organic light emitting device was fabricated in the same manner as in Example 1, except that E-60 was used instead of E19 in forming the light emitting layer.

Example  3

An organic light emitting device was fabricated in the same manner as in Example 1 except that E-93 was used instead of E19 in forming the light emitting layer.

Example  4

An organic light emitting device was fabricated in the same manner as in Example 1, except that the compound represented by the formula H-17 was used instead of the compound represented by the formula H-4 in forming the light emitting layer.

Example  5

An organic light emitting device was fabricated in the same manner as in Example 1 except that the compound represented by the formula H-17 was used instead of the compound represented by the formula H-4 and the compound represented by the formula E-60 was used instead of the compound represented by the formula E19.

Example  6

An organic light emitting device was fabricated in the same manner as in Example 1 except that the compound represented by the formula H-17 was used instead of the compound represented by the formula H-4 and the compound represented by the formula E-93 was used instead of the compound represented by the formula E19.

Example  7

An organic light emitting device was fabricated in the same manner as in Example 1 except for using the compound represented by the formula H-26 instead of the compound represented by the formula H-4.

Example  8

An organic light emitting device was fabricated in the same manner as in Example 1 except for using the compound of the formula H-26 instead of the compound of the formula H-4 and the compound of the formula E-60 instead of the compound of the formula E19.

Example  9

An organic light emitting device was fabricated in the same manner as in Example 1 except that the compound represented by the formula H-26 was used instead of the compound represented by the formula H-4 and the compound represented by the formula E-93 was used instead of the compound represented by the formula E19.

Example  10

An organic light emitting device was fabricated in the same manner as in Example 1, except that the compound represented by the formula H-44 was used instead of the compound represented by the formula H-4 in forming the light emitting layer.

Example  11

An organic light emitting device was fabricated in the same manner as in Example 1 except that the compound represented by the formula H-44 was used instead of the compound represented by the formula H-4 and the compound represented by the formula E-60 was used instead of the compound represented by the formula E19.

Example  12

An organic light emitting device was fabricated in the same manner as in Example 1 except that the compound represented by the formula H-44 was used instead of the compound represented by the formula H-4 and the compound represented by the formula E-93 was used instead of the compound represented by the formula E19.

Example  13

An organic light emitting device was fabricated in the same manner as in Example 1 except for using the compound represented by the formula H-55 instead of the compound represented by the formula H-4 in forming the light emitting layer.

Example  14

An organic light emitting device was fabricated in the same manner as in Example 1 except that a compound represented by the formula H-55 was used instead of the compound represented by the formula H-4 and a compound represented by the formula E-60 was used instead of the compound represented by the formula E19.

Example  15

An organic light emitting device was fabricated in the same manner as in Example 1 except that the compound represented by the formula H-55 was used instead of the compound represented by the formula H-4 and the compound represented by the formula E-93 was used instead of the compound represented by the formula E-5 .

Example  16

An organic light emitting device was fabricated in the same manner as in Example 1 except that the compound represented by the formula H-75 was used instead of the compound represented by the formula H-4 in forming the light emitting layer.

Example  17

An organic light emitting device was fabricated in the same manner as in Example 1 except that the compound represented by the formula H-75 was used instead of the compound represented by the formula H-4 and the compound represented by the formula E-60 was used instead of the compound represented by the formula E19.

Example  18

An organic light emitting device was fabricated in the same manner as in Example 1 except that the compound represented by the formula H-75 was used instead of the compound represented by the formula H-4 and the compound represented by the formula E-93 was used instead of the compound represented by the formula E19.

Comparative Example  1 to 9

An organic light emitting device was fabricated in the same manner as in Example 1 except that Co-evaporation was carried out at a weight ratio of H-4 to E-93 and GD in a weight ratio of 100: 7 at the time of forming the light emitting layer.

Evaluation example

The driving voltage, luminance, luminescent color, and lifetime of the organic luminescent devices of Examples 1 to 18 and Comparative Examples 1 to 9 are shown in Table 1 below.

[Table 1]

As shown in Table 1, the organic light emitting devices of Examples 1 to 18 according to the present invention have excellent driving voltage and efficiency as compared with the organic light emitting devices of Comparative Examples 1 to 9, and have remarkably improved lifetime characteristics Which can be useful in various display and lighting industries.

Claims (10)

A first electrode; A second electrode facing the first electrode; And an organic layer interposed between the first electrode and the second electrode,
Wherein the organic layer comprises (a) a first compound represented by the following formula (1) and (b) a second compound represented by the following formula (2)
[Chemical Formula 1]

In the above formula (1)
Y ₁ , Y ₂ and Y ₃ are the same or different and are each independently selected from N, O, S, CRR ', SiRR', GeRR ', Se, PR, BR and P
At least one of Y ₁ , Y ₂ and Y ₃ is N,
B ₁ and B _{2 each} represent a hydrogen atom, a heavy hydrogen atom, a halogen atom, a cyano group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, A substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, a substituted or unsubstituted alkylthio group having 1 to 20 carbon atoms, a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, An alkylsilyl group having 3 to 50 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 50 carbon atoms, a substituted or unsubstituted ring-forming aromatic hydrocarbon group having 6 to 30 carbon atoms, and a substituted or unsubstituted ring- Lt; / RTI &gt; and &lt; RTI ID = 0.0 &gt;
B ₁ and B ₂ may combine with each other to form a ring selected from a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms and a substituted or unsubstituted heterocyclic group having 5 to 30 ring carbon atoms ,
R, R ', and R ₁ to R ₁₀ each independently represent hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted carbon number A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms An arylamine group, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having O, N or S as a hetero atom, a substituted or unsubstituted silyl group, ratio A nitro group, a halogen group, a selenium group, a tellurium group, an amide group and an ester group, which are substituted or unsubstituted, or a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, And may form a condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero with groups adjacent to each other,
n1 is 1, n2 is an integer of 1 to 3,

(2)

In the above formula (2)
HAr is selected from a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms and a substituted or unsubstituted ring heterocyclic group having 5 to 30 carbon atoms,
L is a linking group which is a single bond or a substituted or unsubstituted alkylene group having 1 to 60 carbon atoms, a substituted or unsubstituted alkenylene group having 2 to 60 carbon atoms, a substituted or unsubstituted alkynylene group having 2 to 60 carbon atoms, Or a substituted or unsubstituted heterocycloalkylene group having 2 to 60 carbon atoms, a substituted or unsubstituted arylene group having 6 to 60 carbon atoms, and a substituted or unsubstituted C2 to C60 substituted or unsubstituted cycloalkylene group having 3 to 60 carbon atoms, Lt; RTI ID = 0.0 &gt;
n3, n4 and m1 are each independently an integer of 1 to 4, a plurality of HAr and a plurality of L are the same or different from each other,
Az is a nitrogen-containing heterocycle represented by the following structural formula 1,
[Structural formula 1]

X ₁ to and X ₆ are the same or different and are each independently N or CR ₁₁ with each other, the X ₁ to X are at least one of ₆ N, at least one is CR _11, at least one R ₁₁ is the And is linked to L of formula (2)
Wherein the one or more R &lt; ₁₁ &gt; s are the same or different from each other and each independently represents hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, A substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms, a substituted or unsubstituted alkylamine group having 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy group having 5 to 30 carbon atoms An arylamine group, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 50 carbon atoms having a hetero atom O, N or S, A substituted or unsubstituted aryl group, a substituted silyl group, a substituted or unsubstituted germanium group, a substituted or unsubstituted boron group, a substituted or unsubstituted aluminum group, a carbonyl group, a phosphoryl group, an amino group, a nitrile group, a hydroxy group, a nitro group, , A tellurium group, an amide group, and an ester group, and may form a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero with groups adjacent to each other. The method according to claim 1,
Wherein each of the L, HAr, B ₁ , B ₂ , R, and R ₁ and R ₁ to R ₁₁ may be further substituted with one or more substituents each independently selected from the group consisting of an alkyl group having 1 to 60 carbon atoms, An alkyl group having 1 to 60 carbon atoms, a cycloalkyl group having 3 to 60 carbon atoms, an aryl group having 6 to 60 carbon atoms, an alkoxy group having 1 to 60 carbon atoms, an aryloxy group having 6 to 30 carbon atoms, an alkylamino group having 1 to 20 carbon atoms, An arylsilyl group having 6 to 30 carbon atoms, an arylalkylamino group having 1 to 50 carbon atoms, an alkenyl group having 2 to 60 carbon atoms, a cyano group, a halogen group and deuterium. The method according to claim 1,
Wherein the organic layer includes a light emitting layer, a hole transporting layer between the light emitting layer and the first electrode, and an electron transporting layer between the light emitting layer and the second electrode,
Wherein the light emitting layer comprises a first compound represented by Formula 1 and an electron second compound represented by Formula 2 in the light emitting layer. The method according to claim 1,
Wherein the light emitting layer comprises a phosphorescent dopant compound. The method according to claim 1,
Wherein the weight ratio of the first compound, the second compound, and the phosphorescent dopant compound is 1: 0.01 to 99: 0.01 to 15. The method according to claim 1,
Wherein the first compound represented by Formula 1 is any one selected from the following Formulas H-1 to H-108:

The method according to claim 1,
Wherein the second compound represented by Formula 2 is any one selected from the following Formulas E-1 to E-100:

The method according to claim 1,
Wherein the organic light emitting device comprises one or more light emitting layers emitting blue, red or green light to emit white light. An illumination comprising the organic light-emitting device according to claim 1. A display device comprising the organic light-emitting device according to claim 1.