KR102372232B1 - Organic light-emitting compounds and Organic light-emitting device comprising the same - Google Patents

Abstract

[화학식 2]

The present invention relates to an organic light emitting 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 facing each other. As a result, the organic light emitting diode according to the present invention has a low driving voltage, excellent efficiency, and can implement long life characteristics, so that it can be usefully used in various display and lighting industries.
[Formula 1]

[Formula 2]

Description

Organic light-emitting compounds and organic light-emitting devices comprising the same

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

An organic light emitting diode (OLED) is a self-luminous device, and has a wide viewing angle, excellent contrast, fast response time, excellent luminance, driving voltage and response speed characteristics, and multicolorization.

In an organic light emitting diode, the most important factor that determines the light emitting characteristics such as efficiency is the light emitting material, and when only one material is used for the light emitting layer as the light emitting material, the maximum emission wavelength shifts to a longer wavelength due to intermolecular interaction, and the color purity decreases or light emission Since there is a problem in that the efficiency of the device is reduced due to the attenuation effect, the two materials are co-deposited using a host/dopant system as a light emitting material in order to increase color purity and increase luminous efficiency through energy transfer. If necessary, two or more materials may be co-deposited.

In addition, although fluorescent materials have been widely used up to now, research on the development of phosphorescent materials has been widely conducted in that they can theoretically improve luminous efficiency up to 4 times compared to fluorescent materials due to the mechanism of organic light emission. .

However, in the case of phosphorescence, it is difficult to synthesize a stable host and dopant compound despite high efficiency, and there are many problems in application due to instability due to a high energy barrier at the light emitting layer interface. In particular, the current efficiency is high, but the driving voltage is high, and thus the power efficiency is lowered, and there is a problem that the device lifespan is remarkably low, so a solution is urgently needed.

Accordingly, the present invention is to solve the above problems, and to provide an organic light emitting compound having excellent efficiency of the organic light emitting device, a low driving voltage, and improving lifespan characteristics, and an organic light emitting device including the same.

The present invention provides an organic light emitting 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 the first and second electrodes facing each other to provide.

[Formula 1]

[Formula 2]

Specific structures of the first compound and the second compound respectively represented by the [Formula 1] and [Formula 2] will be described later.

The organic light emitting diode according to the present invention has a low driving voltage, excellent efficiency, and can implement long life characteristics, so it can be usefully used in various display and lighting industries.

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

The organic light emitting device according to the present invention is a first compound represented by the following [Formula 1] and a second represented by the following [Formula 2] in the organic layer between the first and second electrodes facing each other, preferably in the light emitting layer It is characterized in that it contains a compound.

[Formula 1]

In the above [Formula 1],

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

B ₁ and B ₂ are hydrogen, deuterium, a halogen atom, a cyano group, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group, a substituted or unsubstituted C 1 to C 20 of an alkoxy group, 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, a substituted or unsubstituted 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 aromatic hydrocarbon group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted ring carbon number 5 to It is selected from the heterocyclic group of 30.

The B ₁ and B ₂ may be combined 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 are each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, substituted or unsubstituted C A 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, substituted or An unsubstituted C1-C30 alkylthioxy group, a substituted or unsubstituted C5-C30 arylthioxy group, a substituted or unsubstituted C1-C30 alkylamine group, a substituted or unsubstituted C5-30 An arylamine group, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having O, N or S as a heteroatom, a substituted or unsubstituted silyl group, a substituted or unsubstituted silyl group, or An 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 hydroxyl group, a nitro group, a halogen group, a selenium group, a tellurium group, an amide group, and It is selected from the group consisting of an ester group, and may form a condensed ring of aliphatic, aromatic, aliphatic hetero or aromatic hetero with groups adjacent to each other, n1 is 1, and n2 is an integer of 1 to 3.

[Formula 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 heterocyclic group having 5 to 30 ring carbon atoms.

L is a linking group, a single bond or a substituted or unsubstituted C 1 to C 60 alkylene group, a substituted or unsubstituted C 2 to C 60 alkenylene group, a substituted or unsubstituted C 2 to C 60 alkynylene group, substituted Or an unsubstituted C 3 to C 60 cycloalkylene group, a substituted or unsubstituted C 2 to C 60 heterocycloalkylene group, a substituted or unsubstituted C 6 to C 60 arylene group, and a substituted or unsubstituted C 2 to C 60 It is selected from the heteroarylene group of.

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

Az is a nitrogen-containing ring represented by the following [Structural Formula 1].

[Structural Formula 1]

X _One To X ₆ Are the same as or different from each other, each independently N or CR ₁₁ , wherein X _One To X ₆ At least one of them is N, at least one is CR ₁₁ , and at least one R ₁₁ is connected to L in [Formula 2].

The one or more R ₁₁ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C number A 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, substituted or An unsubstituted C1-C30 alkylthioxy group, a substituted or unsubstituted C5-C30 arylthioxy group, a substituted or unsubstituted C1-C30 alkylamine group, a substituted or unsubstituted C5-30 An arylamine group, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted heteroaryl group having O, N or S as a heteroatom, a substituted or unsubstituted silyl group, a substituted or unsubstituted silyl group, or An 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 hydroxyl group, a nitro group, a halogen group, a selenium group, a tellurium group, an amide group, and It is selected from the group consisting of an ester group, and may form a condensed ring of 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 may each be further substituted with one or more substituents, wherein the one or more substituents are an alkyl group having 1 to 60 carbon atoms, carbon number A heteroaryl group having 5 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 alkylamino group having 1 to 20 carbon atoms. It is selected from 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.

In addition, the carbon number range of the alkyl group or aryl group in the "substituted or unsubstituted alkyl group having 1 to 30 carbon atoms", or "a substituted or unsubstituted aryl group having 5 to 50 carbon atoms", etc. It refers to the total number of carbon atoms constituting the alkyl portion or the aryl portion when viewed as unsubstituted without consideration.

Meanwhile, specific examples of the alkyl group used in the present invention include a methyl group, an ethyl group, a propyl group, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an iso-amyl group, a hexyl group, a heptyl group. , octyl group, stearyl group, trichloromethyl group, trifluoromethyl group, etc., and at least one hydrogen atom of the alkyl group is a deuterium atom, a halogen atom, a hydroxy group, a nitro group, a cyano group, a trifluoromethyl group, a silyl group (referred to as "alkylsilyl group" in this case), a substituted or unsubstituted amino group (-NH ₂ , -NH(R), -N(R')(R"), where R, R' and R" are each Independently an alkyl group having 1 to 24 carbon atoms (referred to as “alkylamino group” in this case), an amidino group, 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 Halogenated alkyl group, C2-C24 alkenyl group, C2-C24 alkynyl group, C1-C24 heteroalkyl group, C5-C24 aryl group, C6-C24 arylalkyl group, C3-C24 hetero It may be substituted with an aryl group or a heteroarylalkyl group having 3 to 24 carbon atoms.

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 iso-amyloxy group, a hexyloxy group, and the like. , may be substituted with the same substituents as in the case of the alkyl group.

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 thereof include phenoxy, naphthoxy, anthracenyloxy, phenanthrenyloxy, fluorenyloxy, indenyloxy and the like, and one or more hydrogen atoms included 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, dimethylfurylsilyl and the like.

The aryl group used in the present invention is an organic radical derived from an aromatic hydrocarbon by removal of one hydrogen, and includes a single or fused ring system containing 5 to 7 members, preferably 5 or 6 members, and the aryl group If there is a substituent, it may be fused with a neighboring substituent 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, phenanthryl group and aromatic groups such as , pyrenyl, indenyl, fluorenyl, tetrahydronaphthyl, peryleneyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like.

In addition, the aryl group may also be further substituted with one or more substituents, and more specifically, at least one hydrogen atom of the aryl group is a deuterium atom, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a silyl group, an amino group (-NH ₂ , -NH(R), -N(R')(R"), R' and R" are each independently an alkyl group having 1 to 10 carbon atoms, in this case referred to as an "alkylamino group"), amidino group, hydrazine group, hydrazone group, carboxyl group, sulfonic acid group, phosphoric acid group, C1-C24 alkyl group, C1-C24 halogenated alkyl group, C1-C24 alkenyl group, C1-C24 alkynyl group, C1-C24 hetero It may be substituted with an alkyl group, 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, or the like.

The heteroaryl group used in the present invention may be any one selected from the following [Formula 1] to [Formula 14].

In the [Structural Formula 1] to [Structural Formula 10],

T ₁ to T ₁₂ are the same as or different from each other, and each independently may be any one selected from C(R ₁₀₁ ), C(R ₁₀₂ )(R ₁₀₃ ), N, N(R ₁₀₄ ), O and S and T ₁ to T ₁₂ are not all carbon atoms at the same time, and R ₁₀₁ to R ₁₀₄ are the same or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, substituted or an unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms having O, N, S or P as a heteroatom. is chosen

In addition, the [Structural Formula 3] may include a compound represented by the following [Structural Formula 3-1] by a resonance structure according to the movement of electrons.

[Structural Formula 3-1]

In the [Formula 3-1], T ₁ to T ₇ are the same as defined in [Formula 1] to [Formula 10].

According to a preferred embodiment of the present invention, the [Structural Formula 1] to [Structural Formula 10] may be selected from the following [Structural Formula 11].

[Structural Formula 11]

In the [Structural Formula 11],

X is the same as the definition of R ₁ to R ₇ in [Formula 1], m is an integer of 1 to 11, and when m is 2 or more, a plurality of Xs may be the same or different from each other.

The first compound represented by [Formula 1] according to the present invention may be any one specifically selected from the following <Formula H-1> to <Formula H-108>, whereby the range of [Formula 1] is limited it is not going to be

The second compound represented by [Formula 2] according to the present invention may be any one specifically selected from the following <Formula E-1> to <Formula E-100>, whereby the range of [Formula 2] is limited it is not going to be

In addition, the organic light emitting device according to the present invention includes an organic layer between the opposing first electrode and the second electrode, the organic layer includes a light emitting layer, and a hole transport layer between the light emitting layer and the first electrode, An electron transport layer is included between the light emitting layer and the second electrode.

The light emitting layer is characterized in that it comprises a first compound represented by [Formula 1] and a second compound represented by [Formula 2] according to the present invention, and according to an embodiment of the present invention, the light emitting layer is a dopant compound may further include.

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 mixing weight ratio of the first compound, the second compound, and the dopant is within the above range, satisfactory energy transfer and light emission may occur.

In addition, 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, and the phosphorescent dopant is not particularly limited, but the following [General Formula A-1] to [General Formula A-1] It may be at least one compound selected from compounds represented by Formula J-1].

[General Formula A-1]

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. In addition, the L ₁ , L ₂ and L ₃ are the same as or different from each other as a ligand, and may each independently include any one selected from the following [Structural Formula D], but are not limited thereto. In addition, * in the following [Structural Formula D] represents a site binding to the metal ion M.

[Structural Formula D]

In the [Structural Formula D],

Wherein R is different or the same as each other and each independently hydrogen, deuterium, halogen, cyano group, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 50 aryl group, a substituted or unsubstituted A heteroaryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 30 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, substituted or An unsubstituted C1-C30 alkylamino group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C6-C30 arylamino group, and a substituted or unsubstituted C6-C30 arylsilyl group It may be any one selected from the group.

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 It may be further substituted with one or more substituents.

In addition, R may be connected to each adjacent substituent with alkylene or alkenylene to form an alicyclic ring and a monocyclic or polycyclic aromatic ring.

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

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

[General Formula B-1]

In the above [General Formula B-1],

M ^A1 represents the same metal ion as defined in [General Formula A-1], and also Y ^A11 , Y ^A14 , Y ^A15 and Y ^A18 each independently represents a carbon atom or a nitrogen atom, Y ^A12 , Y ^A13 , Y ^A16 and Y ^A17 each independently represents a substituted or unsubstituted carbon atom, a substituted or unsubstituted nitrogen atom, an oxygen atom, or a sulfur 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 bonded to M ^A1 .

An exemplary structure of the compound represented by the [General Formula B-1] is as follows, but is not limited thereto.

[General formula C-1]

In the above [general formula C-1],

M ^B1 represents the same metal ion as defined in [General 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 represents 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 , L ^B14 represents a linking group, Q ^B11 , Q ^B12 are Represents a partial structure containing an atom bonded to M ^B1 .

An exemplary structure of the compound represented by the [General Formula C-1] is as follows, but is not limited thereto.

[General formula D-1]

In the above [general formula D-1],

M ^C1 represents the same metal ion as defined in [General Formula A-1] for the metal ion, R ^C11 , R ^C12 are each independently a hydrogen atom, a substituent that connects to each other and forms a 5-membered ring, Represents a substituent, R ^C13 , R ^C14 each independently represents a hydrogen atom, a substituent connected to each other to form a 5-membered ring, and a substituent having nothing to connect to each other, G ^C11 , G ^C12 are each independently a nitrogen atom, a substitution or an unsubstituted carbon atom, L ^C11 , L ^C12 represents a linking group, and Q ^C11 , Q ^C12 represents a partial structure containing an atom bonded to M ^C1 .

An exemplary structure of the compound represented by the [General Formula D-1] is as follows, but is not limited thereto.

[General formula E-1]

In the above [general formula E-1],

M ^D1 represents the same metal ion as defined in [General Formula A-1], G ^D11 , G ^D12 each independently represents a nitrogen atom, a substituted or unsubstituted carbon atom, J ^D11 , J ^D12 , J ^D13 and Each of J ^D14 independently represents a group of atoms necessary to form a 5-membered ring, and L ^D11 and L ^D12 represent a linking group.

An exemplary structure of the compound represented by the [General Formula E-1] is as follows, but is not limited thereto.

[General Formula F-1]

In the above [general formula F-1],

M ^E1 represents the same metal ion as defined in [General Formula A-1], J ^E11 , J ^E12 each independently represents an atomic group necessary to form a 5-membered ring, 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 or a substituted or unsubstituted carbon atom.

An exemplary structure of the compound represented by the [General Formula F-1] is as follows, but is not limited thereto.

[General formula G-1]

In the above [general formula G-1],

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

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

An exemplary structure of the compound represented by the [general formula G-1] is as follows, but is not limited thereto.

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

In the [general formula H-1] to [general formula H-3],

R ¹¹ , R ¹² is a substituent of alkyl, aryl or heteroaryl; In addition, a fused ring may be formed with a substituent adjacent to each other, and q11 and q12 are integers of 0 to 4, preferably 0 to 2.

In addition, when q11 and q12 are 2 to 4, a plurality of R11 and R12 may be the same or different from each other.

L ¹ is a ligand binding to platinum, preferably a ligand capable of forming an ortho metalized platinum complex, a nitrogen-containing heterocyclic ligand, a diketone ligand, or a halogen ligand, more preferably an ortho metal (ortho metal). ) is a ligand that forms a platinum complex, a bipyridyl ligand or a phenanthroline ligand.

n ¹ is an integer from 0 to 3, preferably 0, m ¹ is 1 or 2, preferably 2;

In addition, n ¹ and m ¹ are preferably such that the metal complex represented by the general formula H-1 becomes a neutral complex.

In the above [general formula H-2],

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

In the above [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 , respectively, q ³¹ represents an integer of 0 to 8, 0 to 2 is preferable, and 0 is more desirable.

Examples of specific compounds of the [general formula H-1] to [general formula H-3] are as follows, but are not limited thereto.

[General Formula I-1]

In the above [General Formula I-1],

Ring A, Ring B, Ring C and Ring D represents a nitrogen-containing heterocycle in which any two of the rings A to D may have a substituent, and the other two rings are an aryl ring or heterocyclic ring which may have a substituent. An aryl ring is represented and represented, and a condensed ring may be formed with Ring A and Ring B, Ring A and Ring C and/or Ring B and Ring D. X ¹ , X ² , X ³ and X ⁴ each represents a nitrogen atom coordinated to a platinum atom, and the other two represent a carbon atom or a nitrogen atom. Q ¹ , Q ² , and Q ³ each independently represent a divalent atom (provided) or a bond, but Q ¹ , Q ² and Q ³ do not simultaneously represent a bond. Any two of Z ¹ , Z ² , Z ³ and Z ⁴ represent a coordination bond, and the other two represent a covalent bond, an oxygen atom or a sulfur atom.

Examples of specific compounds of the [General Formula I-1] are as follows, but are not limited thereto.

[General formula J-1]

In the [general formula J-1],

M represents the same metal ion as defined in [General Formula A-1], Ar1 represents a substituted or unsubstituted ring structure, and two azomethine bonds bonded to M (-C=N-) In the above, each nitrogen atom (N) is bonded to the M, and forms a tridentate ligand bonded to M as a whole at 3 positions.

Incidentally, in Ar1, C represents a carbon atom constituting the ring structure represented by Ar1. In addition, R1 and R2 may be the same as or different from each other, and each represents a substituted or unsubstituted alkyl or aryl group, and L represents a monodentate ligand.

In the [General Formula J-1], M is preferably Pt. Moreover, as said Ar1, it is preferable to select from a 5-membered ring, a 6-membered ring, and these condensed cyclic groups.

Examples of specific compounds of the [General Formula J-1] are as follows, but are not limited thereto.

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 includes an anode, a hole transport layer, a light emitting layer, an electron transport layer and a cathode, and may further include a hole injection layer and an electron injection layer if necessary, and in addition to that, an intermediate layer of one or two layers It is also possible to further form, a hole blocking layer or an electron blocking layer may be further formed, and may further include an organic layer having various functions according to the characteristics of the device.

Looking at the organic light emitting device and the method for manufacturing the same according to the present invention, first, an anode is formed by coating a material for an anode electrode on an upper portion of a substrate. Here, as the substrate, a substrate used in a conventional organic light emitting device is used, and an organic substrate or a transparent plastic substrate excellent in transparency, surface smoothness, handling and water resistance is preferable. In addition, as a material for the anode electrode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc., which are transparent and have excellent conductivity, are used.

A hole injection layer is formed by vacuum thermal evaporation or spin coating of a hole injection layer material on the anode electrode. Next, a hole transport layer is formed by vacuum thermal evaporation or spin coating of a hole transport layer material on the hole injection layer.

The hole injection layer material may be used without particular limitation as long as it is commonly used in the art, and as a specific example, 2-TNATA [4,4',4"-tris(2-naphthylphenyl-phenylamino)-triphenylamine] , NPD[N,N'-di(1-naphthyl)-N,N'-diphenylbenzidine)], TPD[N,N'-diphenyl-N,N'-bis(3-methylphenyl)-1,1'- biphenyl-4,4'-diamine], DNTPD[N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine ] can be used.

In addition, the material of the hole transport layer is not particularly limited as long as it is commonly used in the art, for example, N,N'-bis(3-methylphenyl)-N,N'-diphenyl-[1,1 -biphenyl]-4,4'-diamine (TPD) or N,N'-di(naphthalen-1-yl)-N,N'-diphenylbenzidine (α-NPD), etc. can be used.

Then, a thin film may be formed by laminating a light emitting layer on the hole transport layer and selectively depositing a hole blocking layer on the light emitting layer by a vacuum deposition method or a spin coating method. The hole blocking layer serves to prevent this problem by using a material having a very low HOMO (Highest Occupied Molecular Orbital) level because the lifetime and efficiency of the device are reduced when holes are introduced into the cathode through the organic light emitting layer. . In this case, the hole blocking material used is not particularly limited, but has an electron transport ability and has an ionization potential higher than that of a light emitting compound, and typically BAlq, BCP, TPBI, or the like may be used.

Organic light emission by forming an electron injection layer after depositing an electron transport layer on the hole blocking layer through a vacuum deposition method or a spin coating method, and vacuum thermal evaporation of a metal for forming a cathode on the electron injection layer to form a cathode electrode The small is complete. Here, as the metal for forming the cathode, lithium (Li), magnesium (Mg), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), magnesium-silver ( Mg-Ag) may be used, and in order to obtain a top light emitting device, a transmissive cathode using ITO or IZO may be used.

As the material for the electron transport layer, a known electron transport material serving to stably transport electrons injected from an electron injection electrode (Cathode) may be used. Examples of known electron transport materials include quinoline derivatives, in particular tris(8-quinolinolate)aluminum (Alq3), TAZ, Balq, beryllium bis(benzoquinolin-10- Materials such as olate: Bebq2), ADN, and oxadiazole derivatives PBD, BMD, BND, etc. may be used.

In addition, at least one layer selected from the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the hole blocking layer, the electron transport layer and the electron injection layer may be formed by a single molecule deposition method or a solution process, wherein the deposition method means a method of forming a thin film by evaporating a material used as a material for forming each layer through heating in a vacuum or low pressure state, and the solution process is used as a material for forming each layer It refers to a method of mixing a material to be used with a solvent and forming a thin film through a method such as inkjet printing, roll-to-roll coating, screen printing, spray coating, dip coating, spin coating, and the like.

In addition, the organic light emitting diode according to the present invention can be used in a device selected from a flat panel display device, a flexible display device, a device for flat panel lighting of a single color or white color, and a device for a flexible lighting device of a single color or white color.

Hereinafter, preferred examples are presented to help the understanding of the present invention. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereby.

Synthesis example 1: Synthesis of Formula H-4

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

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

<Intermediate 1-a>

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

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

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

<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 at 120 °C overnight. After completion of the reaction, the reaction solution was concentrated by heating and purified by column chromatography to obtain <Intermediate 1-b>. (5.8 g, 23.6%)

Synthesis example 1-(3): Synthesis of Intermediate 1-c

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

<Scheme 3>

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

<Intermediate 1-b> (17.2 g, 61 mmol), iodobenzene (14.9 g, 73 mmol), bis (dibenzylideneacetone) palladium (0) (0.7 g, 1 mmol) in a 500 mL round-bottom flask reactor , tri-tert-butylphosphine tetrahydroborate (1.8 g, 6 mmol), sodium tert-butoxide (11.7 g, 121 mmol), and xylene 180 mL were added. The temperature of the reactor was raised and the mixture was stirred under reflux overnight. The reaction solution was filtered and concentrated under reduced pressure. It was separated and purified by column chromatography to obtain <Intermediate 1-c>. (15.8 g, 72.4%)

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

<Intermediate 1-d> was synthesized according to Scheme 4 below.

<Scheme 4>

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

<Intermediate 1-c> (15.8 g, 44 mmol) was put into a 250 mL round-bottom flask reactor, and 130 mL of dimethylformamide was added and dissolved. 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 the dropwise addition, the mixture was stirred at room temperature overnight. After completion of the reaction, the mixture was extracted with ethyl acetate, heptane and water. The organic layer was separated and purified by column chromatography after concentration under reduced pressure to obtain <Intermediate 1-d>. (14.7 g, 76.3%)

Synthesis example 1-(5): Synthesis of Formula H-4

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

<Scheme 5>

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

<Intermediate 1-d> instead of 1-bromo-2-nitrobenzene in Synthesis Example 1-(1), 9,9'-dimethylfluorene-2-boronic acid instead of N-phenylcarbazole-3- Except for using boronic acid, <Formula H-4> was obtained using the same method. (7.6g, 37.7%)

MS (MALDI-TOF): m/z 600.26[M ⁺ ]

Synthesis example 2: Synthesis of Formula H-17

Synthesis example 2-(1): Synthesis of Intermediate 2-a

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

<Scheme 6>

<Intermediate 2-a>

<Intermediate 2-a> using the same method, except that 4-iododibenzofuran was used instead of 2-bromoaniline and iodobenzene in place of <Intermediate 1-b> in Synthesis Example 1-(3) > was obtained. (29.4 g, 85.2%)

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

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

<Scheme 7>

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

In a 500 mL round-bottom flask reactor, <Intermediate 2-a> (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 mixture was cooled to room temperature and extracted with ethyl acetate, heptane and water. The organic layer was separated and purified by column chromatography after concentration under reduced pressure to obtain <Intermediate 2-b>. (10.3 g, 46.1%)

Synthesis example 2-(3): Synthesis of Intermediate 2-c

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

<Scheme 8>

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

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

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

<Intermediate 2-d> was synthesized according to Scheme 9 below.

<Scheme 9>

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

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

Synthesis example 2-(5): Synthesis of Formula H-17

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

<Scheme 10>

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

<Intermediate 2-d> instead of 1-bromo-2-nitrobenzene in Synthesis Example 1-(1), 9,9'-dimethylfluorene-2-boronic acid instead of N-phenylcarbazole-3- Except for using boronic acid, <Formula H-17> was obtained using the same method. (6.9g, 45.4%)

MS (MALDI-TOF): m/z 574.20 [M ⁺ ]

Synthesis example 3: Synthesis of Formula H-26

Synthesis example 3-(1): Synthesis of Intermediate 3-a

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

<Scheme 11>

<Intermediate 3-a>

In Synthesis Example 1-(3), using the same method as <Intermediate 3->, except that 2-bromoaniline and 4-iododibenzothiophene were used instead of a> was obtained. (19.1 g, 83.6%)

Synthesis example 3-(2): Synthesis of Intermediate 3-b

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

<Scheme 12>

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

<Intermediate 3-b> was obtained in the same manner as in Synthesis Example 2-(2), except that <Intermediate 3-a> was used instead of <Intermediate 2-a>. (7.2g, 48.9%)

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

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

<Scheme 13>

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

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

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

<Intermediate 3-d> was synthesized according to Scheme 14 below.

<Scheme 14>

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

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

Synthesis example 3-(5): Synthesis of Formula H-26

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

<Scheme 15>

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

<Intermediate 3-d> instead of 1-bromo-2-nitrobenzene in Synthesis Example 1-(1), 9,9'-dimethylfluorene-2-boronic acid instead of N-phenylcarbazole-3- Except for using boronic acid, <Formula H-26> was obtained using the same method. (3.8 g, 32.8%)

MS (MALDI-TOF): m/z 590.18[M ⁺ ]

Synthesis example 4: Synthesis of Formula H-44

Synthesis example 4-(1): Synthesis of Intermediate 4-a

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

<Scheme 16>

<Intermediate 4-a>

<Intermediate 4-a> using the same method except that 2-chloroaniline and 3-bromodibenzothiophene were used instead of iodobenzene in place of <Intermediate 1-b> in Synthesis Example 1-(3) got (20.2 g, 85.8%)

Synthesis example 4-(2): Synthesis of Intermediate 4-b

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

<Scheme 17>

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

<Intermediate 4-b> was obtained in the same manner as in Synthesis Example 2-(2), except that <Intermediate 4-a> was used instead of <Intermediate 2-a>. (8.4 g, 47.1%)

Synthesis example 4-(3): Synthesis of Intermediate 4-c

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

<Scheme 18>

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

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

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

<Intermediate 4-d> was synthesized according to Scheme 19 below.

<Scheme 19>

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

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

Synthesis example 4-(5): Synthesis of Formula H-44

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

<Scheme 20>

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

In Synthesis Example 1-(1) instead of 1-bromo-2-nitrobenzene, 3-bromo-N-phenylcarbazole, 9,9'-dimethylfluorene-2-boronic acid instead of <Intermediate 4- Except for using d>, <Formula H-44> was obtained using the same method. (2.9g, 31.6%)

MS (MALDI-TOF): m/z 590.18[M ⁺ ]

Synthesis example 5: Synthesis of Formula H-55

Synthesis example 5-(1): Synthesis of Intermediate 5-a

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

<Scheme 21>

<Intermediate 5-a>

In a 1 L round-bottom flask reactor, 1-bromo-2-nitrobenzene (50 g, 248 mmol), bis (pinacolato) diboron (81.7 g, 322 mmol), 1,1'-bis (diphenyl) Phosphino) ferrocene-palladium (II) dichloride (4.03 g, 5 mmol), potassium acetate (48.6 g, 495 mmol), and toluene 500 mL were added, and the mixture was stirred under reflux overnight. After completion of the reaction, the filtrate was concentrated under reduced pressure by passing it through a celite pad. <Intermediate 5-a> was obtained by separation and purification by column chromatography. (46.8 g, 75.9%)

Synthesis example 5-(2): Synthesis of Intermediate 5-b

<Intermediate 5-b> was synthesized according to Scheme 22 below.

<Scheme 22>

<Intermediate 5-b>

In a 1 L round-bottom flask reactor, 1-hydroxydibenzofuran (30 g, 163 mmol) and pyridine (25.8 g, 3264 mmol) were added, and 300 mL of chloroform was added and dissolved. The reaction solution was cooled to 0 °C under a nitrogen atmosphere. To the cooled solution, trifluoromethanesulfonic anhydride (32.1 g, 196 mmol) was slowly added dropwise over 20 minutes, the temperature was raised to room temperature, and the mixture was stirred overnight. The reaction solution was acidified by dropwise addition of 2-N hydrochloric acid, followed by stirring for 1 hour. After extraction with ethyl acetate, the organic layer was separated, concentrated under reduced pressure, and separated and purified by column chromatography to obtain <Intermediate 5-b>. (46.8 g, 90.9%)

Synthesis example 5-(3): Synthesis of Intermediate 5-c

<Intermediate 5-c> was synthesized according to Scheme 23 below.

<Scheme 23>

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

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

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

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

<Scheme 24>

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

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

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

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

<Scheme 25>

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

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

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

<Intermediate 5-f> was synthesized according to Scheme 26 below.

<Scheme 26>

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

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

Synthesis example 5-(7): Synthesis of Formula H-55

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

<Scheme 27>

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

In Synthesis Example 1-(1) instead of 1-bromo-2-nitrobenzene, 3-bromo-N-phenylcarbazole, 9,9'-dimethylfluorene-2-boronic acid instead of <Intermediate 5- <Formula H-55> was obtained using the same method except that f> was used. (5.1 g, 42.4%)

MS (MALDI-TOF): m/z 574.20 [M ⁺ ]

Synthesis example 6: Synthesis of Formula H-75

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

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

<Scheme 28>

<Intermediate 6-a>

In Synthesis Example 1-(1), methyl 2-bromobenzoate instead of 1-bromo-2-nitrobenzene, 9,9'-dimethylfluorene-2-boronic acid instead of dibenzothiophene-4- <Intermediate 6-a> was obtained in the same manner except that boronic acid was used. (23.8 g, 85.2%)

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

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

<Scheme 29>

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

<Intermediate 6-a> (23.8 g, 75 mmol) was put into a 500 mL round-bottom flask reactor, and 190 mL of tetrahydrofuran was added and dissolved. The reaction solution was cooled to 0 °C under a nitrogen atmosphere. Methylmagnesium bromide (87.2 mL, 262 mmol) was slowly added dropwise to the cooled solution over 30 minutes, and the temperature was raised to room temperature. After 1 hour, the reaction solution was heated to 60 °C and stirred overnight. The reaction solution was acidified by dropwise addition of 2-N hydrochloric acid, followed by stirring for 1 hour. After extraction with ethyl acetate, the organic layer was separated, concentrated under reduced pressure, and separated and purified by column chromatography to obtain <Intermediate 6-b>. (20.4 g, 85.7%)

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

According to Scheme 30 below, Intermediate 6-c was synthesized.

<Scheme 30>

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

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

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

<Intermediate 6-d> was synthesized according to Scheme 31 below.

<Scheme 31>

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

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

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

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

<Scheme 32>

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

<Intermediate 6-d> instead of 1-bromo-2-nitrobenzene in Synthesis Example 1-(1), 9,9'-dimethylfluorene-2-boronic acid instead of N-phenylcarbazole-3- <Intermediate 6-e> was obtained in the same manner except that boronic acid was used. (15.8 g, 74.3%)

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

<Intermediate 6-f> was synthesized according to Scheme 33 below.

<Scheme 33>

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

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

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

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

<Scheme 34>

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

In Synthesis Example 1-(1), using <Intermediate 6-f> instead of 3-bromobiphenyl, 9,9'-dimethylfluorene-2-boronic acid instead of 1-bromo-2-nitrobenzene Except for, <Formula H-75> was obtained using the same method. (5.1 g, 32.6%)

MS (MALDI-TOF): m/z 693.25[M ⁺ ]

Synthesis example 7: Synthesis of Formula E-19

Synthesis example 7-(1): Synthesis of intermediate 7-a

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

<Scheme 35>

<Intermediate 7-a>

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

Synthesis example 7-(2): Synthesis of intermediate 7-b

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

<Scheme 36>

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

In Synthesis Example 1-(1) instead of 1-bromo-2-nitrobenzene, 2,2'-dibromodibenzothiophene, 9,9'-dimethylfluorene-2-boronic acid instead of <Intermediate 7 Except for using -a>, <Intermediate 7-b> was obtained using the same method. (24.9 g, 82.1%)

Synthesis example 7-(3): Synthesis of intermediate 7-c

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

<Scheme 37>

<Intermediate 7-b <Intermediate 7-c>

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

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

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

<Scheme 38>

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

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

Synthesis example 7-(5): Synthesis of intermediate 7-e

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

<Scheme 39>

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

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

Synthesis example 7-(6): Synthesis of Formula E-19

Formula E-19 was synthesized according to Scheme 40 below.

<Scheme 40>

<Intermediate 7-e> <Formula E-19>

2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine, 9,9' instead of 1-bromo-2-nitrobenzene in Synthesis Example 1-(1) -Dimethylfluorene-2-boronic acid was replaced with <Intermediate 7-e>, except that <Formula E-19> was obtained using the same method. (8.2 g, 49.4%)

MS (MALDI-TOF): m/z 607..21[M ⁺ ]

Synthesis example 8: Synthesis of Formula E-60

Synthesis example 8-(1): Synthesis of Intermediate 8-a

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

<Scheme 41>

<Intermediate 8-a>

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

Synthesis example 8-(2): Synthesis of Formula E-60

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

<Scheme 42>

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

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

MS (MALDI-TOF): m/z 656..20[M ⁺ ]

Example 1: Manufacture of organic light emitting device

After patterning so that the light emitting area of the ITO glass has a size of 2 mm × 2 mm, it was washed. After mounting the substrate in a vacuum chamber, the base pressure was 1 × 10 ^-6 torr, and the organic material was placed on the ITO, HATCN (50 Å), NPD (900 Å), the compound prepared by the present invention Chemical formula of the first compound The weight ratio of H-4 and Formula E-19 of the second compound was 5:5, and GD was doped with 7% to form an emission layer with a thickness of 400 Å. ET: A film was formed in the order of Liq = 1:1 (300 Å), Liq (10 Å), and Al (1,000 Å), and measurement was performed at 0.4 mA.

[HATCN] [NPD]

[ET] [Liq] [GD]

Example 2

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Formula E-60 was used instead of Formula E19 when the light emitting layer was formed.

Example 3

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Formula E-93 was used instead of Formula E19 when the light emitting layer was formed.

Example 4

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Formula H-17 was used instead of Formula H-4 when the light emitting layer was formed.

Example 5

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Formula H-17 was used instead of Formula H-4 and Formula E-60 was used instead of Formula E19 when the light emitting layer was formed.

Example 6

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Formula H-17 was used instead of Formula H-4 and Formula E-93 was used instead of Formula E19 when the light emitting layer was formed.

Example 7

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Formula H-26 was used instead of Formula H-4 when the emission layer was formed.

Example 8

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Formula H-26 was used instead of Formula H-4 and Formula E-60 was used instead of Formula E19 when the light emitting layer was formed.

Example 9

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Formula H-26 was used instead of Formula H-4 and Formula E-93 was used instead of Formula E19 when the light emitting layer was formed.

Example 10

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Formula H-44 was used instead of Formula H-4 when the emission layer was formed.

Example 11

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Formula H-44 was used instead of Formula H-4 and Formula E-60 was used instead of Formula E19 when the light emitting layer was formed.

Example 12

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Formula H-44 was used instead of Formula H-4 and Formula E-93 was used instead of Formula E19 when the emission layer was formed.

Example 13

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Formula H-55 was used instead of Formula H-4 when the emission layer was formed.

Example 14

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Formula H-55 was used instead of Formula H-4 and Formula E-60 was used instead of Formula E19 when the emission layer was formed.

Example 15

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Formula H-55 was used instead of Formula H-4 and Formula E-93 was used instead of Formula E-5 when the light emitting layer was formed. .

Example 16

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Formula H-75 was used instead of Formula H-4 when the emission layer was formed.

Example 17

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Formula H-75 was used instead of Formula H-4 and Formula E-60 was used instead of Formula E19 when the light emitting layer was formed.

Example 18

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Formula H-75 was used instead of Formula H-4 and Formula E-93 was used instead of Formula E19 when the emission layer was formed.

comparative example 1 to 9

An organic light emitting diode was manufactured in the same manner as in Example 1, except that Formulas H-4 to E-93 and GD were co-deposited in a weight ratio of 100:7 when the emission layer was formed.

evaluation example

The driving voltage, luminance, emission color, and lifespan of the organic light emitting 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 superior driving voltage and efficiency compared to the organic light emitting devices of Comparative Examples 1 to 9, and particularly have significantly improved lifespan characteristics. can be checked, it can be usefully used in various display and lighting industries.

Claims (10)

a first electrode; a second electrode opposite the first electrode; and an organic layer interposed between the first electrode and the second electrode,
The organic layer includes an emission layer, a hole transport layer between the emission layer and the first electrode, and an electron transport layer between the emission layer and the second electrode,
An organic light emitting device comprising a first compound represented by the [Formula 1] and a second compound represented by the [Formula 2] in the light emitting layer:
[Formula 1]

In the above [Formula 1],
Y ₁ , Y ₂ and Y ₃ are the same as or different from each other, and are each independently any one selected from NR, O, S and CRR',
At least one of Y ₁ , Y ₂ and Y ₃ is NR,
B ₁ and B ₂ are hydrogen, deuterium, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted aromatic hydrocarbon group having 6 to 30 ring carbon atoms, and a substituted or unsubstituted ring C 5 to 30 C 5 Any one selected from heterocyclic groups,
The B ₁ and B ₂ may be combined 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, and ,
R, R', and R ₁ to R ₁₀ are each independently hydrogen, deuterium, a halogen group, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 50 aryl group, and a substituted or unsubstituted It is any one selected from a heteroaryl group having 3 to 50 carbon atoms and having O, N or S as a hetero atom, and can 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 from 1 to 3,

[Formula 2]

In the above [Formula 2],
HAr is any one selected from the heterocyclic group represented by the following [Structural Formula 2],
[Structural Formula 2]

L is a linking group, a single bond, or any one selected from a substituted or unsubstituted arylene group having 6 to 60 carbon atoms and a substituted or unsubstituted heteroarylene group having 2 to 60 carbon atoms,
n3 and m1 are each 1, n4 is an integer of 1 to 2, and a plurality of L's are the same as or different from each other,
Az is a nitrogen-containing ring represented by the following [Structural Formula 1],
[Structural Formula 1]

X ₁ to X ₆ are the same as or different from each other, and each independently represents N or CR ₁₁ , at least one of X ₁ to X ₆ is N, at least one or more is CR ₁₁ , and at least one R ₁₁ is the It is connected to L of [Formula 2],
The at least one R ₁₁ is the same as or different from each other, and each independently represents hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 6 to C 50 aryl group, and a substituted or unsubstituted and heterogeneous Any one selected from a heteroaryl group having 3 to 50 carbon atoms and having O, N or S as an atom. The method of claim 1,
Each of L, B ₁ , B ₂ , R, R′ and R ₁ to R ₁₁ may be further substituted with one or more substituents, wherein the one or more substituents are an alkyl group having 1 to 60 carbon atoms, 5 to 60 carbon atoms An organic light emitting device selected from a heteroaryl group, an aryl group having 6 to 60 carbon atoms, an alkylsilyl group having 1 to 20 carbon atoms, an arylsilyl group having 6 to 30 carbon atoms, a halogen group and deuterium. delete The method of claim 1,
The light emitting layer is an organic light emitting device including a phosphorescent dopant compound. According to claim 1,
The mixing weight ratio of the first compound, the second compound, and the phosphorescent dopant compound is 1: 0.01 to 99: 0.01 to 15 of the organic light emitting device. The method of claim 1,
The first compound represented by the [Formula 1] is an organic light emitting device, characterized in that any one selected from the following <Formula H-1> to <Formula H-108>:

According to claim 1,
The second compound represented by the [Formula 2] is an organic light emitting device which is any one selected from the following compounds:

According to claim 1,
The organic light emitting device further includes one or more light emitting layers emitting blue, red, or green light to emit white light. Illumination comprising the organic light emitting device according to claim 1. A display device comprising the organic light emitting device according to claim 1 .