KR20140128509A - Organic Metal Compounds for OLED and OLED having the same - Google Patents

Abstract

The present invention relates to a compound for an organic light emitting diode and an organic light emitting diode including the same. The compound for an organic light emitting diode is represented by chemical formula 1. In chemical formula 1, M is a group 2 metal or a group 3 metal. X is O or S. At least one among A_1, A_2, A-3 and A_4 is N, and the others are identical to R_1 or are CR_1s which are different from each other. R_1 is a hydrogen, a halogen group, a cyano group, an alkyl group of C1-C30, an aryl group of C6 or C60, a heteroaryl group, a tri(alkyl of C1-C30)silyl group, a di(alkyl of C1-C30) (aryl of C6 or C60) a silyl group, a di(alkyl of C1-C30)heteroaryl silyl group, a tri(aryl of C6 or C60)silyl group, a triheteroaryl silyl group, a di(alkyl of C1-C30)amino group, a di(aryl of C6 or C60)amino group, a diheteroarylamino group, (alkyl of C1-C30) (aryl of C6 or C60) amino group, or a (alkyl of C1-C30)heteroaryl amino group. B is an aromatic five membered ring or an aromatic six membered ring. Y is C or N. and n is 2 or 3.

Description

TECHNICAL FIELD The present invention relates to an organic metal compound for an organic light emitting diode and an organic light emitting diode having the organic metal compound.

The present invention relates to compounds for organic light emitting diodes and more particularly to organometallic compounds.

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

A typical organic light emitting diode may include an anode and a cathode and an organic layer interposed between the anode and the cathode. The organic layer may include an electron injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, a cathode, and the like. When a voltage is applied between the anode and the cathode, holes injected from the anode move to the light emitting layer via the hole transporting layer, and electrons injected from the cathode move to the light emitting layer via the electron transporting layer. The carriers, such as holes and electrons, recombine in the light emitting layer region to produce an exiton, which is changed from the excited state to the ground state to produce light.

The quantum efficiency of such an organic light emitting diode can be improved when electrons and holes injected into the light emitting layer are balanced. Generally, it is known that the electron mobility of the organic layer is not better than the hole mobility. Therefore, there is an attempt to develop an electron injection layer, an electron transport layer, and the like as disclosed in Korean Patent Laid-Open Publication No. 2013-0007510.

However, there is a continuing need for materials that have better electron mobility and are suitable for each device.

An object of the present invention is to provide an organic metal compound having improved electron mobility and an organic light emitting diode using the same.

According to an aspect of the present invention, there is provided a compound for an organic light emitting diode. The compound for the organic light emitting diode is represented by the following general formula (1).

[Chemical Formula 1]

Wherein M is a Group 2 or Group 3 metal, X is O or S, at least one of A ₁ , A ₂ , A ₃ , and A ₄ is N, and the remaining R ₁ are the same or different CR is ₁ (s), R is hydrogen, a halogen group, a cyano group, an aryl group of C1 to C30 alkyl, C6 or C60, the heteroaryl group, tri (alkyl of C1 to C30) alkylsilyl group, a di (C1 to C30 (C6 or C60 aryl) silyl, di (C1 to C30 alkyl) heteroarylsilyl, tri (C6 or C60 aryl) silyl, triheteroarylsilyl, di (C1 to C30 alkyl (C1 to C30 alkyl) amino group, di (C6 or C60 aryl) amino group, diheteroarylamino group, C1 to C30 alkyl (C6 or C60 aryl) amino group, or C1 to C30 alkyl heteroarylamino group, Y is C or N, and n is 2 or 3.

The compound may be represented by the following general formula (2).

(2)

In Formula _{2, M, X, A 1} , A 2, A 3, A 4, Y and n are of the _{M, X, A 1, A} 2 Formula _{1, A 3, A 4,} Y and n, respectively Can be the same. B _1, B _2, and B ₃ are independently N or R ₂ are the same or different CR ₂ (s) with each other and, R ₂ is a hydrogen, a halogen group, a cyano group, an alkyl group of C1 to C30, C6 or C60 (C1 to C30 alkyl) silyl, di (C1 to C30 alkyl) (C6 or C60 aryl) silyl, di (C1 to C30 alkyl) heteroarylsilyl, tri (C6 or C60 aryl) silyl group, triheteroarylsilyl group, di (C1 to C30 alkyl) amino group, di (C6 or C60 aryl) amino group, diheteroarylamino group, C1 to C30 alkyl Or an aryl of C60) amino group, or (C1-C30 alkyl) heteroarylamino group.

At least one of Y, B ₁ , B ₂ , and B ₃ may be N. In one embodiment, Y is N and B ₁ , B ₂ , and B ₃ can be the same or different CR ₂ R ₂ . In other embodiments, Y and B ₂ are N, and B ₁ and B ₃ may be the same or different CR ₂ R ₂ . In yet another embodiment, Y, B ₁ , and B ₂ may be N and B ₃ may be CR ₂ .

On the other hand, A ₁ is N, and A ₂ , A ₃ , and A ₄ may be the same or different CR ₁ (s) for R ₁ .

The compound may be represented by the following formula (3).

(3)

Wherein M, X, and n are the same as M, X, and n in Formula 1, and B ₁ , B ₂ , and B ₃ are independently of each other N or R ₂ are the same or different CR ₂ (s), and, R ₂ is hydrogen, halogen, cyano, C1 to C30 alkyl, C6 or an aryl group of C60, a heteroaryl group, a silyl group tri (alkyl of C1 to C30) group, a di (C1 to C30 of (C1 to C30 alkyl) (C6 or C60 aryl) silyl, di (C1 to C30 alkyl) heteroarylsilyl, tri (C6 or C60 aryl) silyl, triheteroarylsilyl, di An amino group, a di (C6 or C60 aryl) amino group, a diheteroarylamino group, a C1 to C30 alkyl (C6 to C60 aryl) amino group, or a (C1 to C30 alkyl) heteroaryl amino group. Be, Zn, Mg, Al, Ga, or In.

The compound may be represented by the following general formula (4), (5), or (6).

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

The compound may be used either as a host material of an organic light emitting diode, an electron injecting material, or an electron transporting material.

According to another aspect of the present invention, there is provided an organic light emitting diode. The organic light emitting diode includes an anode, a hole conduction layer, a light emitting layer, an electron conduction layer, and a cathode sequentially stacked. Any one of the hole conduction layer, the light emitting layer, and the electron conduction layer may include the compound of Formula 1.

The electron conduction layer includes an electron transport layer and an electron injection layer, and any one of the light emitting layer, the electron transport layer, and the electron injection layer may include the compound of Formula 1. Furthermore, the light emitting layer may include a host material and a dopant material, and any one of the host material, the electron transport layer, and the electron injection layer may include the compound of Formula 1. The host material is a phosphorescent host material and the dopant material may be a phosphorescent dopant material. The light emitting layer may be a light emitting layer emitting blue light.

According to the embodiments of the present invention, when the compound of Chemical Formula 1 is used for an organic light emitting diode, it is expected that the efficiency and the driving voltage of the organic light emitting diode are reduced.

1 is a cross-sectional view illustrating an organic light emitting diode according to an exemplary embodiment of the present invention.

Hereinafter, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments described herein but may be embodied in other forms. Like reference numerals designate like elements throughout the specification.

Organometallic compound

The following Chemical Formula 1 represents an organometallic compound according to an embodiment of the present invention.

In Formula 1, M may be a Group 2 or Group 3 metal. Specifically, M may be Be, Zn, Mg, Al, Ga, or In. X can be O or S; At least one of A ₁ , A ₂ , A ₃ , and A ₄ is N and the remaining R ₁ may be the same or different CR ₁ (s). R ₁ is hydrogen, halogen, cyano, C1 to alkyl groups of C30, C6 or C60 aryl group, a heteroaryl group, tri (alkyl of C1 to C30) alkylsilyl group, a di (C1 to alkyl of C30) (C6 or C60 aryl) silyl group, di (C1 to C30 alkyl) heteroarylsilyl group, tri (C6 or C60 aryl) silyl group, diheteroarylsilyl group, di (C1 to C30 alkyl) Or a C60 to C30 aryl) amino group, a diheteroarylamino group, a C1 to C30 alkyl) (C6 or C60 aryl) amino group, or a (C1 to C30 alkyl) heteroarylamino group. B may be a pentachloric aromatic or a hexacyclic aromatic. Y may be C or N. n can be 2 or 3;

Such an organometallic compound may be a compound for an organic light emitting diode. Specifically, the organic metal compound may be used as one of a hole injecting material, a hole transporting material, a host material, an electron injecting material, and an electron transporting material in an organic light emitting diode. More specifically, such an organometallic compound may be any one of an electron injecting material, an electron transporting material, and a host material. In addition, the organometallic compound has relatively high electron affinity and can have an improved electron transporting ability. Accordingly, when such an organic metal compound is used as any one of an electron injecting material, an electron transporting material, and a host material, the efficiency of the organic light emitting diode and the driving voltage can be reduced.

In embodiments of the present invention, the C1 to C30 alkyl group may be a C1 to C4 alkyl group. The alkyl group may be a straight chain or branched chain alkyl group. Further, the hydrogen of the alkyl group may be substituted with a halogen group specifically F, and / or a cyano group.

In embodiments of the present invention, an aryl group of C6 or C60 may be a C6 aryl group. The hydrogen of the aryl group may be substituted with a halogen group specifically F, and / or a cyano group.

In embodiments of the present invention, the heteroaryl group may be a 5- or 6-membered aromatic ring containing one or more O, N, or S atoms. For example, pyrrole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, imidazole, oxadiazole, thiadiazole, pyridine, pyrazine, pyrimidine or pyridazine. The hydrogen of the heteroaryl group may be substituted with a halogen group specifically F, and / or a cyano group.

The organometallic compound according to one embodiment of the present invention can be represented by the following formula (2).

In Formula _{2, M, X, A 1} , A 2, A 3, A 4, Y and n are of the _{M, X, A 1, A} 2 Formula _{1, A 3, A 4,} Y and n, respectively Can be the same. B _1, B _2, and B ₃ are independently N or R ₂ are the same or different CR ₂ (s) with each other and, R ₂ is a hydrogen, a halogen group, a cyano group, an alkyl group of C1 to C30, C6 or C60 (C1 to C30 alkyl) silyl, di (C1 to C30 alkyl) (C6 or C60 aryl) silyl, di (C1 to C30 alkyl) heteroarylsilyl, tri (C6 or C60 aryl) silyl group, triheteroarylsilyl group, di (C1 to C30 alkyl) amino group, di (C6 or C60 aryl) amino group, diheteroarylamino group, C1 to C30 alkyl Or an aryl of C60) amino group, or (C1-C30 alkyl) heteroarylamino group.

In Formula 2, at least one of Y, B ₁ , B ₂ , and B ₃ may be N. Specifically, Y is N, and B ₁ , B ₂ , and B ₃ may be CR _{2 s in} which R ₂ is the same or different. Or Y and B ₂ are N, and B ₁ and B ₃ may be the same or different CR _{2 s} in R ₂ . Or Y, B ₁ , and B ₂ may be N and B ₃ may be CR ₂ . In this case, the level of the triplet energy of the organometallic compound may be higher than that of the conventional art. Further, the level of the triplet energy of the organometallic compound may be higher than the level of triplet energy of the dopant material in the light emitting layer. In this case, when the organometallic compound is used as a host material, the energy transfer from the triplet of the host material to the triplet of the dopant material can be efficiently performed. When the organometallic compound is used as an electron transport material, Can be restrained in the light emitting layer. In particular, when the dopant material has a band gap large enough to emit blue light, the use of the organometallic compound can provide a great effect.

In the Chemical Formula 1 or 2 and A ₁ is N, R ₁ may be the same or different from each other CR ₁ (s) A _2, A _3, and A _4.

The organometallic compound according to one embodiment of the present invention can be represented by the following general formula (3).

In Formula 3, M, X, and n may be the same as M, X, and n in Formula 1, respectively. B ₁ , B ₂ , and B ₃ may be independently of each other N or R ₂ may be the same or different CR ₂ (s). R ₂ is hydrogen, halogen, cyano, C1 to alkyl groups of C30, C6 or C60 aryl group, a heteroaryl group, tri (alkyl of C1 to C30) alkylsilyl group, a di (C1 to alkyl of C30) (C6 or C60 aryl) silyl group, di (C1 to C30 alkyl) heteroarylsilyl group, tri (C6 or C60 aryl) silyl group, diheteroarylsilyl group, di (C1 to C30 alkyl) Or a C60 to C30 aryl) amino group, a diheteroarylamino group, a C1 to C30 alkyl) (C6 or C60 aryl) amino group, or a (C1 to C30 alkyl) heteroarylamino group.

The organometallic compound according to another embodiment of the present invention can be represented by the following general formula (4), (5), or (6).

Organic light emitting diode

1 is a cross-sectional view illustrating an organic light emitting diode according to an exemplary embodiment of the present invention.

1, an organic light emitting diode includes an anode 10 and a cathode 70, a light emitting layer 40 disposed between the two electrodes, a hole conduction layer 20 disposed between the anode 10 and the light emitting layer 40, And an electron conduction layer 50 disposed between the light emitting layer 40 and the cathode 70. The hole transport layer 20 may include a hole transport layer 25 for transporting holes and a hole injection layer 23 for facilitating injection of holes. In addition, the electron conduction layer 50 may include an electron transport layer 55 for transporting electrons and an electron injection layer 53 for facilitating injection of electrons. In addition, an exciton blocking layer (not shown) may be disposed between the light emitting layer 40 and the electron transporting layer 55.

When a forward bias is applied to the organic light emitting diode, holes are injected from the anode 10 into the light emitting layer 40, and electrons from the cathode 70 are injected into the light emitting layer 40. Electrons and holes injected into the light emitting layer 40 are combined with each other to form excitons, and light is emitted while the excitons transition to the ground state.

The light emitting layer 40 may be made of a single light emitting material, and may include a host material and a dopant material. When the light emitting layer 40 includes a host material and a dopant material, the electrons and holes injected into the light emitting layer 40 are combined in the host material to form an exciton, and then the exciton is transferred to the dopant material to be transitioned to the ground state . At this time, as an example of the charge transporting ability of the host material, the efficiency of the organic light emitting diode can be improved when the electron transporting ability is improved. The light emitting layer 40 including the host material and the dopant material may be a phosphorescent light emitting layer.

On the other hand, the hole injection layer 23 and / or the hole transport layer 25 are layers having a HOMO level between the work function level of the anode 10 and the HOMO level of the light emitting layer 40, ) To enhance the injection or transport efficiency of holes. The electron injection layer 53 and / or the electron transport layer 55 are layers having a LUMO level between the work function level of the cathode 70 and the LUMO level of the light emitting layer 40, ) In order to increase the injection or transport efficiency of electrons. At this time, the hole transporting ability of the hole injecting layer 23 and / or the hole transporting layer 25 is improved and the electron transporting ability of the electron injecting layer 53 and / or the electron transporting layer 55 is improved, Improvement and drive voltage reduction.

A hole injecting material for forming the hole injecting layer 23, a hole transporting material for forming the hole transporting layer 25, a host material, an electron injecting material for forming the electron injecting layer 53 in the organic light emitting diode according to the present embodiment, And the electron transporting material forming the electron transporting layer 55 may be an organometallic compound represented by any one of the above-described Formulas 1 to 6. Specifically, the organometallic compound represented by any one of Chemical Formulas 1 to 6 may be any one of an electron injecting material, an electron transporting material, and a host material. The organometallic compounds represented by any one of formulas (1) to (6) have relatively high electron affinity and can have improved electron transporting ability. Accordingly, when such an organic metal compound is used as any one of an electron injecting material, an electron transporting material, and a host material, the efficiency of the organic light emitting diode and the driving voltage can be reduced.

When at least one of the electron injecting material, the electron transporting material and the host material is an organometallic compound represented by any one of Chemical Formulas 1 to 6, the remaining materials may be known materials.

In the following description, the anode 10, the hole injection layer 23, the hole transport layer 25, the light emitting layer 40, the exciton blocking layer (not shown), the electron transport layer 55, the electron injection layer 53, 70 will be described.

The anode 10 may be a conductive metal oxide, a metal, a metal alloy, or a carbon material. The conductive metal oxide is indium tin oxide (indium tin oxide: ITO), fluorine tin oxide (fluorine tin oxide: FTO), antimony tin oxide (antimony tin oxide, ATO), fluorine-doped tin oxide (FTO), SnO _2, ZnO , Or a combination thereof. The metal or metal alloy suitable as the anode 10 may be Au and CuI. The carbon material may be graphite, graphene, or carbon nanotubes.

The hole injecting layer 23 or the hole transporting layer 25 may include a material commonly used as a hole transporting material and one layer may have a different hole transporting material layer. The hole-transporting material may be, for example, mCP (N, N-dicarbazolyl-3,5-benzene); PEDOT: PSS (poly (3,4-ethylenedioxythiophene): polystyrenesulfonate); NPD (N, N'-di (1-naphthyl) -N, N'-diphenylbenzidine); N, N'-diphenyl-N, N'-di (3-methylphenyl) -4,4'-diaminobiphenyl (TPD); N, N'-diphenyl-N, N'-dinaphthyl-4,4'-diaminobiphenyl; N, N, N'N'-tetra-p-tolyl-4,4'-diaminobiphenyl; N, N, N'N'-tetraphenyl-4,4'-diaminobiphenyl; Porphyrin compound derivatives such as copper (II) 1,10,15,20-tetraphenyl-21H, 23H-porphyrin and the like; TAPC (1,1-Bis [4- [N, N'-Di (p-tolyl) Amino] Phenyl] cyclohexane; Triarylamine derivatives such as N, N, N-tri (p-tolyl) amine and 4,4 ', 4'-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine; Carbazole derivatives such as N-phenylcarbazole and polyvinylcarbazole; Phthalocyanine derivatives such as nonmetal phthalocyanine and copper phthalocyanine; Starburst amine derivatives; Enamnstilbene derivatives; Derivatives of aromatic tertiary amines and styryl amine compounds; And polysilane.

When the light emitting layer 40 is made of a single light emitting material, the light emitting layer 40 may be formed of Alq3 (8-trishydroxyquinoline aluminum), DSA (distyrylarylene), DSA derivative, DSB (distyrylbenzene), DSB derivative, DPVBi (4,4'- diphenyl vinyl) -1,1'-biphenyl, a DPVBi derivative, spiro-DPVBi or spiro-6P (spirosexyphenyl).

If the light emitting layer 40 contains a host material and a dopant material, the dopant material is rubrene (5,6,11,12- tetraphenyl naphthacene), PtOEP (see the formula), Ir (piq) ₃ (the formula Red dopants such as Btp2Ir (acac) (see the following chemical formula); Ir (ppy) ₃ (ppy = phenylpyridine) (refer to formula), Ir (ppy) ₂ (acac) (see the formula), Ir (mpyp) ₃ (see the following formula), C545T (10- (2- benzo Thiazolyl) -1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H, 5H, 11H- [l] benzopyrano [6,7,8- ij] quinolizine Green dopants such as < RTI ID = 0.0 > Or F ₂ Irpic (see the formula), (F ₂ ppy) ₂ Ir (tmd) (see the formula), (see the following formula), Ir (dfppz) _3, ter- fluorene (fluorene), 4,4'- And blue dopants such as bis [4- (di-p-tolylamino) styryl] biphenyl (DPAVBi) and 2,5,8,11-tetra-tert-butylperylene (TBP).

        C545T

On the other hand, the host of the light emitting layer 40 may be an organometallic compound represented by any one of formulas (1) to (6). However, when the electron injecting layer 53 or the electron transporting layer 55 contains the organometallic compound represented by any one of Chemical Formulas 1 to 6, the host may be Alq3, CBP (4,4'-N, N'-dicar Tris (N-phenylbenzimidazol-2-yl) benzene (1,3,5-tris (N-phenylbenzimidazole-2-yl) benzene), TBADN (3-tert-butyl-9,10- ).

The exciton blocking layer serves to prevent triplet excitons or holes from diffusing toward the cathode 70 when the light emitting layer 40 is a phosphorescent light emitting layer, and may be selected arbitrarily from known hole blocking materials. For example, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, and the like can be used.

The electron transporting layer 55 may include the organometallic compound represented by any one of Chemical Formulas 1 to 6 as an electron transporting material. However, when the host material of the light emitting layer 40 or the electron injecting material of the electron injecting layer 53 is an organometallic compound shown in any one of Chemical Formulas 1 to 6, the electron transporting material may be a known electron transporting material, (PF-6P), COTs (PF-6P), and tetrafluoroethylene (PF-6P), as well as TSPO1 (diphenylphosphine oxide-4- (triphenylsilyl) Octasubstituted cyclooctatetraene, TAZ (see below), Bphen (4,7-diphenyl-1,10-phenanthroline), BCP Or Balq (see below formula).

The electron injection layer 53 may include the organometallic compound shown in any one of Chemical Formulas 1 to 6 as an electron injecting material. However, when the host material of the light emitting layer 40 or the electron injecting material of the electron transporting layer 55 is an organometallic compound represented by any one of Chemical Formulas 1 to 6, the electron injecting material may be a known electron injecting material such as LiF , NaCl, CsF, Li2O, BaO, BaF2, or Liq (lithium quinolate).

The cathode 70 is a conductive film having a lower work function than the anode 70 and is made of a metal such as aluminum, magnesium, calcium, sodium, potassium, indium, yttrium, lithium, May be formed using a combination of two or more of them.

The anode 10 and the cathode 70 may be formed using a sputtering method, a vapor deposition method, or an ion beam deposition method. The hole injection layer 23, the hole transport layer 25, the light emitting layer 40, the exciton blocking layer, the electron transport layer 55, and the electron injection layer 53 are formed by vapor deposition or coating, , Spin coating, dipping, printing, doctor blading, or electrophoresis.

The organic light emitting diode may be disposed on a substrate (not shown), which may be disposed under the anode 10 or above the cathode 70. In other words, the anode 10 may be formed on the substrate before the cathode 70, or the cathode 70 may be formed before the anode 10.

The substrate may be a light-transmissive substrate as a flat plate member, in which case the substrate may be glass; Ceramics material; And may be made of a polymer material such as polycarbonate (PC), polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polypropylene (PP) However, the present invention is not limited to this, and the substrate may be a metal substrate capable of light reflection.

Hereinafter, exemplary embodiments of the present invention will be described in order to facilitate understanding of the present invention. It should be understood, however, that the following examples are intended to aid in the understanding of the present invention and are not intended to limit the scope of the present invention.

[Experimental Examples; Examples]

Synthesis Example 1: Synthesis of Compound IV

[Reaction Scheme 1]

≪ Synthesis of ligand (2- (pyrazol-1-yl) pyridin-3-ol)

1H- pyrazole (1H-pyrazole, a1) 6g (87.25 mmol), 2- bromo-pyridin-3-ol (2-bromopyridin-3-ol , b) 16.86g (95.98mmol), K 2 CO 3 25.685g 0.97 g (3.75 mmol) of CuI, 0.94 g (8.16 mmol) of L-proline and 150 ml of DMSO were added to the flask and stirred for two days in a nitrogen atmosphere. As a result, 5.6 g (40% yield) of ligand (III) was obtained as a white solid.

GC-Mass (161.16 g / mol, measured: 160 g / mol)

1H, NMR (200 MHz, DMSO): 11.54 (s, IH), 9.14 (s, IH), 7.98 (m, 2H), 7.50 )

≪ Synthesis of organometallic compound (IV) >

Ligand (2- (pyrazol-1-yl ) pyridin-3-ol) 4g (24.51mmol), BeSO 4 · 4H 2 O 2.17g (12.26mmol), stirred at 60 ℃ in a nitrogen atmosphere into a 300ml of ethanol for 3 hours . Then, 14.85 ml of triethylamine was poured into the solution, and the mixture was gradually cooled to room temperature and stirred for 3 days. The resultant was washed with ethanol in a filtration filter and then dried to obtain 2.6 g (64% yield) of the product. 2.6 g of the resultant was sublimed and purified to obtain 1.8 g of the organometallic compound (IV) as a white solid.

 GC-Mass (calculated: 331.29 g / mol, measured: 330 g / mol)

N, 24.57; N, 25.52; O, 9.72, found: C, 58.57; H, 3.65; N, 24.57). Elemental analysis (theory: C, 58.35

2H), 7.76 (m, 4H), 7.25 (s, 4H), 6.76 (s, 2H)

Synthesis Example 2: Synthesis of Compound V

[Reaction Scheme 2]

<Synthesis of Ligand (2- (1,2,4-triazol-1-yl) pyridin-3-ol)

1H-1,2,4- triazole (1H-1,2,4-triazole) 5g (71.67mmol), 2- bromo-pyridin-3-ol _{13.86g (78.83mmol), K 2 CO} 3 21.10g ( 0.59 g (3.08 mmol) of CUI, 0.77 g (0.09 mmol) of L-proline, and 120 ml of DMSO were added and stirred in a nitrogen atmosphere for two days. As a result, 1 g of the ligand (9% yield) was obtained as a light yellow solid.

GC-Mass (theory: 162.15 g / mol, measurement: 161 g / mol)

(M, 2H), 7.96 (m, 2H), 7.48 (d, IH)

&Lt; Synthesis of organometallic compound (V) >

Ligand (2- (1,2,4-triazol-1 -yl) pyridin-3-ol) 0.5g (3.08mmol), BeSO 4 · 4H2O (0.27g, 1.54mmol) and 80ml of ethanol were put into a nitrogen for 3 hours Lt; RTI ID = 0.0 &gt; 60 C. &lt; / RTI &gt; Thereafter, 1.87 ml of triethylamine was added slowly to the room temperature after the injection, and the mixture was stirred for 3 days. The resulting filtrate was washed with ethanol and dried to obtain 0.2 g (39% yield) of the product. 0.2 g of the resultant was sublimed and purified to obtain 0.1 g of the organometallic compound (V) as a white solid.

GC-Mass (theory: 331.29 g / mol, measurement: 330 g / mol)

N, 33.62; N, 33.82; O, 9.66, found: C, 50.56; H, 3.09; N, 33.62). Elemental analysis (C, 50.76; H,

(D, 2H), 8.27 (m, 4H), 7.85 (m, 4H)

Synthesis Example 3: Synthesis of Compound VI

[Reaction Scheme 3]

<Synthesis of ligand (2- (5-methyl-1,2,3,4-tetrazol-1-yl) pyridin-

3 g (43.63 mmol) of 5-methyl-1H-tetrazole, 8.43 g (47.99 mmol) of 2-bromopyridin-3-ol and 12.84 g (92.92 mmol) of K ₂ CO ₃ , 0.36 g (1.88 mmol) of CUI, 0.47 g (4.08 mmol) of L-proline, and 70 ml of DMSO were added and stirred in a nitrogen atmosphere for two days. As a result, 0.5 g (6% yield) of a ligand was obtained.

GC-Mass (177.16 g / mol, measured: 176 g / mol)

1 H-NMR (200 MHz, DMSO): 11.12 (s, IH), 8.17 (m, IH), 7.45

&Lt; Synthesis of organometallic compound (VI) >

A ligand (2- (5-methyl-1,2,3,4 -tetrazole-1-yl) pyridin-3-ol) 0.5g (2.82mmol), BeSO 4 · 4H2O 0.25g (1.41mmol) and 70ml of ethanol And the mixture was stirred at 60 DEG C in a nitrogen atmosphere for 3 hours. Then, 1.71 ml of triethylamine was slowly brought to room temperature after the injection and stirred for 3 days. The resultant was washed with ethanol in a filtration filter and then dried to obtain 0.16 g (31% yield) of the product. 0.16 g of the resultant was sublimed and purified to obtain 0.1 g of the organometallic compound (VI) as a white solid.

GC-Mass (theory: 361.32 g / mol, measurement: 360 g / mol)

N, 38.64; N, 38.77; O, 8.86 Measured: C, 46.76; H, 3.59; N, 38.64). Elemental analysis (C, 46.54; H, 3.35;

(M, 2H), 7.21 (m, 4H), 3.12 (s, 6H)

Production Example 1: Organic light-emitting diode manufacture

(ITO / PEDOT: PSS / TAPC / mCP / Compound IV: F ₂ Irpic / TSPO1 / LiF / Al)

The anode ITO substrate was cleaned with ultrasonic waves for 30 minutes using pure water and isopropyl alcohol. The cleaned ITO substrate was surface-treated with ultraviolet light of short wavelength and then PEDOT: PSS (poly (3,4-ethylenedioxythiophene): poly (styrenesulfonate)) was spin-coated. After spin coating, a hole injecting or transporting material TAPC (1,1-Bis [4- [N, N'-Di (p-tolyl) Amino] Phenyl] Cyclohexane and mCP (N, N-dicarbazolyl- -benzene) was deposited at a rate of 0.1 nm / s under a pressure of 1 × 10 ^-6 torr to form a hole transport layer. Thereafter, Compound IV, which was synthesized through Synthesis Example 1, as a blue phosphorescent host material and F ₂ Irpic (Bis (4,6-difluorophenylpyridinato-N, C 2) picolinatoiridium), a phosphorescent dopant, was irradiated at a pressure of ¹ × 10 ^-6 torr at 0.015 nm / s to form a light emitting layer. As an electron transport material, TSPO1 (diphenylphosphine oxide-4- (triphenylsilyl) phenyl) was deposited at a rate of 0.1 nm / s under a pressure of 1 × 10 ^-6 torr to form an electron transport layer. Thereafter, LiF as an electron injecting material was vapor-deposited at a pressure of ¹ x 10 ^-6 torr at a rate of 0.01 nm / s to form an electron injecting layer of 1 nm. Thereafter, Al was vapor-deposited at a rate of 0.5 nm / sec under a pressure of ¹ x 10 ^-6 torr to form a cathode of 100 nm, thereby forming an organic light-emitting diode. After the device was formed, the device was sealed using a CaO wetting agent and a glass cover glass.

The organic light emitting diode according to the present example exhibited a quantum efficiency of 19.7%, a current efficiency of 32.4 cd / A, a power efficiency of 22.5 lm / W at a voltage of 5 V and x = 0.14 and y = 0.29 based on CIE 1931 color coordinates, And showed phosphorescence characteristics.

Production Example 2: Organic light-emitting diode manufacture

(ITO / PEDOT: PSS / TAPC / mCP / compound Ⅴ: F ₂ Irpic / TSPO1 / LiF / Al)

An organic light emitting diode was prepared and sealed in the same manner as in Production Example 1, except that Compound V synthesized in Synthesis Example 2 was used as a blue phosphorescent host material in the light emitting layer.

The organic light emitting diode according to the present example exhibited a quantum efficiency of 19.1%, a current efficiency of 31.5 cd / A, a power efficiency of 20.8 lm / W at a voltage of 5 V and x = 0.14 and y = 0.29 based on CIE 1931 color coordinates. And showed phosphorescence characteristics.

Production Example 3: Organic light-emitting diode manufacture

(ITO / PEDOT: PSS / TAPC / mCP / compound Ⅵ: F ₂ Irpic / TSPO1 / LiF / Al)

An organic light emitting diode was prepared and sealed in the same manner as in Production Example 1, except that the compound (VI) synthesized in Synthesis Example 2 was used as a blue phosphorescent host material in the light emitting layer.

The organic light emitting diode according to the present example exhibited a quantum efficiency of 17.5%, a current efficiency of 28.8 cd / A, a power efficiency of 18.1 lm / W at a voltage of 5 V and an x = 0.14 and y = 0.29 based on CIE 1931 color coordinates, Luminescence characteristics.

Comparative Example 1: Manufacture of organic light emitting diode

(ITO / PEDOT: PSS / TAPC / mCP / mCP: F ₂ Irpic / TSPO1 / LiF / Al)

An organic light emitting diode was prepared and sealed in the same manner as in Production Example 1, except that mCP was used as a blue phosphorescent host material in the light emitting layer.

The organic light emitting diode according to the present example exhibited quantum efficiency of 14.3%, current efficiency of 23.6 cd / A, power efficiency of 14.8 lm / W at a voltage of 5 V, and x = 0.14 and y = 0.29 based on the CIE 1931 color coordinate.

Comparative Example 2: Fabrication of organic light emitting diode

(ITO / PEDOT: PSS / TAPC / mCP / Be (bq) 2: F ₂ Irpic / TSPO1 / LiF / Al)

(Bq) 2 (bis (10-hydroxybenzo [h] quinolinato) beryllium) was used as a blue phosphorescent host material in the light emitting layer. The organic light emitting diode was prepared and sealed by the same method as in Production Example 1.

The organic light emitting diode according to the present example exhibited a quantum efficiency of 7.0%, a current efficiency of 14.2 cd / A, a power efficiency of 8.9 lm / W at a voltage of 5 V, and x = 0.19 and y = 0.29 based on CIE 1931 color coordinates.

It can be seen from the above results that the organic light emitting diodes according to Production Examples 1 to 3 have improved quantum efficiency, current efficiency, and power efficiency, as compared with the organic light emitting diode according to the comparative examples, without changing the color coordinates.

 While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, but, on the contrary, This is possible.

Claims (16)

1. A compound for an organic light emitting diode represented by the following Formula 1:
[Chemical Formula 1]

In Formula 1,
M is a Group 2 or Group 3 metal,
X is O or S,
At least one of A ₁ , A ₂ , A ₃ and A ₄ is N and the remaining R ₁ are the same or different CR ₁ (s), R ₁ is hydrogen, a halogen group, a cyano group, (C1 to C30 alkyl) silyl group, di (C1 to C30 alkyl) silyl group, di (C1 to C30 alkyl) (C6 or C60 aryl) silyl group, (C1 to C30 alkyl) amino group, di (C6 or C60 aryl) amino group, diheteroarylamino group, (C1 to C30 aryl) silyl group, C30 alkyl) (C6 or C60 aryl) amino group, or a (C1 to C30 alkyl) heteroarylamino group,
B is a pentachloric aromatic or hexagonal ring aromatic,
Y is C or N,
n is 2 or 3; The compound according to claim 1, wherein the compound is represented by the following formula (2):
(2)

In Formula 2,
M, X, A _1, A _2, A _3, A _4, Y and n are respectively the same as M, X, A _1, A _2, A _3, A _4, and Y and n is represented by Formula 1,
B _1, B _2, and B ₃ are independently N or R ₂ are the same or different CR ₂ (s) with each other and, R ₂ is a hydrogen, a halogen group, a cyano group, an alkyl group of C1 to C30, C6 or C60 (C1 to C30 alkyl) silyl, di (C1 to C30 alkyl) (C6 or C60 aryl) silyl, di (C1 to C30 alkyl) heteroarylsilyl, tri (C6 or C60 aryl) silyl group, triheteroarylsilyl group, di (C1 to C30 alkyl) amino group, di (C6 or C60 aryl) amino group, diheteroarylamino group, C1 to C30 alkyl Or an aryl of C60) amino group, or (C1-C30 alkyl) heteroarylamino group. The method of claim 2,
And at least one of Y, B ₁ , B ₂ , and B ₃ is N. The method of claim 3,
Y is N,
B ₁ , B ₂ , and B ₃ are CR _{2 s in} which R ₂ is the same or different. The method of claim 3,
Y and B &lt; ₂ &gt; are N,
B ₁ and B ₃ are CR _{2 s in} which R ₂ is the same or different. The method of claim 3,
Y, B ₁ , and B ₂ are N,
And B &lt; ₃ &gt; is CR &lt; _{2 &} gt ;. The method according to claim 1 or 2,
A &lt; ₁ &gt; is N,
A ₂ , A ₃ , and A ₄ are those wherein R ₁ is the same or different CR ₁ (s). The method according to claim 1,
The compound is an organic light emitting diode compound represented by the following formula (3): &lt; EMI ID =
(3)

In Formula 3,
M, X, and n are each the same as M, X, and n in Formula 1, and B ₁ , B ₂ , and B ₃ are independently of each other N or R ₂ are the same or different CR ₂ (C 1 to C 30 alkyl) silyl, di (C 1 to C 30 alkyl) (C 6 to C 30 alkyl) silyl, and R ₂ is hydrogen, halogen, cyano, a C1 to C30 alkyl group , a C6 or C60 aryl group, a heteroaryl group, (C1 to C30 alkyl) silyl, di (C1 to C30 alkyl) heteroarylsilyl, tri (C6 or C60 aryl) silyl, triheteroarylsilyl, di C6 or C60 aryl) amino group, diheteroarylamino group, (C1 to C30 alkyl) (C6 or C60 aryl) amino group, or (C1 to C30 alkyl) heteroarylamino group. The method according to claim 1,
And M is Be, Zn, Mg, Al, Ga, or In. The method according to claim 1,
The compound is an organic light-emitting diode compound represented by the following general formula (4), (5), or (6)
[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

The method according to claim 1,
Wherein the compound is used as one of a host material, an electron injecting material, and an electron transporting material of an organic light emitting diode. An organic light emitting diode comprising an anode, a hole conduction layer, a light emitting layer, an electron conduction layer, and a cathode sequentially stacked,
Wherein one of the hole transporting layer, the light emitting layer and the electron transporting layer comprises the compound of claim 1. The method of claim 12,
Wherein the electron conduction layer includes an electron transporting layer and an electron injection layer,
Wherein one of the light emitting layer, the electron transporting layer, and the electron injecting layer comprises the compound of claim 1. 14. The method of claim 13,
Wherein the light emitting layer comprises a host material and a dopant material,
Wherein one of the host material, the electron transporting layer, and the electron injecting layer comprises the compound of claim 1. 15. The method of claim 14,
Wherein the host material is a phosphorescent host material and the dopant material is a phosphorescent dopant material. 16. The method of claim 15,
Wherein the light emitting layer is a light emitting layer emitting blue light.

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