KR101953767B1 - Novel organometallic compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel organometallic compound and an organic light emitting device using the same.

Description

TECHNICAL FIELD The present invention relates to a novel organometallic compound and an organic light emitting device using the same.

The present invention relates to a novel organometallic compound and an organic light emitting device comprising the same.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, excellent characteristics of luminance, driving voltage and response speed, and much research has been conducted.

The organic light emitting device generally has a structure including an anode and a cathode, and an organic layer between the anode and the cathode. The organic material layer may have a multilayer structure composed of different materials in order to improve the efficiency and stability of the organic light emitting device. For example, the organic material layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out.

There is a continuing need for the development of new materials for the organic materials used in such organic light emitting devices.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to a novel organometallic compound and an organic light emitting device comprising the same.

The present invention provides an organometallic compound represented by any of the following formulas (1) to (3).

[Chemical Formula 1]

(2)

(3)

In the above Formulas 1 to 3,

M is iridium (Ir), platinum (Pt), osmium (Os), titanium (Ti), zirconium (Zr), or hafnium

The ring A is a pyridine ring and the ring B is connected to the ortho position of N,

T is a substituted or unsubstituted silyl group,

And X ₁ to X ₆ 2 dogs neighborhood of the C is connecting to the formula (1a) and the CC bond, and the rest each independently N or CR _3,

R ₁ to R ₃ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-6 alkyl; Substituted or unsubstituted C _1-6 haloalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Or substituted or unsubstituted C _1-60 heteroaryl containing at least one of N, O and S,

a1 and a2 each independently represent an integer of 0 to 4,

b1 and b2 are each independently an integer of 1 to 4,

b3 is 1 or 2,

a2 + b1 is 4 or less,

n is 0, 1 or 2,

[Formula 1a]

In formula (1a)

X ₁₁ to X ₁₄ in formula (1) or (2) are each independently CR ₄ ,

X ₁₁ to X ₁₄ in Formula 3 are each independently N or CR ₄ , at least one of X ₁₁ to X ₁₄ is N,

Y ₁ is O, S, or Se,

R ₄ is hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-6 alkyl; Substituted or unsubstituted C _1-6 haloalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Or substituted or unsubstituted C _1-60 heteroaryl containing at least one of N, O and S,

* Represents a part connected to the B ring of the above formulas (1) to (3).

The present invention also provides a plasma display panel comprising: a first electrode; A second electrode facing the first electrode; And at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes an organic electroluminescent Device.

The organometallic compound represented by the formula (1) can be used as a material for an organic material layer of an organic light emitting device, and can improve a light emitting efficiency and a lifetime characteristic in an organic light emitting device. In particular, the organometallic compound represented by Formula 1 may be included in the light emitting layer and used as a phosphorescent dopant.

Fig. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3 and a cathode 4. Fig.
2 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 7, an electron transporting layer 8 and a cathode 4 It is.

Hereinafter, the present invention will be described in detail in order to facilitate understanding of the present invention.

The present invention provides a compound represented by the above formula (1).

는 다른 치환기에 연결되는 결합을 의미한다. In the present specification,

Quot; means a bond connected to another substituent.

As used herein, the term " substituted or unsubstituted " A halogen group; Cyano; A nitrile group; A nitro group; A hydroxy group; A carbonyl group; An ester group; Imide; An amino group; Phosphine oxide groups; An alkoxy group; An aryloxy group; An alkyloxy group; Arylthioxy group; An alkylsulfoxy group; Arylsulfoxy group; Silyl group; Boron group; An alkyl group; Cycloalkyl groups; An alkenyl group; An aryl group; Aralkyl groups; An aralkenyl group; An alkylaryl group; An alkylamine group; An aralkylamine group; A heteroarylamine group; An arylamine group; Arylphosphine groups; Or heteroaryl containing at least one of N, O and S atoms, or a substituted or unsubstituted one in which at least two of the above-exemplified substituents are connected . For example, when the "substituent group to which two or more substituents are connected" is a biphenyl group, the biphenyl group may be an aryl group substituted with one phenyl group, or may be interpreted as a substituent group in which two phenyl groups are connected.

In the present specification, the carbon number of the carbonyl group is not particularly limited, but it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the ester group may be substituted with a straight-chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms in the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the boron group specifically includes, but is not limited to, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, and a phenylboron group.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a n-butyl group, an isobutyl group, a tert-butyl group, But are not limited to, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, But are not limited to, dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl and 5-methylhexyl.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3- 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group or the like as the monocyclic aryl group, but is not limited thereto. Examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, a fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

And the like. However, the present invention is not limited thereto.

In the present specification, heteroaryl is heteroaryl containing at least one of O, N, Si and S as a hetero atom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heteroaryl include a thiophene group, a furane group, a furyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, A pyridazinyl group, a pyrazinopyranyl group, an isoquinoline group, a pyridazinyl group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, A benzothiazole group, a benzothiophene group, a benzofuranyl group, a phenanthroline group, a thiazolyl group, an isoaryl group, a thiazolyl group, an isothiazolyl group, An oxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group and the arylamine group is the same as the aforementioned aryl group. In the present specification, the alkyl group in the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the alkyl group described above. In the present specification, the heteroaryl among the heteroarylamines can be applied to the heteroaryl described above. In the present specification, the alkenyl group in the aralkenyl group is the same as the above-mentioned alkenyl group. In the present specification, the description of the aryl group described above can be applied except that arylene is a divalent group. In this specification, the description of the above-mentioned heteroaryl can be applied except that the heteroarylene is a divalent. In the present specification, the description of the above-mentioned aryl group or cycloalkyl group can be applied except that the hydrocarbon ring is not a monovalent group and two substituents are bonded to each other. In the present specification, the description of heteroaryl described above can be applied, except that the heterocycle is not monovalent and two substituents are bonded to each other.

Meanwhile, the organometallic compound according to the present invention is represented by any one of formulas (1) to (3). The compound represented by any one of Chemical Formulas 1 to 3 is substituted with at least one silyl group and has a ligand having an N-atom-containing heterocyclic ring to improve the driving voltage, lifetime and efficiency of an organic light emitting device employing such an organic metal compound Effect.

In the general formulas (1) to (3), T represents a substituted or unsubstituted silyl group, which may be represented by SiR ₁₁ R ₁₂ R ₁₃ . Wherein R ₁₁ to R ₁₃ each independently represent hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-6 alkyl; Substituted or unsubstituted C _1-6 haloalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Or substituted or unsubstituted C _1-60 heteroaryl containing one or more of N, O and S.

More specifically, R ₁₁ to R ₁₃ may each independently be substituted or unsubstituted C _1-10 alkyl, and more particularly, each independently, may be unsubstituted C _1-10 alkyl.

For example, the R ₁₁ to R ₁₃ is R ₁₁ to R ₁₃ each independently represent a methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec- may be a butyl, or tert- butyl, double in each Methyl.

According to one embodiment, in the above general formulas (1) to (3), M may specifically be iridium (Ir).

In the above Chemical Formulas 1 to 3, R ₁ to R ₄ are each independently hydrogen; heavy hydrogen; C _1-10 alkyl unsubstituted or substituted by deuterium; Or C _6-10 aryl which is unsubstituted or substituted by deuterium.

More specifically, in the above Chemical Formulas 1 to 3, R ₁ to R ₄ are each independently hydrogen; heavy hydrogen; methyl; Methyl substituted with deuterium; ethyl; Isopropyl; Isobutyl; Or phenyl.

In the above formulas (1) to (3), a1 represents the number of R ₁ , and when a1 is 2 or more, two or more R _{1 s} may be the same or different. The description of a2 can be understood with reference to the description of a1 and the structure of the formula (1).

Specifically, in the above formulas (1) to (3), a1 and a2 each independently represent 0 or 1.

Further, in the above Chemical Formulas 1 to 3, b1 to b3 are T substituents, that is, as shown the number of SiR ₁₁ R ₁₂ R _13, b1 is 2 or more, if two or more SiR ₁₁ R ₁₂ R ₁₃ are the same or be different from each other . b2 and b3 can be understood with reference to the description of b1 and the structures of formulas (2) and (3).

Specifically, in Formulas 1 to 3, b1 to b3 may be 1.

In the above general formulas (1) to (3), two adjacent X ₁ to X ₆ are C connected by the CC bond in the above formula (1a), and the others are independently N or CR ₃ . Accordingly, the B ring may have various structures according to the bonding position of the formula (1a).

Specifically, in the above formulas (1) and (2), the B ring may have any one of the structures represented by the following b11 to b16:

In the above formulas b11 to b16,

X ₁₁ to X ₁₄ are each independently CR ₄ , wherein R ₄ is as defined above,

Y ₁ is O, S, or Se,

* Represents a moiety connected to A rings and M in the above formulas (1) and (2), respectively.

In the above formula (3), the ring B may specifically have one of the structures represented by the following b21 to b26:

In the above formulas b21 to b26, T and b3 are as defined above,

X ₁₁ to X ₁₄ are each independently N or CR ₄ , at least one of X ₁₁ to X ₁₄ is N, R ₄ is as defined above,

Y ₁ is O, S, or Se,

* Represents a moiety connected to A ring and M in Formula 3 above.

Specifically, the organometallic compound may be a compound represented by any one of the following formulas (1-1) to (3-1)

[Formula 1-1]

 [Formula 2-1]

[Formula 3-1]

In the above Formulas 1-1 to 3-1,

M, X ₁ to X ₆ , X ₁₁ to X ₁₄ , Y ₁ , R ₁ and R ₂ , R ₁₁ to R ₁₃ , a 1, a 2, b 1, b 2, b 3 and n are as defined above.

More specifically, in Formula 1-1,

R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; C _1-10 alkyl unsubstituted or substituted by deuterium; Or C _6-10 aryl which is unsubstituted or substituted by deuterium, more specifically methyl,

R ₁₁ to R ₁₃ are each independently a substituted or unsubstituted C _1-10 alkyl,

The ring B has any one of the structures represented by the above-mentioned b11 to b16,

In the structure of the b11 to b16, X ₁₁ to X ₁₄ are each, independently, is CR _4, Y ₁ is O, and S, or Se, R ₄ is hydrogen; heavy hydrogen; C _1-10 alkyl unsubstituted or substituted by deuterium; Or C _6-10 aryl which is unsubstituted or substituted by deuterium,

a1 and a2 are each independently 0 or 1,

b1 is 1,

n may be 1 or 2.

In the above formula (2-1)

R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; C _1-10 alkyl unsubstituted or substituted by deuterium; Or C _6-10 aryl which is unsubstituted or substituted by deuterium,

R ₁₁ to R ₁₃ are each independently a substituted or unsubstituted C _1-10 alkyl,

The ring B has any one of the structures represented by the above-mentioned b11 to b16,

In the structure of the b11 to b16, X ₁₁ to X ₁₄ are each, independently, is CR _4, Y ₁ is O, and S, or Se, R ₄ is hydrogen; heavy hydrogen; C _1-10 alkyl unsubstituted or substituted by deuterium; Or C _6-10 aryl which is unsubstituted or substituted by deuterium,

a1 and a2 are each independently 0 or 1,

b2 is 1,

n may be 1 or 2.

In the above formula (3-1)

R ₁ and R ₂ are each independently hydrogen; heavy hydrogen; C _1-10 alkyl unsubstituted or substituted by deuterium; Or C _6-10 aryl which is unsubstituted or substituted by deuterium,

The ring B may have the structure of any one of the structures of the following formulas b21-1 to b21-4:

In Formulas b21-1 to b21-4,

Y ₁ is O, S or Se,

R ₁₁ to R ₁₃ each independently represent a substituted or unsubstituted C _1-10 alkyl group, more specifically, a methyl group,

* Represents a moiety connected to A rings and M in Formulas 1 and 2,

a1 and a2 are each independently 0 or 1,

b3 is 1,

n may be 0 or 2.

More specifically, the organometallic compound may be selected from the group consisting of the following compounds.

The organometallic compound represented by any one of Chemical Formulas 1 to 3 may include a silyl group in the ligand to increase the lifetime of the organic light emitting device using the silyl group. The organometallic compound represented by the above formula (3) enriches electrons in the compound by introducing an N-atom-containing heterocyclic ring such as benzofurpyridine instead of a hetero ring containing no N atom such as dibenzofuran in the ligand The effect of pushing the electrons can be shown. Therefore, the organic light emitting device using the organic light emitting device can have high efficiency, high luminance and long life.

Here, the organometallic compound represented by Formula 1 may be prepared through a ligand exchange reaction as shown in Reaction Scheme 1 below, but is not limited thereto. The above production method can be more specific in the production example to be described later.

[Reaction Scheme 1]

In the above Reaction Scheme 1,

또는

이고, D ₁ is

or

ego,

또는

이되, D₁이

일 때, E₁이

은 아니며, E ₁ is

or

Provided that, D ₁ is

E ₁ < / _RTI >

And,

X is SO ₃ CF ₃ , BF ₄ , or PF ₆ ,

M, X ₁ to X ₆ , R ₁ , R ₂ , T, a ₁ , a ₂ , b 1 and n are as defined in formula (1).

The reaction can be carried out in a polar solvent, specifically, in an alcoholic solvent such as methanol, ethanol and the like.

It is possible to prepare the organometallic compound represented by the above formula (1) to be prepared by appropriately substituting the starting materials compounds (Ia) and (Ib) with reference to the structures of the above reaction schemes 1 and 1.

The organometallic compound represented by Formula 2 may also be prepared through a ligand exchange reaction as shown in Reaction Scheme 2, but is not limited thereto. The above production method can be more specific in the production example to be described later.

[Reaction Scheme 2]

In the above Reaction Scheme 2,

또는

이고, D ₂ is

or

ego,

또는

이되, D₂가

일 때, E₂가

은 아니며, E ₂ is

or

Provided that, D ₂ is

E2 < / RTI &_gt;

And,

X is SO ₃ CF ₃ , BF ₄ , or PF ₆ ,

M, X ₁ to X ₆ , R ₁ , R ₂ , T, a ₁ , a ₂ , b ₂ and n are as defined in the formula (2).

It is possible to prepare the organometallic compound represented by the above formula (1) to be prepared by appropriately substituting the starting materials compounds (IIa) and (IIb) with reference to the structures of the above-mentioned Reaction Schemes 2 and 2.

The organometallic compound represented by Formula 3 may also be prepared through a ligand exchange reaction as shown in Reaction Scheme 3, but is not limited thereto. The above production method can be more specific in the production example to be described later.

[Reaction Scheme 3]

In Scheme 3,

또는

이고, D ₃ is

or

ego,

또는

이되, D₃이

일 때, E₃이

은 아니며, E ₃ is

or

However, D ₃

Two days time, E ₃

And,

X is SO ₃ CF ₃ , BF ₄ , or PF ₆ ,

M, X ₁ to X ₆ , R ₁ , R ₂ , T, a ₁ , a ₂ , b 3 and n are as defined in formula (3).

It is possible to prepare the organometallic compound represented by the above formula (1) to be prepared by appropriately substituting the starting materials, compounds (IIIa) and (IIIb), by referring to the structures of the above reaction schemes 3 and 3.

According to another embodiment of the present invention, there is provided an organic light emitting device comprising an organic metal compound represented by any one of Chemical Formulas 1 to 3.

For example, the organic light emitting device includes a first electrode; A second electrode facing the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers contains an organometallic compound represented by any one of Chemical Formulas 1 to 3 can do.

In addition, the organic layer may include a light emitting layer, and the light emitting layer may include an organic metal compound represented by any one of Chemical Formulas 1 to 3. In the light emitting layer, the organometallic compound represented by any one of Chemical Formulas 1 to 3 may serve as a dopant. Specifically, in the light emitting layer, the organometallic compound represented by Formula 1 may be included as a phosphorescent dopant.

At this time, the light emitting layer may further include a known host. Specifically, the weight ratio of the host to the organometallic compound represented by any one of Chemical Formulas 1 to 3 in the light emitting layer may be 99: 1 to 80:20, but is not limited thereto.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, in the organic light emitting device of the present invention, in addition to the light emitting layer as the organic material layer, a hole injecting layer and a hole transporting layer between the first electrode and the light emitting layer, and an electron transporting layer and an electron injecting layer between the light emitting layer and the second electrode are further included . ≪ / RTI > Further, at least one of an electron blocking layer and a hole blocking layer may be further disposed between the hole transporting layer and the light emitting layer, and between the light emitting layer and the electron transporting layer. However, the structure of the organic light emitting device is not limited thereto, and may include fewer or more organic layers.

Meanwhile, the organic light emitting device according to the present invention may be a normal type organic light emitting device in which an anode, one or more organic layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present invention may be an inverted type organic light emitting device in which a cathode, at least one organic material layer, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting diode according to an embodiment of the present invention is illustrated in FIGS.

Fig. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3 and a cathode 4. Fig. In such a structure, the organic metal compound represented by any one of Chemical Formulas 1 to 3 may be included in the light emitting layer.

2 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 7, an electron transporting layer 8 and a cathode 4 It is. In such a structure, the organic metal compound represented by any one of Chemical Formulas 1 to 3 may be included in the light emitting layer.

In addition, the organic light emitting device according to an embodiment of the present invention may include a substrate, an anode, a hole injecting layer, a hole transporting layer, a light emitting layer, a hole blocking layer, an electron transporting layer, an electron injecting layer and a cathode. The organometallic compound represented by any one of formulas (1) to (3) may be included in the light emitting layer.

The organic light emitting device according to the present invention may be manufactured by materials and methods known in the art except that at least one of the organic material layers includes an organometallic compound represented by any one of Chemical Formulas 1 to 3 have. In addition, when the organic light emitting diode includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention can be manufactured by sequentially laminating a first electrode, an organic layer, and a second electrode on a substrate. At this time, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form an anode Forming an organic material layer including a hole injection layer, a hole transporting layer, a light emitting layer and an electron transporting layer thereon, and then depositing a material usable as a cathode on the organic material layer. In addition to such a method, an organic light emitting device can be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

In addition, the compound represented by any one of Chemical Formulas 1 to 3 may be formed into an organic layer by a solution coating method as well as a vacuum deposition method in the production of an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating and the like, but is not limited thereto.

In addition to such a method, an organic light emitting device can be manufactured by sequentially depositing an organic material layer and a cathode material on a substrate from a cathode material (WO 2003/012890). However, the manufacturing method is not limited thereto.

In one example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode and the second electrode is a cathode.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted to the organic material layer. Specific examples of the positive electrode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SNO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

The negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

The hole injecting layer is a layer for injecting holes from an electrode. The hole injecting material has a hole injecting effect, and has a hole injecting effect on the light emitting layer or a light emitting material. A compound which prevents the migration of excitons to the electron injecting layer or the electron injecting material and is also excellent in the thin film forming ability is preferable. It is preferred that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

The hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer and transports holes from the anode or the hole injection layer to the light emitting layer by using a hole transport material. Is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material as described above. The host material is a condensed aromatic ring derivative or a heterocyclic compound. Specific examples of the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds. Examples of the heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Specifically, as the host material, one or a mixture of two or more selected from the group consisting of a compound represented by the following formula (4) and a compound represented by the following formula (5) may be used:

[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas (4) and (5)

Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ are each independently substituted or unsubstituted C _6-60 aryl; Or substituted or unsubstituted C _1-60 heteroaryl containing at least one of N, O and S,

L is a bond; Substituted or unsubstituted C _6-60 arylene; Or a substituted or unsubstituted C _2-60 heteroarylene containing at least one heteroatom selected from O, N, Si and S,

R _a to R _e each independently represent hydrogen, deuterium; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-6 alkyl; Substituted or unsubstituted C _1-6 haloalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Or substituted or unsubstituted C _2-60 heteroaryl containing at least one heteroatom selected from the group consisting of N, O and S,

p, q and r each independently represent an integer of 0 to 3;

More specifically, as the host material, one or a mixture of two or more selected from the group consisting of a compound represented by the following formula (4a) and a compound represented by the following formula (5a) can be used:

[Chemical Formula 4a]

[Chemical Formula 5a]

The dopant material may further include an aromatic amine derivative, a styrylamine compound, a boron complex, a fluoranthene compound, a metal complex, and the like in addition to the compound represented by any one of Chemical Formulas 1 to 3 above. Specific examples of the aromatic amine derivatives include condensed aromatic ring derivatives having substituted or unsubstituted arylamino groups, and examples thereof include pyrene, anthracene, chrysene, and peripherrhene having an arylamino group. Examples of the styrylamine compound include substituted or unsubstituted Wherein at least one aryl vinyl group is substituted with at least one aryl vinyl group, and at least one substituent selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group is substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like. Examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto.

The electron transporting layer is a layer that receives electrons from the electron injecting layer and transports electrons to the light emitting layer. The electron transporting material is a material capable of transferring electrons from the cathode well to the light emitting layer. Do. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transporting layer can be used with any desired cathode material as used according to the prior art. In particular, an example of a suitable cathode material is a conventional material with a low work function followed by an aluminum layer or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer for injecting electrons from the electrode. The electron injection layer has the ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron injection effect with respect to the light emitting layer or the light emitting material. A compound which prevents migration to a layer and is excellent in a thin film forming ability is preferable. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A nitrogen-containing 5-membered ring derivative, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, But is not limited thereto.

The organic light emitting device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

The organic metal compound represented by any one of Chemical Formulas 1 to 3 may be included in an organic solar cell or an organic transistor in addition to an organic light emitting device.

The organic metal compound represented by any one of Chemical Formulas 1 to 3 and the organic light emitting device including the organic metal compound will be described in detail in the following examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

Manufacturing example  One

Step 1-1: Preparation of Compound A1

2,5-bromopyridine (15 g, 63.63 mmol, 1 eq) and phenylboronic acid (8.1 g, 66.49 mmol, 1.1 eq) were added to a round bottom flask in a nitrogen atmosphere, (1.4 g, 1.20 mmol, 0.02 eq) of tetrakis- (triphenylphosphine) palladium was added thereto, followed by heating and stirring at 40 ° C for 5 hours. After the completion of the reaction, the temperature was lowered, and the aqueous layer was separated and the organic layer was removed. After dissolving it with CHCl ₃ , it was washed with water. Magnesium sulfate and acidic clay were added and stirred, followed by filtration and concentration under reduced pressure. Then, Compound A1 (yield: 77%) was isolated by column chromatography under the conditions of ethyl acetate: hexane = 1: 100.

Step 1-2: Preparation of compound A2

To a round bottom flask was added compound A1 (14g, 59.80mmol, 1eq) , 4, 4, 5, 5-tetramethyl- [1, 3, 2] -dioxaboralane (30.4, 119.61mmol, 2eq), Pd (dppf) Cl 2 ( 0.28 g, 0.18 mmol, 0.002 eq) and 300 ml of dioxane. The mixture was stirred at reflux for 18 hours. The temperature was lowered to room temperature and the solvent was concentrated under reduced pressure. The concentrate was completely dissolved in CHCl ₃ and then washed with water. The solution in which the product was dissolved was concentrated to ethanol to precipitate A2 (yield 80%).

Step 1-3: Preparation of compound A3

In a nitrogen atmosphere, A2 (15 g, 53.35 mmol, 1 eq), chlorotrimethylsilane (6.4 g, 58.69 mmol, 1.1 eq) was dissolved in tetrahydrofuran

After adding 2M aqueous potassium carbonate solution (90 ml), tetrakis- (triphenylphosphine) palladium (1.8 g, 1.60 mmol, 0.03 eq) was added thereto and stirred at reflux for 18 hours. After the completion of the reaction, the temperature was lowered, and the aqueous layer was separated and the organic layer was removed. After dissolving it with CHCl ₃ , it was washed with water. Magnesium sulfate and acidic clay were added and stirred, followed by filtration and concentration under reduced pressure. Subsequently, Compound A3 (yield: 83%) was isolated by column chromatography under the presence of hexane.

Step 1-4: Preparation of compound A4

Iridium chloride (15 g, 50.24 mmol, 1 eq) and Compound A3 (28.6 g, 125.60 mmol, 2.5 eq) were added to 1000 ml of 2-ethoxyethanol and 330 ml of distilled water and the mixture was heated and stirred for 18 hours. The temperature was lowered to room temperature, filtered and washed with 3 L of ethanol to prepare a solid compound A4 (yield 53%).

Step 1-5: Preparation of Compound A

AgOTf (4.7 g, 18.23 mmol) containing A4 (15 g, 8.68 mmol) prepared in the above Step 1-2 and 800 ml of methylene chloride was dissolved in 300 ml of methanol, and the mixture was stirred at room temperature . After 24 hours of filtration, the filtered filtrate was blown off and Toluene precipitated to give Compound A (yield 70%) without further purification.

Step 2-1: Preparation of compound B1

4, 5, 5-tetramethyl- [1,3,2] -dioxaboralane (20.6, 80.94 mmol, 2eq), 4-bromodibenzo [b, d] furan (10 g, 40.47 mmol, , Pd (dppf) Cl ₂ (0.1 g, 0.08 mmol, 0.002 eq) and 300 ml of dioxane were added thereto, followed by stirring at reflux for 18 hours. The temperature was lowered to room temperature and the solvent was concentrated under reduced pressure. The concentrate was completely dissolved in CHCl ₃ and then washed with water. The solution in which the product was dissolved was concentrated to ethanol to precipitate B1 (yield 92%).

Step 2-2: Preparation of compound B

Compound 2-bromopyridine (10g, 63.29mmol, 1eq) and Compound B1 (19.5g, 66.46mmol, 1.05eq) were dissolved in tetrahydrofuran in a round bottom flask under nitrogen atmosphere and 2M aqueous potassium carbonate solution (0.7 g, 0.63 mmol, 0.01 eq) of tetrakis- (triphenylphosphine) palladium and stirred at reflux for 18 hours. After the completion of the reaction, the temperature was lowered, and the aqueous layer was separated and the organic layer was removed. After dissolving it with CHCl ₃ , it was washed with water. Magnesium sulfate and acidic clay were added and stirred, followed by filtration and concentration under reduced pressure. Subsequently, Compound B (90% yield) was isolated by column chromatography under the conditions of ethyl acetate: hexane = 1: 10.

Step 3-1: Preparation of Compound 1

Compound A (8 g, 7.69 mmol, 1 eq), compound B (4.7 g, 19.23 mmol, 2.5 eq), 50 ml of MeOH and 50 ml of EtOH were placed in a round bottom flask under nitrogen atmosphere and stirred for 48 hours at a reaction temperature of 90 ° C. After completion of the reaction, the reaction product was filtered and purified by column chromatography under the conditions of ethyl acetate: hexane = 1: 4 to prepare Compound 1 (yield 27%).

Manufacturing example  2

Step 1-1: Compound C1  Produce

Compound C1 was prepared in the same manner as Intermediate Al except that 2,4-dibromopyridine was used instead of 2,5-dibromopyridine.

Step 1-2: Preparation of compound C2

Compound C2 was prepared in the same manner as Intermediate A2 except for using C1 instead of A1.

Step 1-3: Preparation of Compound C3

Compound C3 was prepared in the same manner as Intermediate A3 except for using C2 instead of A2.

Step 1-4: Preparation of compound C4

Compound C4 was prepared in the same manner as Intermediate A4 except that C3 was used instead of A3.

Step 1-5: Preparation of compound C

Compound C was prepared in the same manner as Compound A except that C4 was used instead of A4.

Step 2-1: Preparation of compound 2

Compound 2 was prepared in the same manner as Compound 1 except that C was used instead of A.

Manufacturing example  3

Step 1-1: Compound D1's  Produce

Compound D1 was prepared in the same manner as Intermediate Al except that 2,3-dibromopyridine was used instead of 2,5-dibromopyridine.

Step 1-2: Compound Of D2  Produce

Compound D2 was prepared in the same manner as Intermediate A2 except for using D1 instead of A1.

Step 1-3: Preparation of compound D3

Compound D3 was prepared in the same manner as Intermediate A3 except for using D2 instead of A2.

Step 1-4: Preparation of compound D4

Compound D4 was prepared in the same manner as Intermediate A4 except for using D3 instead of A3.

Step 1-5: Preparation of compound D

Compound D was prepared in the same manner as Compound A except for using D4 instead of A4.

Step 2-1: Preparation of compound 3

Compound 3 was prepared in the same manner as Compound 1 except that D was used instead of A.

Manufacturing example  4

Step 1-1: Compound E1  Produce

Compound E1 was prepared in the same manner as Intermediate B1 except that 3-bromodibenzo [b, d] furan was used instead of 4-bromodibenzo [b, d] furan.

Step 1-2: Preparation of Compound E

Compound E was prepared in the same manner as Compound B except that E1 was used instead of B1.

Step 2-1: Preparation of compound 4

Compound 4 was prepared in the same manner as Compound 1 except that Compound E was used instead of Compound B.

Manufacturing example  5

Step 1-1: Compound F1's  Produce

Compound F1 was prepared in the same manner as Intermediate B1 except that 2-bromodibenzo [b, d] furan was used instead of 4-bromodibenzo [b, d] furan.

Step 1-2: Preparation of Compound F

Compound F was prepared in the same manner as Compound B except that F1 was used instead of B1.

Step 2-1: Preparation of compound 5

Compound 5 was prepared in the same manner as Compound 1 except that F was used instead of Compound B.

Manufacturing example  6

Step 1-1: Compound G1's  Produce

Compound G1 was prepared in the same manner as Intermediate B1 except for using 1-bromodibenzo [b, d] furan instead of 4-bromodibenzo [b, d] furan.

Step 1-2: Preparation of Compound G

Compound G was prepared in the same manner as Compound B except that G1 was used instead of B1.

Step 2-1: Preparation of compound 5

Compound 6 was prepared in the same manner as Compound 1 except that G was used in place of Compound B.

Manufacturing example  7

Step 1-1: Compound H1  Produce

Compound H1 was prepared in the same manner as Intermediate B1 except that 4-bromodibenzo [b, d] thiophene was used instead of 4-bromodibenzo [b, d] furan.

Step 1-2: Preparation of compound H

Compound H was prepared in the same manner as Compound B except that H1 was used instead of B1.

Step 2-1: Preparation of Compound 7

Compound 7 was prepared in the same manner as Compound 1 except that H was used instead of Compound B.

Manufacturing example  8

Step 1-1: Compound I1  Produce

Compound I1 was prepared in the same manner as Intermediate B1 except for using 4-bromodibenzo [b, d] selenophene instead of 4-bromodibenzo [b, d] furan.

Step 1-2: Preparation of Compound (I)

Compound I was prepared in the same manner as Compound B except that I1 was used instead of B1.

Step 2-1: Preparation of compound 8

Compound 8 was prepared in the same manner as Compound 1 except that Compound I was used instead of Compound B.

Manufacturing example  9

Step 1-1: Compound J1  Produce

4,6-dibromodibenzo [b, d] furan (10 g, 30.68 mmol, 1 eq) was dissolved in 100 ml of tetrahydrofuran and the temperature was lowered to -78 ° C. After holding for 30 minutes, normal-butylithium (2.2 g, 33.74 mmol, 1.1 eq) was added. After one hour, iodomethane-d3 (4.7 g, 32.21 mmol, 1.05 eq) was added and stirred for 4 hours while slowly warming to room temperature. Water was added to terminate the reaction, and Compound J1 (yield 90%) was obtained by column chromatography under a condition of ethyl acetate: hexane = 1:10.

Step 1-2: Preparation of compound J2

Compound I was prepared in the same manner as Compound B1, except that J1 was used instead of 4-bromodibenzo [b, d] furan.

Step 1-3: Preparation of compound J

Compound J was prepared in the same manner as Compound B except that J2 was used instead of B1.

Step 2-1: Preparation of compound 9

Compound 9 was prepared in the same manner as Compound 1 except that J was used instead of Compound B.

Manufacturing example  10

Step 1-1: Compound Ten  Produce

Compound 10 was prepared in the same manner as Compound 1 except that C was used instead of A and J was used instead of B.

Manufacturing example  11

Step 1-1: Compound Eleven  Produce

Compound 11 was prepared in the same manner as Compound 1 except that D was used instead of A and J was used instead of B.

Manufacturing example  12

Step 1-1: Compound Of K1  Produce

Compound K1 was prepared in the same manner as Compound A4 except that B was used instead of A3.

Step 1-2: Preparation of compound K

Compound K was prepared in the same manner as Compound A except that K1 was used instead of A4.

Step 2-1: Preparation of compound 12

Compound 12 was prepared in the same manner as Compound 1 except that K was used instead of A and A3 was used instead of B.

Manufacturing example  13

Step 1-1: Compound L1  Produce

Compound L1 was prepared in the same manner as in the preparation of Compound A4 except that E was used instead of A3.

Step 1-2: Preparation of Compound L

Compound L was prepared in the same manner as Compound A except that L1 was used instead of A4.

Step 2-1: Preparation of compound 13

Compound 13 was prepared in the same manner as Compound 1 except that L was used instead of A and A3 was used instead of B.

Manufacturing example  14

Step 1-1: Compound M1's  Produce

Compound M1 was prepared in the same manner as Compound A4 except that G was used instead of A3.

Step 1-2: Preparation of compound M

Compound M was prepared in the same manner as Compound A except that M1 was used instead of A4.

Step 2-1: Preparation of compound 14

Compound 14 was prepared in the same manner as Compound 1 except that M was used instead of A and A3 was used instead of B.

Manufacturing example  15

Step 1-1: Compound O1  Produce

The compound O1 was prepared in the same manner as the compound A1 except for using 2-bromopyridine instead of 2,5-bromopyridine and (4-chlorophenyl) boronic acid instead of phenylboronic acid.

Step 1-2: Preparation of compound O2

Compound O2 was prepared in the same manner as compound A2 except that O1 was used instead of A1.

Step 1-3: Preparation of compound O3

Compound O3 was prepared in the same manner as Compound A3 except that O2 was used instead of A2.

Step 1-4: Preparation of compound O4

Compound O4 was prepared in the same manner as Compound A4 except that O3 was used instead of A3.

Step 1-5: Preparation of compound O

Compound O was prepared in the same manner as Compound A except that O4 was used instead of A4.

Step 2-1: Preparation of compound 15

Compound 15 was prepared in the same manner as Compound 1 except that O was used instead of A.

Manufacturing example  16

Step 1-1: Compound P1  Produce

Compound P1 was prepared in the same manner as Compound A1 except that 3-bromopyridine was used instead of 2,5-bromopyridine and (3-chlorophenyl) boronic acid was used instead of phenylboronic acid.

Step 1-2: Compound P2  Produce

Compound P2 was prepared in the same manner as Compound A2 except that P1 was used instead of A1.

Step 1-3: Preparation of compound P3

Compound P3 was prepared in the same manner as Compound A3 except that P2 was used instead of A2.

Step 1-4: Preparation of compound P4

Compound P4 was prepared in the same manner as Compound A4 except that P3 was used instead of A3.

Step 1-5: Preparation of compound P

Compound P was prepared in the same manner as Compound A except that P4 was used in place of A4.

Step 2-1: Preparation of compound 16

Compound 16 was prepared in the same manner as Compound 1 except that P was used instead of A.

Manufacturing example  17

Step 1-1: Compound 17  Produce

Compound 17 was prepared in the same manner as Compound 1 except that K was used instead of A and O3 was used instead of B.

Manufacturing example  18

Step 1-1: Compound Q1  Produce

Compound Q1 was prepared in the same manner as Intermediate Al except that 2-bromopyridine was used instead of 2,5-dibromopyridine.

Step 1-2: Preparation of compound Q2

Compound Q2 was prepared in the same manner as Intermediate A4 except for using Q1 in place of A3.

Step 1-3: Preparation of compound Q

Compound Q was prepared in the same manner as Compound A except that Q2 was used instead of A4.

Step 2-1: Preparation of compound R1

Method for preparing Compound A1 except that 3-bromo-6-chloropyridin-2-amine was used instead of 2,5-bromopyridine and (2,3-dimethoxyphenyl) boronic acid was used instead of phenylboronic acid , The compound R1 was prepared.

Step 2-2: Preparation of compound R2

Compound R1 (11.8 g, 48.34 mmol, 1 eq) was dissolved in tetrahydrofuran, acetic acid (0.3 M, 161 ml) was added, and the temperature was lowered to 0 ° C. tert-Butyl nitrite (10.34 g, 87.01 mmol, 1.8 eq) was slowly dropped, stirred at 0 ° C for 2 hours and slowly warmed to room temperature. After 4 hours, the reaction was terminated. Compound R2 (yield: 34%) was isolated by column chromatography under the conditions of ethyl acetate: hexane = 1: 100.

Step 2-3: Preparation of compound R3

Compound (R2) (5 g, 23.45 mmol, 1 eq) was dissolved in 100 ml of dichloromethane, and then cooled to 0 ° C. Tribromobrane (17.62 g, 70.34 mmol, 3 eq) was diluted in 100 ml dichloromethane and then slowly added dropwise. After slowly raising the temperature to room temperature, the reaction was terminated after 3 hours. The resulting reaction was filtered and washed with water to produce compound R3 (69% yield).

Step 2-4: Preparation of compound R4

Potassium carbonate (10 g, 100.40 mmol, 1 eq) was added to the flask and dissolved in 80 ml of water. Compound R3 was dissolved in 300 ml of acetonitrile and placed in a flask. perfluoro-1-butanesulfonyl fluoride (22.7 g, 75.30 mmol, 1.5 eq) was slowly added dropwise and the mixture was stirred at room temperature for 18 hours. After completion of the reaction, the reaction mixture was precipitated in ethanol to obtain a compound R4 (yield 89%).

Step 2-5: Preparation of compound R5

Compound R5 was prepared in the same manner as compound B1 was prepared except that R4 was used instead of 4-bromodibenzo [b, d] furan.

Step 2-6: Preparation of compound R6

Compound R6 was prepared in the same manner as compound B except for using R5 instead of B1.

Step 2-7: Preparation of compound R7

Compound R7 was prepared in the same manner as compound B1 except for using R6 instead of 4-bromodibenzo [b, d] furan.

Step 2-8: Preparation of compound R

Compound R was prepared in the same manner as Compound A1 except that R7 was used instead of 2,5-bromopyridine and chlorotrimethylsilane was used in place of phenylboronic acid.

Step 3-1: Preparation of compound 18

Compound 18 was prepared in the same manner as Compound 1 except that Q was used instead of A and R was used instead of B.

Manufacturing example  19

Step 1-1: Compound S1  Produce

Compound S1 was prepared in the same manner as in the preparation of Compound A4, except that R was used instead of A3.

Step 1-2: Compound Of S  Produce

Compound S was prepared in the same manner as Compound A except that S1 was used instead of A4.

Step 2-1: Compound 19's  Produce

Compound 19 was prepared in the same manner as Compound 1 except that S was used instead of A and Q1 was used instead of B.

Example  One

A thin glass substrate coated with ITO (indium tin oxide) at a thickness of 1,300 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, a Fischer Co. product was used as a detergent, and distilled water, which was filtered with a filter of Millipore Co., was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically cleaned with a solvent of isopropyl alcohol, acetone and methanol in order, dried and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

The following hexanitrile hexaazatriphenylene (HAT) compound was thermally vacuum deposited on the ITO transparent electrode prepared above to form a hole injection layer having a thickness of 500 Å.

The HT-1 compound was thermally vacuum deposited to a thickness of 800 Å on the hole injection layer, and HT-2 compound was sequentially vacuum deposited to a thickness of 500 Å to form a hole transport layer.

Subsequently, a host (H1) and a compound 1 synthesized as a phosphorescent dopant in the above production example were vacuum deposited on the hole transport layer at a weight ratio of 88:12 to form a 350 Å thick light emitting layer.

Et 2 material and LiQ (Lithium Quinolate) were vacuum deposited on the hole blocking layer at a weight ratio of 1: 1 to form a hole blocking layer having a thickness of 250 ANGSTROM Thereby forming an electron transporting layer.

Lithium fluoride (LiF) was sequentially deposited on the electron transport layer to a thickness of 10 Å, and aluminum was deposited thereon to a thickness of 1000 Å to form a cathode. The deposition rate of the organic material was maintained at 0.4 to 0.7 Å / sec, the lithium fluoride at the cathode was maintained at a deposition rate of 0.3 Å / sec, and the deposition rate of aluminum was maintained at 2 Å / sec. ^-7 to 5 x 10 < ^-8 > torr.

Example  2 to 16

The organic light emitting devices of Examples 2 to 16 were fabricated in the same manner as in Example 1, except that the compound described in Table 1 was used instead of Compound 1 as the phosphorescent dopant in the formation of the light emitting layer. In this case, when a mixture of two kinds of compounds is used as the host, the parenthesized means the weight ratio between the host compounds, and the H2 substance is as described above.

Comparative Example  1 to 5

The organic light emitting devices of Comparative Examples 1 to 5 were fabricated in the same manner as in Example 1, except that the compound described in Table 1 was used instead of Compound 1 as a host in forming the light emitting layer.

Experimental Example  One

The voltage, efficiency, color coordinates, and lifetime were measured by applying currents to the organic light emitting devices fabricated in Examples 1 to 16 and Comparative Examples 1 to 5, and the results are shown in Table 1 below.

T95 means the time required for the luminance to be reduced to 95% from the initial luminance.

Host
matter Dopant
matter Dopant
Concentration (%) Voltage
(V
@ 10 mA / cm ² ) efficiency
(cd / A
@ 10 mA / cm ² ) Color coordinates
(x, y) life span
(T95, h,
@ 50 mA / cm ² ) Example 1 H1 One 12 2.91 79 (0.350, 0.629) 152 Example 2 H1 2 12 2.93 80 (0.351, 0.628) 155 Example 3 H1 3 12 3.05 76 (0.350, 0.631) 131 Example 4 H1 4 12 2.91 79 (0.364, 0.625) 212 Example 5 H1 9 12 2.96 78 (0.349, 0.631) 161 Example 6 H1 14 12 2.95 77 (0.352, 0.630) 143 Example 7 H1 16 12 3.00 75 (0.352, 0.631) 140 Example 8 H1 18 12 2.97 81 (0.353, 0.631) 318 Example 9 H1: H2
(50:50) One 12 3.49 85 (0.357, 0.622) 340 Example 10 H1: H2
(50:50) 6 12 3.61 85 (0.354, 0.621) 343 Example 11 H1: H2
(50:50) 9 12 3.50 86 (0.355, 0.623) 362 Example 12 H1: H2
(50:50) 10 12 3.53 85 (0.359, 0.622) 366 Example 13 H1: H2
(50:50) 12 12 3.48 87 (0.357, 0.623) 342 Example 14 H1: H2
(50:50) 13 12 3.50 88 (0.360, 0.625) 391 Example 15 H1: H2
(50:50) 18 12 3.40 90 (0.355, 0.621) 419 Example 16 H1: H2
(50:50) 19 12 3.40 89 (0.355, 0.620) 413 Comparative Example 1 H1 D1 12 3.10 60 (0.323, 0.631) 40 Comparative Example 2 H1 D2 12 3.07 71 (0.343, 0.630) 57 Comparative Example 3 H1 D3 12 3.09 75 (0.351, 0.620) 126 Comparative Example 4 H1: H2
(50:50) D1 12 3.50 67 (0.450, 0.540) 140 Comparative Example 5 H1: H2
(50:50) D3 12 3.60 80 (0.360, 0.616) 283

As shown in Table 1, when the compound of the present invention was used as a phosphorescent dopant, it was confirmed that the phosphorescent dopant exhibited excellent lifetime characteristics in comparison with Comparative Examples using the compounds of D1 to D3. In addition, in Examples 1 to 3 and 8, the lifetime characteristics were increased up to 250% as compared with Comparative Examples 2 and 3. From these results, it can be seen that the life time difference is remarkable depending on the presence or absence of the silyl substituent and the substitution position.

1: substrate 2: anode
3: light emitting layer 4: cathode
5: Hole injection layer 6: Hole transport layer
7: light emitting layer 8: electron transporting layer

Claims (15)

An organometallic compound represented by the following formula (3)
(3)

In Formula 3,
M is iridium (Ir)
The ring A is a pyridine ring and the ring B is connected to the ortho position of N,
R ₁ and R ₂ are each independently hydrogen,
a1 and a2 each independently represent an integer of 0 to 4,
The ring B has any one of the structures represented by the following formulas b21 to b26,

In the above formulas b21 to b26,
T is SiR ₁₁ R ₁₂ R ₁₃ , and R ₁₁ to R ₁₃ are each independently hydrogen; Or unsubstituted C _1-10 alkyl,
X ₁₁ to X ₁₄ are each independently N or CR ₄ , at least one of X ₁₁ to X ₁₄ is N,
Y ₁ is O, S, or Se,
R < ₄ > is hydrogen,
* Represents a moiety connected to A ring and M in Formula 3,
b3 is 1 or 2,
n is 0, 1 or 2;
delete delete delete delete delete delete The method according to claim 1,
The compound is an organometallic compound represented by the following formula (3-1): < EMI ID =
[Formula 3-1]

In Formula 3-1,
M, X ₁₁ to X ₁₄ , Y ₁ , R ₁ , R ₂ , a ₁ , a ₂ , b 3 and n are as defined in claim 1,
R ₁₁ to R ₁₃ each independently represent hydrogen; Or unsubstituted C _1-10 alkyl.
delete 9. The method of claim 8,
And R < ₁₁ > to R < ₁₃ > are each methyl.
9. The method of claim 8,
and b3 is 1, an organometallic compound.
The method according to claim 1,
Wherein the compound is any one selected from the group consisting of the following compounds:

A first electrode; A second electrode facing the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes at least one layer of the organic material layer according to any one of claims 1, 8, 10, 11 And an organometallic compound according to any one of claims 1 to 12.
14. The method of claim 13,
Wherein the organic compound layer containing the compound is a light emitting layer.
15. The method of claim 14,
Wherein the compound is included as a dopant.

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