KR20160013790A - Organic optoelectric device and display device - Google Patents

Abstract

The present invention relates to an organic optoelectronic element and a display device. The organic optoelectronic device comprises: an anode and a cathode facing each other; a light emitting layer disposed between the anode and the cathode; a hole transport layer disposed between the anode and the light emitting layer; and a hole transport auxiliary layer disposed between the hole transport layer and the light emitting layer. The light emitting layer comprises a first compound of at least one represented by chemical formula 1 and a second compound of at least one represented by chemical formula 2. In addition, the hole transport layer comprises a third compound represented by a combination of a moiety represented by chemical formula 3, a moiety represented by chemical formula 4, and a moiety represented by chemical formula 5. The chemical formula 1 to the chemical formula 5 are the same as described in the specification.

Description

TECHNICAL FIELD [0001] The present invention relates to an organic optoelectronic device,

Organic optoelectronic devices and display devices.

Organic optoelectronic devices are devices that can switch between electrical and optical energy.

Organic optoelectronic devices can be roughly classified into two types according to the operating principle. One is an optoelectronic device in which an exciton formed by light energy is separated into an electron and a hole, the electron and hole are transferred to different electrodes to generate electric energy, and the other is a voltage / Emitting device that generates light energy from energy.

Examples of organic optoelectronic devices include organic optoelectronic devices, organic light emitting devices, organic solar cells, and organic photo conductor drums.

In recent years, organic light emitting diodes (OLEDs) have attracted considerable attention due to the demand for flat panel display devices. The organic light emitting diode is a device for converting electrical energy into light by applying an electric current to the organic light emitting material, and usually has an organic layer inserted between an anode and a cathode.

One embodiment provides an organic optoelectronic device capable of realizing high efficiency characteristics.

Another embodiment provides a display device comprising the organic opto-electronic device.

According to an embodiment, there is provided a light emitting device comprising: an anode and a cathode facing each other; a light emitting layer positioned between the anode and the cathode; a hole transporting layer positioned between the anode and the light emitting layer; Wherein the light emitting layer comprises at least one first compound represented by the following general formula (1) and at least one second compound represented by the following general formula (2), and the hole transporting auxiliary layer is represented by the following general formula And a third compound represented by a combination of a moiety represented by the following formula (4) and a moiety represented by the following formula (5).

[Chemical Formula 1]

In Formula 1,

Each Z is independently N, C or CR ^a ,

At least one of Z is N,

R ¹ to R ¹⁰ and R ^a are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group or a combination thereof,

The total number of 6-membered rings substituted in the triphenylene group in Formula 1 is 6 or less,

L ¹ is a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group or a substituted or unsubstituted terphenylene group,

n1 to n3 are each independently 0 or 1,

n1 + n2 + n3? 1,

 (2)

In Formula 2,

Y ¹ is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroaryl Or a combination thereof,

Ar ¹ is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,

R ¹¹ to R ¹⁴ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heteroaryl group, or combinations thereof ,

At least one of R ¹¹ to R ¹⁴ and Ar ¹ includes a substituted or unsubstituted triphenylene group or a substituted or unsubstituted carbazole group,

[Chemical Formula 3]

In the above formulas 3 to 5,

X ¹ is O, S, NR ^b , SO ₂ , PO or CO,

X ² is O, S, SO ₂ , PO, CR ^c R ^d or NR ^e ,

R ⁵⁵ , R ⁵⁶ and R ^b to R ^e are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl Or a combination thereof, or is bonded to c * in Formula 5,

Ar ² and Ar ³ are each independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group,

L ² , L ^a and L ^b each independently represents a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, A substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group or a combination thereof,

The adjacent two * in the above formula (3) combine with the two * in the above formula (4) to form a fused ring,

Any of a *, b *, R ^b to R ^e in the above formula (3) or (4) is connected by sigma bond to c * in the above formula (5)

The remaining a *, b *, and R ^b to R ^e , which are not bonded to c * in Formula 5, are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl , A substituted or unsubstituted C3 to C30 heteroaryl group, or combinations thereof.

According to another embodiment, there is provided a display device including the organic opto-electronic device.

A high-efficiency organic optoelectronic device can be realized.

1 is a cross-sectional view schematically showing an organic optoelectronic device according to one embodiment.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

As used herein, unless otherwise defined, at least one of the substituents or at least one hydrogen in the compound is substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a hydroxy group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, A C1 to C30 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, , A C1 to C10 trifluoroalkyl group such as a fluoro group or a trifluoromethyl group, or a cyano group.

A substituted or unsubstituted C1 to C20 amine group, a nitro group, a substituted or unsubstituted C3 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C10 alkylsulfinyl group, A C1 to C10 trifluoroalkyl group such as a C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, a C1 to C20 alkoxy group, a fluoro group and a trifluoromethyl group, Two adjacent substituents may be fused to form a ring. For example, the substituted C6 to C30 aryl group may be fused with another adjacent substituted C6 to C30 aryl group to form a substituted or unsubstituted fluorene ring.

Means one to three heteroatoms selected from the group consisting of N, O, S, P and Si in one functional group, and the remainder being carbon unless otherwise defined .

As used herein, unless otherwise defined, the term "alkyl group" means an aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" which does not contain any double or triple bonds.

The alkyl group may be an alkyl group of C1 to C30. More specifically, the alkyl group may be a C1 to C20 alkyl group or a C1 to C10 alkyl group. For example, C1 to C4 alkyl groups mean that from 1 to 4 carbon atoms are included in the alkyl chain and include methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec- Indicating that they are selected from the group.

Specific examples of the alkyl group include a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, And the like.

As used herein, the term " aryl group "means a substituent in which all the elements of the cyclic substituent have p-orbital, and these p-orbital forms a conjugation, and monocyclic, Fused ring polycyclic (i. E., Rings that divide adjacent pairs of carbon atoms) functional groups.

As used herein, the term "heteroaryl group" means that the aryl group contains 1 to 3 hetero atoms selected from the group consisting of N, O, S, P, and Si, and the remainder is carbon. When the heteroaryl group is a fused ring, it may contain 1 to 3 heteroatoms in each ring.

More specifically, the substituted or unsubstituted C6 to C30 aryl group and / or the substituted or unsubstituted C2 to C30 heteroaryl group may be substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthra A substituted or unsubstituted phenanthryl group, a substituted or unsubstituted naphthacenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted naphthacenyl group, A substituted or unsubstituted aryl group, a substituted m-terphenyl group, a substituted or unsubstituted chrysenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group , A substituted or unsubstituted thiophenyl group, a substituted or unsubstituted pyrrolyl group, a substituted or unsubstituted pyrazolyl group, a substituted or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted pyrazolyl group, A substituted or unsubstituted thiazolyl group, a substituted or unsubstituted oxadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group , A substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted benzothiophenyl group, A substituted or unsubstituted quinolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted quinoxalinyl group, a substituted or unsubstituted naphthyridinyl group , A substituted or unsubstituted benzoxazine group, a substituted or unsubstituted benzothiazine group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazine group, a substituted or unsubstituted A substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted carbazole group, a substituted or unsubstituted dibenzothiophenyl group, a substituted or unsubstituted thiophene group, a substituted or unsubstituted thiophene group, A combination thereof, or a combination thereof may be in a fused form, but is not limited thereto.

In the present specification, the hole property refers to a property of forming holes by donating electrons when an electric field is applied, and has a conduction property along the HOMO level so that the injection of holes formed in the anode into the light emitting layer, Quot; refers to the property of facilitating the movement of the hole formed in the light emitting layer to the anode and the movement of the hole in the light emitting layer.

In addition, the electron characteristic refers to a characteristic that electrons can be received when an electric field is applied. The electron characteristic has a conduction characteristic along the LUMO level so that electrons formed in the cathode are injected into the light emitting layer, electrons formed in the light emitting layer migrate to the cathode, It is a characteristic that facilitates movement.

Hereinafter, an organic optoelectronic device according to one embodiment will be described.

The organic optoelectronic device is not particularly limited as long as it is an element capable of converting electric energy and optical energy. Examples of the organic optoelectronic device include organic light emitting devices, organic solar cells, and organic photoconductor drums.

Here, the organic light emitting device, which is an example of the organic optoelectronic device, is exemplarily described, but the present invention is not limited thereto and can be applied to other organic optoelectronic devices as well.

In the drawings, the thickness is enlarged to clearly represent the layers and regions. Like parts are designated with like reference numerals throughout the specification. Whenever a portion of a layer, film, region, plate, or the like is referred to as being "on" another portion, it includes not only the case where it is "directly on" another portion, but also the case where there is another portion in between. Conversely, when a part is "directly over" another part, it means that there is no other part in the middle.

1 is a cross-sectional view schematically showing an organic optoelectronic device according to one embodiment.

Referring to FIG. 1, an organic optoelectronic device according to one embodiment includes an anode 10 and a cathode 20 facing each other, and an organic layer 30 positioned between the anode 10 and the cathode 20.

The anode 10 can be made of a conductor having a high work function to facilitate, for example, hole injection, and can be made of, for example, a metal, a metal oxide, and / or a conductive polymer. The anode 10 is made of a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, or an alloy thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of ZnO and Al or a metal and an oxide such as SnO ₂ and Sb; Conductive polymers such as poly (3-methylthiophene), poly (3,4- (ethylene-1,2-dioxy) thiophene), polypyrrole and polyaniline, It is not.

The cathode 20 may be made of a conductor having a low work function to facilitate electron injection, for example, and may be made of a metal, a metal oxide, and / or a conductive polymer. The cathode 20 is made of a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium or the like or an alloy thereof; Layer structure materials such as LiF / Al, LiO ₂ / Al, LiF / Ca, LiF / Al and BaF ₂ / Ca.

The organic layer 30 includes a hole transporting layer 31, a light emitting layer 32 and a hole transporting auxiliary layer 33 located between the hole transporting layer 31 and the light emitting layer 32.

The hole transport layer 31 is a layer for facilitating hole transport from the anode 10 to the light emitting layer 32, for example, an amine compound, but is not limited thereto.

The amine compound may comprise, for example, at least one aryl group and / or heteroaryl group. The amine compound can be represented, for example, by the following formula (a) or (b), but is not limited thereto.

[Formula a] [Formula b]

In the above formula (a) or (b)

Each of Ar ^a to Ar ^g is independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof ,

At least one of Ar ^a to Ar ^c and at least one of Ar ^d to Ar ^g is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group,

Ar ^h is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof.

The light emitting layer 32 includes at least two kinds of host and a dopant, and the host has a first compound having a bipolar characteristic having a relatively high electron characteristic and a second compound having a bipolar characteristic having a relatively high hole characteristic 2 < / RTI >

The first compound is a compound having a bipolar characteristic having a relatively high electron characteristic, and may be represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

Each Z is independently N, C or CR ^a ,

At least one of Z is N,

R ¹ to R ¹⁰ and R ^a are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group or a combination thereof,

The total number of 6-membered rings substituted in the triphenylene group in Formula 1 is 6 or less,

L ¹ is a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group or a substituted or unsubstituted terphenylene group,

n1 to n3 are each independently 0 or 1, and n1 + n2 + n3? 1.

The 6-membered ring substituted in the triphenylene group refers to all 6-membered rings directly or indirectly connected to the triphenylene group, and includes a 6-membered ring composed of a carbon atom, a nitrogen atom or a combination thereof.

The first compound may be represented by, for example, the following formula (I-1) or (I-II) depending on the bonding position of the triphenylene group.

[Chemical Formula 1-I] [Chemical Formula 1-II]

In the above formula (I-I) or (II-II), Z, R ¹ to R ¹⁰ , L ¹ and n ¹ to n 3 are as described above.

The first compound comprises a triphenylene group and at least one nitrogen-containing heteroaryl group. Since the first compound includes a ring containing at least one nitrogen, it can have a structure which is easy to receive electrons when an electric field is applied, and thus the driving voltage of the organic optoelectronic device to which the first compound is applied can be lowered.

In addition, the first compound includes a triphenylene structure susceptible to holes and a nitrogen-containing ring portion that is susceptible to electrons, thereby forming a bipolar structure so that the flow of holes and electrons can be appropriately balanced, The efficiency of the organic optoelectronic device to which the first compound is applied can be improved.

The first compound represented by Formula 1 has at least one kink structure centering on an arylene group and / or a heteroarylene group.

The bending structure refers to a structure in which two connecting portions of an arylene group and / or a heteroarylene group do not form a straight line structure. For example, in the case of phenylene, o-phenylene and m-phenylene, in which the connecting portions do not have a linear structure, have the bending structure and the connecting portions have a linear structure, phenylene does not have the bending structure.

In the formula (1), the bending structure may be formed around a linking group (L) and / or an arylene group / heteroarylene group.

For example, when n1 in the above formula (1) is 0, that is, in the structure having no linking group (L), it may form a bending structure around an arylene group / heteroarylene group and may be a compound represented by the following formula .

[Chemical Formula 1a] [Chemical Formula 1b]

In the above general formula (1a) or (1b), Z, R ¹ to R ¹⁰ are as described above.

For example, when n1 in Formula 1 is 1, a bending structure may be formed around a linking group (L ¹ ). For example, L ¹ may be a substituted or unsubstituted phenylene group having a bending structure, a substituted or unsubstituted A biphenylene group or a bivalent substituted or unsubstituted terphenylene group.

And L < ¹ > may be selected from, for example, a substituted or unsubstituted group listed in Group 1 below.

[Group 1]

In the group 1,

R ¹⁵ to R ⁴² are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted amine group, a substituted or unsubstituted C6 to C30 arylamine group, a substituted or unsubstituted C6 to C30 heteroaryl amine A substituted or unsubstituted C1 to C30 alkoxy group, a halogen group, a halogen-containing group, a cyano group, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a ferrocenyl group or a combination thereof.

The first compound preferably has at least two bending structures, and may have, for example, two to four bending structures.

The first compound has the above-described bending structure to appropriately localize the charge and effectively control the flow of the conjugate system, thereby improving the lifetime of the organic optoelectronic device to which the composition is applied.

In addition, by limiting the total number of 6-membered rings included in the substituent substituted in the triphenylene group to 6 or less in R ¹ to R ⁶ in the general formula (1), it is possible to reduce the phenomenon that the compound is pyrolyzed at a high temperature during the deposition process have.

In addition, the first compound effectively prevents the stacking of the compounds according to the structure, thereby lowering the process stability and lowering the deposition temperature. Such an anti-stacking effect can be further enhanced when the linking group (L ¹ ) of the above formula ( ¹ ) is included.

The first compound may be represented by, for example, any one of the following formulas (1c) to (1t).

[Chemical Formula 1c] [Chemical Formula 1d]

[Formula 1e] [Formula 1f]

[Chemical Formula 1g] [Chemical Formula 1h]

[Chemical Formula 1i] [Chemical Formula 1j]

[Chemical Formula 1k] [Chemical Formula 11]

[Formula 1m] [Formula 1n]

≪ EMI ID =

[Chemical Formula 1q] [Chemical Formula 1r]

[Formula 1s] [Formula 1t]

In the above Chemical Formulas 1c to 1t,

Z and R ¹ to R ¹⁰ are each as defined above,

R ⁶⁰ to R ⁷⁷ each independently represents hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted amine group, a substituted or unsubstituted C6 to C30 arylamine group, a substituted or unsubstituted C6 to C30 heteroaryl amine A substituted or unsubstituted C1 to C30 alkoxy group, a halogen group, a halogen-containing group, a cyano group, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a ferrocenyl group or a combination thereof.

The first compound may be, for example, a compound listed in the following Group 2, but is not limited thereto.

[Group 2]

The first compound may be used alone or in combination of two or more.

The second compound may be represented by, for example, the following formula (2).

(2)

In Formula 2,

Y ¹ is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroaryl Or a combination thereof,

Ar ¹ is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,

R ¹¹ to R ¹⁴ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heteroaryl group, or combinations thereof ,

At least one of R ¹¹ to R ¹⁴ and Ar ¹ includes a substituted or unsubstituted triphenylene group or a substituted or unsubstituted carbazole group.

The compound represented by Formula 2 is a compound having bipolar characteristics with a relatively high hole property and is used together with the first compound to improve charge mobility and stability in the light emitting layer, It is possible to prevent accumulation of holes and / or electrons at the interface between the hole transporting layer and the light emitting layer, and to increase the balance of the charges. Therefore, the luminous efficiency and lifetime characteristics of the organic optoelectronic device can be remarkably improved.

The compound represented by the formula (2) may be represented by at least one of the following formulas (II-1) to (II-III).

[Chemical Formula 2-I] [Chemical Formula 2-II]

[Chemical Formula 2-III]

In the above Formulas 2-1 to 2-III,

Y ¹ to Y ³ each independently represents a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C6 to C30 arylene group, C2-C30 heteroarylene groups or combinations thereof,

Ar ¹ , Ar ^1a and Ar ^1b are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group or a combination thereof,

R ¹¹ to R ¹⁴ and R ⁴³ to R ⁵⁴ each independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heteroaryl Or a combination thereof.

The compound represented by Formula 2-I has a structure in which two carbazole groups having a substituent are connected.

Ar ^1a and Ar ^1b in the above formula (II) are substituents having a hole or electron characteristic, and each independently represents a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, An unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted fluorenyl group , A substituted or unsubstituted pyridyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted pyrazinyl group, A dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof.

At least one of Ar ^1a and Ar ^1b in Formula 2-1 may be a substituent having an electron characteristic, for example, a substituent represented by the following Formula A.

(A)

In the above formula (A)

Each Z is independently N or CR ^b ,

A1 and A2 are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,

Wherein at least one of Z, Al and A2 comprises N,

a and b are each independently 0 or 1;

The substituent represented by the above formula (A) may be one of the functional groups listed in the following group 3, for example.

[Group 3]

At least one of Ar ^1a and Ar ^1b in Formula 2-I may be a substituent having a hole property, for example, a substituent listed in Group 4 below.

[Group 4]

The compound represented by Formula 2-I may be selected from the compounds listed in the following Group 5, but is not limited thereto.

[Group 5]

The compound represented by Formula 2-II or 2-III is a structure in which a substituted or unsubstituted carbazole group and a substituted or unsubstituted triphenylene group are bonded.

Ar ¹ in the above formula (II-II) is a substituent having a hole or electron characteristic, and examples thereof include a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, A substituted or unsubstituted thiophenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted fluorenyl group, A substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted dibenzothiophenyl group, A substituted or unsubstituted dibenzofuranyl group, or a combination thereof.

The compound represented by Formula 2-II may be selected from the compounds listed in the following Group 6, but is not limited thereto.

[Group 6]

The compound represented by Formula 2-III may be selected from compounds listed in the following Group 7, but is not limited thereto.

[Group 7]

The second compound may be used alone or in combination of two or more.

In the light-emitting layer 32, the first compound and the second compound may be contained as a host, and may be included at a weight ratio of about 1: 10 to 10: 1, for example. By being included in the above range, the bipolar characteristic can be implemented more effectively, and the efficiency and lifetime can be simultaneously improved.

The light emitting layer 32 may further include at least one compound other than the first compound and the second compound described above as a host.

The light emitting layer 32 may further include a dopant. The dopant may be a material that emits light by mixing with the host in a trace amount and may be a metal complex such as a metal complex that emits light by multiple excitation that excites the triplet state. The dopant may be, for example, an inorganic, organic, or organic compound, and may include one or more species.

The dopant may be a red, green or blue dopant, for example a phosphorescent dopant. Examples of the phosphorescent dopant include organic metal compounds including Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh and Pd or combinations thereof. The phosphorescent dopant may be, for example, a compound represented by the following formula (Z), but is not limited thereto.

(Z)

L ₂ MX

In the above formula (Z), M is a metal, L and X are the same or different from each other and are ligands that complex with M.

M may be Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd or combinations thereof, Lt; / RTI >

The hole transporting auxiliary layer 33 includes a third compound having a bipolar characteristic having a relatively high hole property.

As described above, the luminescent layer 32 includes a first compound having a relatively high bipolar characteristic and a second compound having a relatively high hole characteristic, both of which have relatively high electron characteristics, The luminous efficiency can be remarkably improved.

In the device in which the electron characteristic or the hole characteristic is biased toward the light emitting layer, the recombination of carriers occurs at the interface between the light emitting layer and the electron or charge transport layer, and the formation of the excitons is relatively large. As a result, a roll-off phenomenon in which the efficiency is drastically reduced due to the interaction between the molecular excitons in the light emitting layer and the charge at the interface of the hole transporting layer occurs, and the luminescent lifetime characteristics also sharply drop.

In order to solve such a problem, the first and second compounds are simultaneously introduced into the light emitting layer so that the light emitting region is not shifted to either the electron transporting layer or the hole transporting layer, and further the bipolar characteristic Transporting layer and the light-emitting layer, it is possible to manufacture a device capable of preventing charge from being accumulated on the interface between the hole transporting layer and the light-emitting layer and adjusting the carrier balance in the light-emitting layer. As a result, the roll-off characteristics of the organic optoelectronic device can be improved and the lifetime characteristics can be remarkably improved

The third compound may be a compound represented by a combination of a moiety represented by the following formula (3), a moiety represented by the following formula (4), and a moiety represented by the following formula (5).

[Chemical Formula 3]

In the above formulas 3 to 5,

X ¹ is O, S, NR ^b , SO ₂ , PO or CO,

X ² is O, S, SO ₂ , PO, CR ^c R ^d or NR ^e ,

R ⁵⁵ , R ⁵⁶ and R ^b to R ^e are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl Or a combination thereof, or is bonded to c * in Formula 5,

Ar ² and Ar ³ are each independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group,

L ² , L ^a and L ^b each independently represents a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, A substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group or a combination thereof,

The adjacent two * in the above formula (3) combine with the two * in the above formula (4) to form a fused ring,

Any of a *, b *, R ^b to R ^e in the above formula (3) or (4) is connected by sigma bond to c * in the above formula (5)

The remaining a *, b *, and R ^b to R ^e , which are not bonded to c * in Formula 5, are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl , A substituted or unsubstituted C3 to C30 heteroaryl group, or combinations thereof.

The third compound may be represented by, for example, any one of the following formulas (6) to (17).

[Chemical Formula 6] < EMI ID =

[Chemical Formula 8]

[Chemical Formula 10]

[Chemical Formula 12]

[Chemical Formula 14]

[Chemical Formula 16]

In Formulas 6 to 17, X ¹ , X ² , R ⁵⁵ , R ⁵⁶ , Ar ² , Ar ³ , L ² , L ^a and L ^b are as described above.

The third compound may be selected from compounds listed in the following Group 8, but is not limited thereto.

[Group 8]

[E-1] [E-2] [E-3] [E-4]

[E-5] [E-6] [E-7] [E-8]

[E-9] [E-10] [E-11] [E-12]

[E-13] [E-14] [E-15] [E-16]

[E-17] [E-18] [E-19] [E-20]

[E-21] [E-22] [E-23] [E-24]

[E-25] [E-26] [E-27] [E-28]

[E-29] [E-30] [E-31] [E-32]

[E-33] [E-34] [E-35] [E-36]

[E-37] [E-38] [E-39] [E-40]

[E-41] [E-42] [E-43] [E-44]

[E-45] [E-46] [E-47] [E-48]

[E-49] [E-50] [E-51] [E-52]

[E-53] [E-54] [E-55] [E-56]

[E-57] [E-58] [E-59] [E-60]

[E-61] [E-62] [E-63] [E-64]

[E-65] [E-66] [E-67] [E-68]

[E-69] [E-70] [E-71] [E-72]

[E-73] [E-74] [E-75] [E-76]

[E-77] [E-78] [E-79] [E-80]

[E-82] [E-83] [E-84] [E-85]

[E-86] [E-87] [E-88] [E-89]

[E-90] [E-91] [E-92] [E-93]

[E-94] [E-95] [E-96] [E-97]

[E-98] [E-99] [E-100] [E-101]

[E-102] [E-103] [E-104] [E-105]

[E-106] [E-107] [E-108] [E-109]

[E-110] [E-111] [E-112] [E-113]

[E-114] [E-115] [E-116] [E-117]

[E-118] [E-119] [E-120] [E-121]

[E-122] [E-123] [E-124] [E-125]

[E-126] [E-127] [E-128] [E-129]

[E-130] [E-131] [E-132] [E-133]

[F-1] [F-2] [F-3] [F-4]

[F-5] [F-6] [F-7] [F-8]

[F-9] [F-10] [F-11] [F-12]

[F-13] [F-14] [F-15] [F-16]

[F-17] [F-18] [F-19] [F-20]

[F-21] [F-22] [F-23] [F-24]

[F-25] [F-26] [F-27] [F-28]

[G-1] [G-2] [G-3] [G-4]

[G-5] [G-6] [G-7] [G-8]

[G-9] [G-10] [G-11] [G-12] [G-13]

[G-14] [G-15] [G-16] [G-17]

[G-18] [G-19] [G-20] [G-21]

[G-22] [G-23] [G-24] [G-25]

[G-26] [G-27] [G-28] [G-29]

[G-30] [G-31] [G-32] [G-33]

[G-34] [G-35] [G-36] [G-37]

[G-38] [G-39] [G-40] [G-41]

[G-42] [G-43] [G-44] [G-45]

[G-46] [G-47] [G-48] [G-49]

[G-50] [G-51] [G-52] [G-53]

[G-54] [G-55] [G-56] [G-57]

[G-58] [G-59] [G-60] [G-61]

[G-62] [G-63] [G-64] [G-65]

[G-66] [G-67] [G-68] [G-69]

[G-70] [G-71] [G-72] [G-73]

[G-74] [G-75] [G-76] [G-77]

[G-78] [G-79] [G-80] [G-81]

[G-82] [G-83] [G-84] [G-85]

[G-86] [G-87] [G-88] [G-89]

[G-90] [G-91] [G-92] [G-93]

[H-1] [H-2] [H-3] [H-4]

[H-5] [H-6] [H-7]

[H-8] [H-9] [H-10] [H-11]

[H-13] [H-14] [H-15] [H-16] [H-17]

[H-18] [H-19] [H-20]

[I-1] [I-2] [I-3] [I-4]

[I-5] [I-6] [I-7] [I-8]

[I-9] [I-10] [I-11] [I-12]

[I-13] [I-14] [I-15] [I-16]

[I-17] [I-18] [I-19] [I-20]

[I-21] [I-22] [I-23] [I-24]

[I-25] [I-26] [I-27] [I-28]

[I-29] [I-30] [I-31] [I-32]

[I-33] [I-34] [I-35] [I-36]

[I-37] [I-38] [I-39] [I-40]

[I-41] [I-42] [I-43] [I-44]

[I-45] [I-46] [I-47] [I-48]

[I-49] [I-50] [I-51] [I-52]

[I-53] [I-54] [I-55] [I-56]

[I-57] [I-58] [I-59] [I-60]

[I-61] [I-62] [I-63] [I-64]

[I-65] [I-66] [I-67] [I-68]

[I-69] [I-70] [I-71] [I-72]

[I-73] [I-74] [I-75] [I-76]

[I-77] [I-78] [I-79] [I-80]

[I-81] [I-82] [I-83] [I-84]

[I-85] [I-86] [I-87] [I-88]

[I-89] [I-90] [I-91] [I-92]

[I-93] [I-94] [I-95] [I-96]

[I-97] [I-98] [I-99] [I-100]

[I-101] [I-102] [I-103] [I-104]

[I-105] [I-106] [I-107] [I-108]

[I-109] [I-110] [I-111] [I-112]

[I-113] [I-114] [I-115] [I-116]

[I-117] [I-118] [I-119] [I-120]

[I-121] [I-122] [I-123] [I-124]

[I-125] [I-126] [I-127] [I-128]

[J-1] [J-2] [J-3]

[J-4] [J-5] [J-6]

[J-7] [J-8] [J-9]

[J-10] [J-11] [J-12]

[J-13] [J-14] [J-15]

[J-16] [J-17]  [J-18]

[J-19]  [J-20]  [J-21]

[J-22] [J-23] [J-24]

[J-25] [J-26] [J-27]

[J-28] [J-29] [J-30]

[J-31] [J-32]  [J-33]

[J-34] [J-35]  [J-36]

[J-37] [J-38] [J-39]

[J-40] [J-41]  [J-42]

[J-43] [J-44]  [J-45]

[J-46]  [J-47]  [J-48]

[J-49] [J-50] [J-51]

[J-52]  [J-53]  [J-54]

[J-55] [J-56] [J-57]

[J-58]  [J-59]  [J-60]

[J-61] [J-62] [J-63]

[J-64] [J-65]  [J-66]

[J-67] [J-68]  [J-69]

[J-70]  [J-71] [J-72]

[J-73] [J-74] [J-75]

[J-76] [J-77] [J-78]

[J-79] [J-80] [J-81]

[J-82] [J-83] [J-84]

[J-85] [J-86] [J-87]

[J-88] [J-89]  [J-90]

[J-91] [J-92]  [J-93]

[J-94] [J-95]  [J-96]

[J-97] [J-98]  [J-99]

[J-100] [J-101] [J-102]

[J-103]  [J-104]  [J-105]

[J-106]  [J-107] [J-108]

[J-109] [J-110] [J-111]

[J-112] [J-113] [J-114]

[J-115] [J-116]  [J-117]

[J-118] [J-119] [J-120]

[J-121] [J-122] [J-123]

[J-124] [J-125] [J-126]

[J-127] [J-128] [J-129]

[J-130] [J-131]  [J-132]

[J-133]  [J-134] [J-135]

[J-136] [J-137] [J-138]

[J-139] [J-140] [J-141]

[J-142] [J-143] [J-144]

[J-145] [J-146] [J-147]

[J-148] [J-149] [J-150]

[J-151] [J-152] [J-153]

[J-154] [J-155] [J-156]

[J-157] [J-158] [J-159]

[J-160]  [J-161] [J-162]

[J-163] [J-164] [J-165]

[J-166] [J-167]  [J-168]

[J-169] [J-170]  [J-171]

[J-172] [J-173] [J-174]

[J-175] [J-176] [J-177]

[J-178] [J-179] [J-180]

[J-181] [J-182] [J-183]

[J-184] [J-185] [J-186]

[J-187] [J-188] [J-189]

[J-190] [J-191] [J-192]

[J-193] [J-194] [J-195]

[J-196] [J-197] [J-198]

[J-199] [J-200] [J-201]

[J-202] [J-203] [J-204]

[J-205] [J-206] [J-207]

[J-208] [J-209] [J-210]

[J-211] [J-212] [J-213]

[J-214] [J-215] [J-216]

[J-217] [J-218] [J-219]

[J-220] [J-221] [J-222]

[J-223] [J-224] [J-225]

[J-226] [J-227] [J-228]

[J-229] [J-230] [J-231]

[J-232] [J-233] [J-234]

[J-235] [J-236] [J-237]

[J-238] [J-239] [J-240]

[J-241] [J-242] [J-243]

[J-244] [J-245] [J-246]

[J-247] [J-248] [J-249]

[J-250]  [J-251] [J-252]

[J-253] [J-254] [J-255]

[J-256] [J-257] [J-258]

[J-259] [J-260] [J-261]

[J-262] [J-263] [J-264]

[J-265] [J-266] [J-267]

[J-268] [J-269] [J-270]

[J-271] [J-272] [J-273]

[J-274] [J-275] [J-276]

[J-277] [J-278] [J-279]

[J-280] [J-281] [J-282]

[J-283] [J-284] [J-285]

[J-286] [J-287] [J-288]

[J-289] [J-290] [J-291]

[J-292] [J-293] [J-294]

[J-295] [J-296] [J-297]

[J-298] [J-299] [J-300]

[J-301] [J-302] [J-303]

[J-304] [J-305] [J-306]

[J-307] [J-308] [J-309]

[J-310] [J-311] [J-312]

[J-313] [J-314] [J-315]

[J-316] [J-317] [J-318]

[J-319] [J-320] [J-321]

[J-322] [J-323] [J-324]

[J-325] [J-326] [J-327]

[J-328] [J-329] [J-330]

[J-331]   [J-332] [J-333]

[J-334] [J-335] [J-336]

[J-337] [J-338] [J-339]

[J-340] [J-341] [J-342]

[J-343] [J-344] [J-345]

[J-346] [J-347] [J-348]

[J-349] [J-350] [J-351]

[J-352] [J-353] [J-354]

[J-355] [J-356] [J-357]

[J-358] [J-359] [J-360]

[J-361] [J-362] [J-363]

[J-364] [J-365] [J-366]

[J-367] [J-368] [J-369]

[J-370] [J-371] [J-372]

[J-373] [J-374] [J-375]

[J-376] [J-377] [J-378]

[J-379] [J-380] [J-381]

[J-382] [J-383] [J-384]

[J-385] [J-386] [J-387]

[J-388] [J-389] [J-390]

[J-391] [J-392] [J-393]

[J-394] [J-395] [J-396]

[J-397] [J-398] [J-399]

[J-400] [J-401] [J-402]

The organic layer 30 may further include an electron transport layer 34. The electron transporting layer 34 is a layer for facilitating the electron transfer from the cathode 20 to the light emitting layer 32, and may be optionally omitted.

The organic layer 30 may optionally include a hole injection layer (not shown) positioned between the anode 10 and the hole transport layer 31 and / or an electron injection layer (not shown) located between the cathode 20 and the electron transport layer 34 (Not shown).

The organic light emitting device described above can be applied to an organic light emitting display.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

Synthesis of first compound

Synthesis Example 1: Synthesis of Intermediate I-1

[Reaction Scheme 1]

In a nitrogen atmosphere, 100 g (326 mmol) of 2-bromotriphenylene was dissolved in 1 L of dimethylformamide (DMF), followed by addition of bis (pinacolato) diboron 2.66 g (3.26 mmol) of 99.2 g (391 mmol) of (1,1'-bis (diphenylphosphine) ferrocene) dichloropalladium (II) Then, 80 g (815 mmol) of potassium acetate was added and the mixture was refluxed by heating at 150 ° C. for 5 hours. After completion of the reaction, water was added to the reaction mixture, and the mixture was filtered and dried in a vacuum oven. Was separated and purified by flash column chromatography to obtain 113 g (98%) of the compound I-1.

HRMS (70 eV, EI +): m / z calcd for C24H23BO2: 354.1791, found: 354.

Elemental Analysis: C, 81%; H, 7%

Synthesis Example 2: Synthesis of Intermediate I-2

[Reaction Scheme 2]

32.7 g (107 mmol) of 2-bromotriphenylene was dissolved in 0.3 L of tetrahydrofuran (THF) in a nitrogen atmosphere, and 3-chlorophenyl boronic acid ) (20 g, 128 mmol) and tetrakis (triphenylphosphine) palladium (1.23 g, 1.07 mmol) were added and stirred. 36.8 g (267 mmol) of saturated potassium carbonate in water was added, and the mixture was refluxed by heating at 80 DEG C for 24 hours. After the completion of the reaction, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM), and the water was removed with anhydrous MgSO 4. The extract was filtered and concentrated under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain 22.6 g (63%) of the compound I-2.

HRMS (70 eV, EI +): m / z calcd for C24H15Cl: 338.0862, found: 338.

Elemental Analysis: C, 85%; H, 5%

Synthesis Example 3: Synthesis of Intermediate I-3

[Reaction Scheme 3]

22.6 g (66.7 mmol) of the above compound I-2 was dissolved in 0.3 L of dimethylformamide (DMF) in a nitrogen atmosphere, 25.4 g (100 mol) of bis (pinacolato diboron) 0.54 g (0.67 mmol) of (1, 1'-bis (diphenylphosphine) ferrocene) dichloropalladium (II) (167 mmol) of potassium acetate, and the mixture was heated at 150 캜 for 48 hours to reflux. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The residue thus obtained was separated and purified by flash column chromatography to obtain 18.6 g (65%) of the compound I-3.

HRMS (70 eV, EI +): m / z calcd for C30H27BO2: 430.2104, found: 430.

Elemental Analysis: C, 84%; H, 6%

Synthesis Example 4: Synthesis of Intermediate I-4

[Reaction Scheme 4]

100 g (282 mmol) of the above compound I-1 was dissolved in 1 L of tetrahydrofuran (THF) in a nitrogen atmosphere, 95.9 g of 1-bromo-2-iodobenzene (339 mmol) of tetrakis (triphenylphosphine) palladium and 3.26 g (2.82 mmol) of tetrakis (triphenylphosphine) palladium were added and stirred. 97.4 g (705 mmol) of saturated potassium carbonate in water was added and the mixture was refluxed by heating at 80 DEG C for 53 hours. After the completion of the reaction, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain 95.1 g (88%) of the compound I-4.

HRMS (70 eV, EI +): m / z calcd for C24H15Br: 382.0357, found: 382.

Elemental Analysis: C, 75%; H, 4%

Synthesis Example 5: Synthesis of Intermediate I-5

[Reaction Scheme 5]

90 g (235 mmol) of the above compound I-4 was dissolved in 0.8 L of dimethylformamide (DMF) in a nitrogen atmosphere, 71.6 g (282 mmol) of bis (pinacolato diboron) 1.92 g (2.35 mmol) of (1,1'-bis (diphenylphosphine) ferrocene) dichloropalladium (II) (1,1'-bis (diphenylphosphine) ferrocene dichloropalladium (588 mmol), and the mixture was heated at 150 占 폚 for 35 hours to reflux. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The residue thus obtained was separated and purified by flash column chromatography to obtain 74.8 g (74%) of Compound I-5.

HRMS (70 eV, EI +): m / z calcd for C30H27BO2: 430.2104, found: 430.

Elemental Analysis: C, 84%; H, 6%

Synthesis Example 6: Synthesis of Intermediate I-6

[Reaction Scheme 6]

After 50 g (116 mmol) of the compound I-3 was dissolved in 0.5 L of tetrahydrofuran (THF) in a nitrogen atmosphere, 39.4 g of 1-bromo-3-iodobenzene (139 mmol) and tetrakis (triphenylphosphine) palladium (1.34 g, 1.16 mmol) were added and stirred. 40.1 g (290 mmol) of saturated potassium carbonate in water was added, and the mixture was refluxed by heating at 80 DEG C for 12 hours. After the completion of the reaction, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain 42.6 g (80%) of the compound I-6.

HRMS (70 eV, EI +): m / z calcd for C30 H19 Br: 458.0670, found: 458.

Elemental Analysis: C, 78%; H, 4%

Synthesis Example 7: Synthesis of Intermediate I-7

[Reaction Scheme 7]

40 g (87.1 mmol) of the above compound I-6 was dissolved in 0.3 L of dimethylformamide (DMF) in a nitrogen atmosphere, 26.5 g (104 mmol) of bis (pinacolato diboron) And 0.71 g (0.87 mmol) of (1,1'-bis (diphenylphosphine) ferrocene) dichloropalladium (II) ((1,1'-bis (diphenylphosphine) ferrocene) dichloropalladium (218 mmol) were added, and the mixture was refluxed by heating at 150 占 폚 for 26 hours. After completion of the reaction, water was added to the reaction solution, the mixture was filtered, and then dried in a vacuum oven. The residue thus obtained was separated and purified by flash column chromatography to obtain 34 g (77%) of Compound I-7.

HRMS (70 eV, EI +): m / z calcd for C36H31BO2: 506.2417, found: 506.

Elemental Analysis: C, 85%; H, 6%

Synthesis Example 8: Synthesis of Compound A-33

[Reaction Scheme 17]

20 g (39.5 mmol) of the compound 1-7 was dissolved in 0.2 L of tetrahydrofuran (THF) in a nitrogen atmosphere, and then 2-chloro-4,6-diphenyl-1,3,5-triazine 0.46 g (0.4 mmol) of tetrakis (triphenylphosphine) palladium (10.6 g, 39.5 mmol) was added to the solution, and the mixture was stirred . 13.6 g (98.8 mmol) of saturated potassium carbonate in water was added and the mixture was refluxed by heating at 80 DEG C for 23 hours. After the completion of the reaction, water was added to the reaction solution, and the mixture was extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgSO 4, followed by filtration and concentration under reduced pressure. The residue thus obtained was separated and purified by flash column chromatography to obtain Compound A-33 (17.9 g, 74%).

HRMS (70 eV, EI +): m / z calcd for C45 H29 N3: 611.2361, found: 611.

Elemental Analysis: C, 88%; H, 5%

Synthesis of second compound

Synthesis Example 9: Synthesis of Compound C-10

[Reaction Scheme 20]

A mixture of 10 g (34.83 mmol) of phenylcarbazolylboronic acid, 11.77 g (38.31 mmol) of the compound 2 and 14.44 g (104.49 mmol) of potassium carbonate, 0.80 g of tetrakis- (triphenylphosphine) palladium (0.7 mmmol) was suspended in 140 ml of toluene and 50 ml of distilled water, followed by stirring under reflux for 12 hours. The mixture is then extracted with dichloromethane and distilled water, and the organic layer is subjected to silica gel filtration. Subsequently, the organic solution was removed, and the residue was subjected to silica gel column chromatography with hexane: dichloromethane = 7: 3 (v / v), and the resulting solid was recrystallized from dichloromethane and n-hexane to obtain 14.4 g of the compound C-10 (yield: 88%).

HRMS (70 eV, EI +): m / z calcd for C36H23N: 469.18, found: 469

Elemental Analysis: C, 92%; H, 5%

Synthesis Example 10: Synthesis of Compound B-10

[Reaction Scheme 21]

Step 1: Synthesis of Compound J

A mixture of 26.96 g (81.4 mmol) of N-phenylcarbazole-3-boronic acid pinacolate, 23.96 g (97.36 mmol) of 3-bromocarbazole and 230 mL of tetrahydrofuran and 100 mL of a 2 M- The mixture was heated under reflux for 12 hours under an air stream. After the completion of the reaction, the reactants are poured into methanol to remove solids, and then the solids are dissolved again in chlorobenzene. Activated carbon and anhydrous magnesium sulfate are added and stirred. The solution was filtered and then recrystallized using chlorobenzene and methanol to obtain 22.6 g of Compound J (yield: 68%).

HRMS (70 eV, EI +): m / z calcd for C30 H20 N2: 408.16, found: 408

Elemental Analysis: C, 88%; H, 5%

Step 2: Synthesis of compound B-10

After dissolving 400 ml of toluene in 22.42 g (54.88 mmol) of the compound represented by the compound J, 20.43 g (65.85 mmol) of 2-bromo-4,6-diphetylpyridine and 7.92 g (82.32 mmol) 1.65 g (1.65 mmol) of dibenzylidenamine and 1.78 g (4.39 mmol) of tertiary butyl are added dropwise. The reaction solution was heated at 110 DEG C for 12 hours under a stream of nitrogen and stirred. After completion of the reaction, methanol is poured into the reaction product to filter out the resulting solids, and the solids are again dissolved in chlorobenzene, and activated carbon and anhydrous magnesium sulfate are added thereto and stirred. The solution was filtered and then recrystallized using chlorobenzene and methanol to obtain 28.10 g (yield: 80%) of Compound B-10.

HRMS (70 eV, EI +): m / z calcd for C 47 H 31 N 3: 637.25, found: 637

Elemental Analysis: C, 89%; H, 5%

Synthesis Example 11: Synthesis of Compound B-31

[Reaction Scheme 22]

9.78 g (30.95 mmol) of phenylcarbazolylbromide, 9.78 g (34.05 mmol) of phenylcarbazolylboronic acid and 12.83 g (92.86 mmol) of potassium carbonate, tetrakis- (triphenylphosphine) palladium 0) (1.07 g, 0.93 mmmol) was suspended in 120 ml of toluene and 50 ml of distilled water, followed by stirring under reflux for 12 hours. The mixture is then extracted with dichloromethane and distilled water, and the organic layer is subjected to silica gel filtration. Subsequently, the organic solution was removed and the resulting solid was recrystallized from dichloromethane and n-hexane to obtain 13.8 g (yield: 92%) of the compound B-31.

HRMS (70 eV, EI +): m / z calcd for C36H24N2: 484.19, found: 484

Elemental Analysis: C, 89%; H, 5%

Synthesis Example 12: Synthesis of Compound B-43

[Reaction Scheme 24]

12.33g (34.05mmol) of biphenylcarbazolylboronic acid and 12.83g (92.86mmol) of potassium carbonate, 12.33g (30.95mmol) of biphenylcarbazolyl bromide, tetrakis- (triphenylphosphine) 1.07 g (0.93 mmmol) of palladium (0) was suspended in 120 ml of toluene and 50 ml of distilled water, followed by stirring under reflux for 12 hours. The mixture is then extracted with dichloromethane and distilled water, and the organic layer is subjected to silica gel filtration. Subsequently, the organic solution was removed and the product solid was recrystallized from dichloromethane and n-hexane to obtain 18.7 g (yield: 92%) of the compound B-43.

HRMS (70 eV, EI +): m / z calcd for C48H32N2: 636.26, found: 636

Elemental Analysis: C, 91%; H, 5%

Synthesis of the third compound

Synthesis Example 13: Synthesis of Intermediate M-1

21.5 g (94.3 mmol) of 4-dibenzothiophene boronic acid and 20.3 g (94.3 mmol) of methyl 2-bromobenzoate were added to a round bottom flask and toluene (313 ml) was added to dissolve the solution. 19.5 g ) Was dissolved in 100 ml of tetrahydrofuran, and the mixture was stirred. 1.09 g (0.94 mmol) of tetrakistriphenylphosphine palladium was added thereto, and the mixture was stirred under reflux for 12 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was extracted with ethyl acetate. The extract was dried with magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography using n-hexane / ethyl acetate (9: 1 v / v) to obtain 27.6 g (92% yield) of intermediate M-1.

? LC-Mass (theory: 318.07 g / mol, measured: M + = 318.13 g / mol)

Synthesis Example 14: Synthesis of Intermediate M-2

27.4 g (86 mmol) of M-1 was added to a round-bottomed flask heated and reduced in pressure and dried, and diethyl ether (430 ml) was added to dissolve it. The mixture was cooled to 0 ° C and stirred under a nitrogen atmosphere. 72 ml (215 mmol) of 3.0 M methylmagnesium bromide diethyl ether solution was slowly added thereto, followed by stirring at room temperature and under nitrogen atmosphere for 12 hours. The reaction solution was cooled to 0 캜 and a small amount of distilled water was added to terminate the reaction. Then, 108 ml of 2.0 M ammonium chloride aqueous solution was added, and the mixture was extracted with diethyl ether. The extract was then dried with magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was used in the next reaction without further purification, and 27.1 g (yield 99%) of intermediate M-2 was obtained.

Synthesis Example 15: Synthesis of Intermediate M-3

27.1 g (85.1 mmol) of M-2 was added to a round-bottomed flask dried under reduced pressure and dissolved in anhydrous dichloromethane (255 ml), cooled to 0 ° C, and stirred under a nitrogen atmosphere. 12.1 g (85.1 mmol) of boron tri-fluoride diethyl etherate was slowly added thereto, followed by stirring at room temperature and under nitrogen atmosphere for 4 hours. The reaction mixture was cooled to 0 ° C and a small amount of distilled water was added to terminate the reaction. 85 ml of 1.0 M sodium bicarbonate aqueous solution was added thereto, followed by extraction with dichloromethane. The extract was then dried with magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography using n-hexane / dichloromethane (9: 1 v / v) to obtain 19.4 g (yield 76%) of intermediate M-3.

LC-Mass (theory: 300.10 g / mol, measurement: M + = 300.21 g / mol)

Synthesis Example 16: Synthesis of Intermediate M-4

19 g (63.3 mmol) of M-3 was added to 190 ml of anhydrous tetrahydrofuran, and the mixture was cooled to -20 ° C and stirred under a nitrogen atmosphere. 31 ml (76 mmol) of 2.5 M n-butyllithium n-hexane solution was slowly added thereto, followed by stirring at room temperature and under nitrogen atmosphere for 6 hours. The reaction solution was cooled to -20 占 폚, 14.3 g (76 mmol) of triisopropyl borate was slowly added thereto, and the mixture was stirred at room temperature and under nitrogen atmosphere for 6 hours. The reaction solution was cooled to 0 占 폚 and a small amount of distilled water was added thereto to terminate the reaction. Then, 114 ml of a 2.0 M aqueous hydrochloric acid solution was added, and the mixture was extracted with diethyl ether. The extract was then dried with magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The residue was dissolved in acetone and recrystallized by adding n-hexane. The resulting solid was filtered under reduced pressure to obtain 16.3 g (yield 75%) of Intermediate M-4.

LC-Mass (theory: 344.10 g / mol, measured: M + = 344.19 g / mol)

Synthesis Example 17: Synthesis of Intermediate M-5

32.5 g (94.3 mmol) of M-4 and 26.7 g (94.3 mmol) of 1-bromo-4-iodobenzene were placed in a round bottom flask and toluene (313 ml) was added to dissolve the solution. 19.5 g (141.5 mmol) 117 ml of a dissolved aqueous solution was added and stirred. 1.09 g (0.94 mmol) of tetrakistriphenylphosphine palladium was added thereto, and the mixture was refluxed and stirred for 12 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was extracted with ethyl acetate. The extract was dried with magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography using n-hexane / dichloromethane (9: 1 v / v) to give 39.5 g (92% yield) of intermediate M-5.

LC-Mass (454.04 g / mol, M + = 454.12 g / mol, M + 2 = 456.11 g / mol)

Synthesis Example 18: Synthesis of Intermediate M-6

(94.3 mmol) of 4-dibenzofuranboronic acid and 23.5 g (94.3 mmol) of methyl 2-bromo-4-chlorobenzoate were added to a round bottom flask, and toluene (313 ml) was added to dissolve the solution. 19.5 g 117 mmol) was added and stirred. 1.09 g (0.94 mmol) of tetrakistriphenylphosphine palladium was added thereto, and the mixture was refluxed and stirred for 12 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was extracted with ethyl acetate. The extract was dried with magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography using n-hexane / ethyl acetate (9: 1 v / v) to give 30.2 g (95% yield) of intermediate M-6.

LC-Mass (theory: 336.06 g / mol, measured: M + = 336.14 g / mol)

Synthesis Example 19: Synthesis of Intermediate M-7

29 g (86 mmol) of M-6 was added to a round bottomed flask heated and reduced in pressure, dissolved in anhydrous diethyl ether (430 ml), cooled to 0 ° C, and stirred under a nitrogen atmosphere. 72 ml (215 mmol) of 3.0 M methylmagnesium bromide diethyl ether solution was slowly added thereto, followed by stirring at room temperature and under nitrogen atmosphere for 12 hours. Subsequently, the reaction solution was cooled to 0 deg. C and a small amount of distilled water was added to terminate the reaction. Then, 108 ml of 2.0 M ammonium chloride aqueous solution was added, and the mixture was extracted with diethyl ether. The extract was then dried with magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was used in the next reaction without further purification and 28.7 g (yield 99%) of intermediate M-7 was obtained.

Synthesis Example 20: Synthesis of Intermediate M-8

28.7 g (85.1 mmol) of M-7 was added to a round-bottomed flask heated and reduced in pressure and dried, and 255 ml of anhydrous dichloromethane was added to dissolve it. The solution was cooled to 0 ° C and stirred under a nitrogen atmosphere. 12.1 g (85.1 mmol) of boron trifluoride diethyl etherate was slowly added thereto, followed by stirring at room temperature and under nitrogen atmosphere for 4 hours. The reaction mixture was cooled to 0 ° C and a small amount of distilled water was added to terminate the reaction. 85 ml of 1.0 M sodium bicarbonate aqueous solution was added thereto, followed by extraction with dichloromethane. The extract was then dried with magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography using n-hexane / dichloromethane (9: 1 v / v) to obtain 20.6 g (yield 76%) of intermediate M-8.

LC-Mass (theory: 318.08 g / mol, measured: M + = 318.19 g / mol)

Synthesis Example 21: Synthesis of Intermediate M-28

21.5 g (94.3 mmol) of 4-dibenzothiophene boronic acid and 23.5 g (94.3 mmol) of methyl 2-bromo-4-chlorobenzoate were added to a round-bottomed flask and dissolved in toluene (313 ml) g (141.5 mmol) of triethylamine was added and stirred. 1.09 g (0.94 mmol) of tetrakistriphenylphosphine-palladium was added thereto, and the mixture was stirred under reflux for 12 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was extracted with ethyl acetate. The extract was dried with magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography using n-hexane / ethyl acetate (9: 1 v / v) to obtain 31 g (yield 93%) of intermediate M-28.

LC-Mass (theory: 352.03 g / mol, measured: M + = 352.07 g / mol)

Synthesis Example 22: Synthesis of Intermediate M-29

30.3 g (86 mmol) of M-28 was added to a round bottomed flask heated and reduced in pressure, dissolved in anhydrous diethyl ether (430 ml), cooled to 0 ° C and stirred in a nitrogen atmosphere. 72 ml (215 mmol) of 3.0 M methylmagnesium bromide diethyl ether solution was slowly added thereto, followed by stirring at room temperature for 12 hours under a nitrogen atmosphere. The reaction solution was cooled to 0 ° C and a small amount of distilled water was added thereto to complete the reaction. 108 ml of 2.0 M ammonium chloride aqueous solution was added, and the mixture was extracted with diethyl ether. The extract was dried with magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was used in the next reaction without further purification, and 30 g (yield 99%) of intermediate M-29 was obtained.

LC-Mass (theory: 352.07 g / mol, measured: M + = 352.21 g / mol)

Synthesis Example 23: Synthesis of Intermediate M-30

30 g (85.1 mmol) of M-29 was added to a round-bottomed flask dried under reduced pressure, dissolved in anhydrous dichloromethane (255 ml), cooled to 0 ° C and stirred under a nitrogen atmosphere. 12.1 g (85.1 mmol) of boron tri-fluoride diethyl sulfate was slowly added thereto, followed by stirring at room temperature under a nitrogen atmosphere for 4 hours. The reaction mixture was cooled to 0 ^° C and a small amount of distilled water was added thereto to terminate the reaction. 85 ml of 1.0 M aqueous sodium bicarbonate was added thereto, and the mixture was extracted with dichloromethane. The extract was dried with magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography using n-hexane / dichloromethane (9: 1 v / v) to obtain 21.1 g (yield 74%) of intermediate M-30.

LC-Mass (theory: 334.06 g / mol, measured: M + = 334.16 g / mol)

Synthesis Example 24: Compound I-23

A round bottom flask was charged with 10.4 g (30.9 mmol) of intermediate M-30, 8.8 g (30.9 mmol) of (9,9-dimethyl-9H-fluoren- (46.35 mmol) were added, and 155 ml of toluene was added to dissolve. Thereto, 0.178 g (0.31 mmol) of Pd (dba) 2 and 0.125 g (0.62 mmol) of tri-tertiary-butylphosphine were added in this order, and the mixture was refluxed under nitrogen atmosphere for 12 hours. After extraction with toluene and distilled water, the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography using n-hexane / dichloromethane (8: 2 v / v) to obtain 16.2 g (yield 90%) of compound I-23.

LC-Mass (theory: 598.23 g / mol, measured: M + = 598.33 g / mol)

Synthesis Example 25: Compound I-4

9.9 g (30.9 mmol) of Intermediate M-8, 9.9 g (30.9 mmol) of bis (4-biphenyl) amine and 4.5 g (46.35 mmol) of sodium di-t-butoxide were added to a round bottom flask and 155 ml of toluene was added to dissolve . Thereto, 0.178 g (0.31 mmol) of Pd (dba) 2 and 0.125 g (0.62 mmol) of tri-tertiary-butylphosphine were added in this order, and the mixture was refluxed under nitrogen atmosphere for 12 hours. After extraction with toluene and distilled water, the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography using n-hexane / dichloromethane (8: 2 v / v) to obtain 16.6 g (yield 89%) of compound I-4.

LC-Mass (theory: 603.26 g / mol, measured: M + = 603.29 g / mol)

Synthesis Example 26: Compound E-113

(30.9 mmol) of intermediate M-5, 7.6 g (30.9 mmol) of biphenyl-4-yl-phenylamine and 4.5 g (46.35 mmol) of sodium di-t-butoxide were added to a round bottom flask and 155 ml of toluene was added . 0.178 g (0.31 mmol) of Pd (dba) 2 and 0.125 g (0.62 mmol) of tri-tertiary-butylphosphine were added in this order, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. After extraction with toluene and distilled water, the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography using n-hexane / dichloromethane (8: 2 v / v) to obtain 17.3 g (yield 93%) of compound E-113.

LC-Mass (theoretical value: 619.23 g / mol, measured: M + = 619.11 g / mol)

Synthesis Example 27: Compound E-23

(30.9 mmol) of Intermediate M-5, 9.9 g (30.9 mmol) of bis (4-biphenyl) amine and 4.5 g (46.35 mmol) of sodium di-t-butoxide were added to a round bottom flask and 155 ml of toluene was added to dissolve . 0.178 g (0.31 mmol) of Pd (dba) 2 and 0.125 g (0.62 mmol) of tri-tertiary-butylphosphine were added in this order, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. After extraction with toluene and distilled water, the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography using n-hexane / dichloromethane (8: 2 v / v) to obtain 19.8 g (yield 92%) of compound E-23.

LC-Mass (theoretical value: 695.26 g / mol, measurement: M + = 695.37 g / mol)

Fabrication of organic light emitting device

Example 1-1

Glass substrate coated with ITO (Indium tin oxide) thin film with thickness of 1500Å was washed with distilled water ultrasonic wave. After the distilled water was cleaned, the substrate was ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, or methanol, dried and transferred to a plasma cleaner, the substrate was cleaned using oxygen plasma for 10 minutes, and then the substrate was transferred to a vacuum deposition machine. N4, N4'-diphenyl-N4, N4'-bis (9-phenyl-9H-carbazol-3-yl) biphenyl-4,4'- Diamine (Compound A) was vacuum-deposited to form a hole injection hole having a thickness of 700 Å. The hole injection layer was formed by vacuum deposition of N4, N4'-diphenyl-N4 and N4'-bis (9- Layer was formed on the hole injection layer and 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile (HAT- CN) (Compound B) was deposited to a thickness of 50 ANGSTROM and then N- (biphenyl-4-yl) -9,9-dimethyl-N- (4- Phenyl) -9H-fluorene-2-amine (N- (4-fluorophenyl) -9H-carbazol- 9H-fluoren-2-amine (Compound C) was deposited to a thickness of 700 Å to form a hole transport layer. Compound I-23 obtained in Synthesis Example 24 was vacuum-deposited on the hole transport layer to form a hole transporting auxiliary layer having a thickness of 320 Å. Subsequently, Compound A-33 obtained in Synthesis Example 8 and Compound B-10 obtained in Synthesis Example 10 were simultaneously used as a host on the hole transporting auxiliary layer and tris (4-methyl-2,5-diphenylpyridine) iridium (III) (compound D) was doped to 10 wt%, and a 400 Å thick light emitting layer was formed by vacuum deposition. Compound A-33 and Compound B-10 were used in a weight ratio of 1: 1.

Subsequently, 8- (4- (4- (naphthalen-2-yl) -6- (naphthalen-3-yl) -1,3,5-triazin- (Compound E) and Liq at the same time in the ratio of 1: 1 to 1: 1. 1 ratio to form an electron transport layer having a thickness of 300 ANGSTROM and an anode was formed by sequentially vacuum-depositing Liq 15 ANGSTROM and Al 1200 ANGSTROM on the electron transport layer to prepare an organic light emitting device.

The organic light emitting device has a structure having six organic thin film layers. Specifically,

A-33: B-10: D = X: X: 10%] (A), the hole transporting layer (ITO / A (700 Å) / B (50 Å) / C 400 Å / E: Liq 300 Å / Liq 15 Å / Al 1200 Å.

(X = weight ratio)

Examples 1-2

An organic light emitting device was fabricated in the same manner as in Example 1-1, except that Compound E-23 obtained in Synthesis Example 27 was used instead of Compound I-23 in the hole transporting assisting layer.

Example 2-1

An organic luminescent device was fabricated in the same manner as in Example 1-1, except that Compound B-31 obtained in Synthesis Example 11 was used instead of Compound B-10 in the light emitting layer.

Example 2-2

An organic light emitting device was fabricated in the same manner as in Example 2-1, except that Compound E-23 obtained in Synthesis Example 27 was used instead of Compound I-23 in the hole transporting assisting layer.

Example 3-1

An organic luminescent device was fabricated in the same manner as in Example 1-1, except that Compound C-10 obtained in Synthesis Example 9 was used instead of Compound B-10 in the light emitting layer.

Example 3-2

An organic luminescent device was fabricated in the same manner as in Example 3-1, except that Compound E-23 obtained in Synthesis Example 27 was used instead of Compound I-23 in the hole transporting assisting layer.

Example 4-1

An organic light emitting device was fabricated in the same manner as in Example 1-1 except that Compound B-43 obtained in Synthesis Example 12 was used instead of Compound B-10 in the light emitting layer.

Example 4-2

An organic luminescent device was fabricated in the same manner as in Example 4-1, except that Compound E-23 obtained in Synthesis Example 27 was used instead of Compound I-23 in the hole transporting assisting layer.

Example 4-3

An organic luminescent device was fabricated in the same manner as in Example 4-1, except that Compound I-4 obtained in Synthesis Example 25 was used instead of Compound I-23 in the hole transporting auxiliary layer.

Example 4-4

An organic light emitting device was prepared in the same manner as in Example 4-1 except that the compound E-113 obtained in Synthesis Example 26 was used instead of the compound I-23 in the hole transporting auxiliary layer.

Comparative Example 1

An organic light emitting device was fabricated in the same manner as in Example 1-1, except that the hole transporting auxiliary layer was not used.

Comparative Example 2

An organic light emitting device was fabricated in the same manner as in Example 2-1 except that the hole transporting auxiliary layer was not used.

Comparative Example 3

An organic light emitting device was fabricated in the same manner as in Example 3-1 except that the hole transporting auxiliary layer was not used.

Comparative Example 4

An organic light emitting device was fabricated in the same manner as in Example 4-1 except that the hole transporting auxiliary layer was not used.

evaluation

The luminous efficiency and roll-off characteristics of the organic luminescent devices according to Examples 1-1 to 4-4 and Comparative Examples 1 to 4 were evaluated.

The specific measurement method is as follows, and the results are shown in Table 1.

(1) Measurement of change in current density with voltage change

For the organic light emitting device manufactured, the current flowing through the unit device was measured using a current-voltmeter (Keithley 2400) while raising the voltage from 0 V to 10 V, and the measured current value was divided by the area to obtain the result.

(2) Measurement of luminance change according to voltage change

For the organic light-emitting device manufactured, luminance was measured using a luminance meter (Minolta Cs-1000A) while increasing the voltage from 0 V to 10 V, and the result was obtained.

(3) Measurement of luminous efficiency

The current efficiency (cd / A) at the same current density (10 mA / cm 2) was calculated using the luminance, current density and voltage measured from the above (1) and (2).

(4) Roll-off measurement

The decrease in efficiency was calculated as% (Max value - value at 6000 cd / m ² / Max value) among the characteristic values of the above (3)

(5) Life measurement

The time at which the luminance (cd / m ² ) was maintained at 6000 cd / m ² and the current efficiency (cd / A) decreased to 97% was measured and the results were obtained.

Hole transporting auxiliary layer The light- Luminous efficiency
(cd / A) Roll-off
(%) Lifetime T97 (h) The first compound The second compound First compound: second compound
(wt: wt) Example 1-1 I-23 A-33 B-10 1: 1 55.1 10.4 350 Examples 1-2 E-23 A-33 B-10 1: 1 55.7 9.7 370 Comparative Example 1 - A-33 B-10 1: 1 45.1 17.3 350 Example 2-1 I-23 A-33 B-31 1: 1 57.0 8.6 150 Example 2-2 E-23 A-33 B-31 1: 1 55.9 9.1 170 Comparative Example 2 - A-33 B-31 1: 1 49.1 10.4 150 Example 3-1 I-23 A-33 C-10 1: 1 52.8 15.3 450 Example 3-2 E-23 A-33 C-10 1: 1 53.5 14.3 430 Comparative Example 3 - A-33 C-10 1: 1 42.3 24.8 450 Example 4-1 I-23 A-33 B-43 1: 1 57.2 9.2 750 Example 4-2 E-23 A-33 B-43 1: 1 58.3 8.9 760 Example 4-3 I-4 A-33 B-43 1: 1 58.1 8.1 650 Example 4-4 E-113 A-33 B-43 1: 1 56.2 9.2 700 Comparative Example 4 - A-33 B-43 1: 1 44.0 20.7 720

Referring to Table 1, the organic luminescent devices according to Examples 1-1 to 4-4 were compared with the organic luminescent devices according to Comparative Examples 1 to 4, respectively, so that their lifetime characteristics were not greatly affected, and the luminous efficiency and the roll- Can be confirmed to be remarkably improved at the same time.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

10: anode 20: cathode
30: organic layer 31: hole transport layer
32: light emitting layer 33: hole transporting auxiliary layer
34: electron transport layer

Claims (15)

The anode and cathode,
A light emitting layer positioned between the anode and the cathode,
A hole transporting layer positioned between the anode and the light emitting layer, and
A hole transporting auxiliary layer disposed between the hole transporting layer and the light emitting layer,
/ RTI >
Wherein the light emitting layer comprises at least one first compound represented by the following Formula 1 and at least one second compound represented by the following Formula 2,
Wherein the hole transporting auxiliary layer comprises at least one third compound represented by a combination of a moiety represented by the following formula (3), a moiety represented by the following formula (4), and a moiety represented by the following formula
Organic optoelectronic devices:
[Chemical Formula 1]

In Formula 1,
Each Z is independently N, C or CR ^a ,
At least one of Z is N,
R ¹ to R ¹⁰ and R ^a are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group or a combination thereof,
The total number of 6-membered rings substituted in the triphenylene group in Formula 1 is 6 or less,
L ¹ is a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group or a substituted or unsubstituted terphenylene group,
n1 to n3 are each independently 0 or 1,
n1 + n2 + n3? 1,
(2)

In Formula 2,
Y ¹ is a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroaryl Or a combination thereof,
Ar ¹ is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,
R ¹¹ to R ¹⁴ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heteroaryl group, or combinations thereof ,
At least one of R ¹¹ to R ¹⁴ and Ar ¹ includes a substituted or unsubstituted triphenylene group or a substituted or unsubstituted carbazole group,
[Chemical Formula 3]

In the above formulas 3 to 5,
X ¹ is O, S, NR ^b , SO ₂ , PO or CO,
X ² is O, S, SO ₂ , PO, CR ^c R ^d or NR ^e ,
R ⁵⁵ , R ⁵⁶ and R ^b to R ^e are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl Or a combination thereof, or is bonded to c * in Formula 5,
Ar ² and Ar ³ are each independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group,
L ² , L ^a and L ^b each independently represents a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, A substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group or a combination thereof,
The adjacent two * in the above formula (3) combine with the two * in the above formula (4) to form a fused ring,
Any of a *, b *, R ^b to R ^e in the above formula (3) or (4) is connected by sigma bond to c * in the above formula (5)
The remaining a *, b *, and R ^b to R ^e , which are not bonded to c * in Formula 5, are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl , A substituted or unsubstituted C3 to C30 heteroaryl group, or combinations thereof.
The method of claim 1,
Wherein the first compound is represented by the following Formula 1-I or Formula 1-II:
[Chemical Formula 1-I] [Chemical Formula 1-II]

In the above formula (I-I) or (II-II)
Each Z is independently N, C or CR ^a ,
At least one of Z is N,
R ¹ to R ¹⁰ and R ^a are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C12 aryl group or a combination thereof,
The total number of 6-membered rings substituted in the triphenylene group in the above-mentioned Formulas I-I and I-II is 6 or less,
L ¹ is a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group or a substituted or unsubstituted terphenylene group,
n1 to n3 are each independently 0 or 1,
n1 + n2 + n3? 1.
The method of claim 1,
L ¹ in the formula (1) represents a single bond, a substituted or unsubstituted phenylene group having a kink structure, a substituted or unsubstituted biphenylene group having a bending structure or a substituted or unsubstituted terphenylene group device.
4. The method of claim 3,
Wherein L ¹ is a single bond in the formula (1) or to an organic optoelectronic one selected from substituted or unsubstituted groups listed in the group 1 element:
[Group 1]

In the group 1,
R ¹⁵ to R ⁴² are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted amine group, a substituted or unsubstituted C6 to C30 arylamine group, a substituted or unsubstituted C6 to C30 heteroaryl amine A substituted or unsubstituted C1 to C30 alkoxy group, a halogen group, a halogen-containing group, a cyano group, a hydroxyl group, an amino group, a nitro group, a carboxyl group, a ferrocenyl group or a combination thereof.
The method of claim 1,
Wherein the first compound has at least two fold structures.
The method of claim 1,
Wherein the second compound is represented by at least one of the following general formulas (II-1) to (II-III):
[Chemical Formula 2-I] [Chemical Formula 2-II]

[Chemical Formula 2-III]

In the above Formulas 2-1 to 2-III,
Y ¹ to Y ³ each independently represents a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C6 to C30 arylene group, C2-C30 heteroarylene groups or combinations thereof,
Ar ¹ , Ar ^1a and Ar ^1b are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group or a combination thereof,
R ¹¹ to R ¹⁴ and R ⁴³ to R ⁵⁴ each independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 hetero Aryl groups or combinations thereof.
The method of claim 6,
Ar ¹ , Ar ^1a and Ar ^1b in the formula (2-I) each independently represent a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, A substituted or unsubstituted thiophene group, a substituted or unsubstituted thiophene group, a substituted or unsubstituted thiophene group, a substituted or unsubstituted thiophene group, or an unsubstituted anthracenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted benzofuranyl group, A substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted pyrazinyl group, a substituted or unsubstituted triazinyl group, An unsubstituted dibenzothiophenylene group, or a combination thereof.
The method of claim 6,
Wherein the compound represented by Formula 2-I is selected from the compounds listed in the following Group 5:
[Group 5]

The method of claim 6,
Wherein the compound represented by Formula 2-II is selected from the compounds listed in Group 6 below:
[Group 6]

The method of claim 6,
Wherein the compound represented by Formula 2-III is selected from the compounds listed in Group 7 below:
[Group 7]

The method of claim 1,
Wherein the third compound is represented by any one of the following formulas (6) to (17):
[Chemical Formula 6] < EMI ID =

[Chemical Formula 8]

[Chemical Formula 10]

[Chemical Formula 12]

[Chemical Formula 14]

[Chemical Formula 16]

In the above formulas 6 to 17,
X ¹ is O, S, NR ^b , SO ₂ , PO or CO,
X ² is O, S, SO ₂ , PO, CR ^c R ^d or NR ^e ,
R ⁵⁵ , R ⁵⁶ and R ^b to R ^e are each independently selected from the group consisting of hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C32 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl Or a combination thereof,
Ar ² and Ar ³ are each independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group,
L ² , L ^a and L ^b each independently represents a single bond, a substituted or unsubstituted C1 to C30 alkylene group, a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, A substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group, or a combination thereof.
The method of claim 1,
And the hole transporting auxiliary layer is in contact with the hole transporting layer and the light emitting layer, respectively.
The method of claim 1,
Wherein the light emitting layer comprises the first compound and the second compound in a weight ratio of 1:10 to 10: 1.
The method of claim 1,
Wherein the light emitting layer further comprises a phosphorescent dopant.
A display device comprising the organic opto-electronic device according to any one of claims 1 to 14.

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