KR101869843B1 - Organic optoelectric device and display device - Google Patents

Abstract

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,
And a hole transporting auxiliary layer disposed between the hole transporting layer and the light emitting layer, 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) And the hole transporting auxiliary layer comprises at least one third compound represented by the following general formula (3), and a display device comprising the organic optoelectronic device.
(1) to (3) are 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 of the biggest problems in long life full color displays is the lifetime of blue organic light emitting devices. Therefore, much research is underway to develop a long-lived blue organic light-emitting device. In order to solve such a problem, the present invention provides a long-life blue organic light emitting device.

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), wherein the hole transporting auxiliary layer is represented by the following general formula And at least one third compound which is at least one of the first compound and the second compound.

[Chemical Formula 1]

In Formula 1,

Each Z is independently N 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,

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 and Y ² are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group or a combination thereof,

Ar ^1a and Ar ^1b are 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 ¹⁶ 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 group, or combinations thereof ,

(3)

In Formula 3,

L ² to L ⁷ are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group or a combination thereof,

n4 to n9 each independently represents an integer of 0 to 3,

R ¹⁷ to R ²² each independently represent hydrogen, deuterium, halogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, A substituted or unsubstituted C1 to C20 alkylthio group, a substituted or unsubstituted C6 to C30 aralkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 C30 aryloxy group, a substituted or unsubstituted C6 to C30 arylthio group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted C2 to C30 amino group, a substituted or unsubstituted C3 to C30 silyl group , A cyano group, a nitro group, a hydroxyl group or a carboxyl group, or a combination thereof,

R ¹⁷ to R ²² are each independently present, or R ¹⁷ and R ¹⁸ , R ¹⁹ and R ²⁰ , and R ²¹ and R ²² are connected to each other to form a fused ring,

"Substitution" in the above Chemical Formulas 1 to 3 means that at least one of the hydrogen atoms is replaced by a substituent selected from the group consisting of deuterium, a halogen group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, a substituted or unsubstituted C1 to C40 silyl group, C30 alkyl group, C3 to C30 cycloalkyl group, C2 to C30 heterocycloalkyl group, C6 to C30 aryl group, C2 to C30 heteroaryl group, C1 to C20 alkoxy group, fluoro group, C1 to C10 trifluoroalkyl group or cyano group ≪ / RTI >

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 and 2 are cross-sectional views 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 "heterocyclic group" means a heteroatom selected from the group consisting of N, O, S, P and Si in a ring compound such as an aryl group, a cycloalkyl group, a fused ring thereof, Containing at least one and the remainder being carbon. When the heterocyclic group is a fused ring, the heterocyclic group or the ring may include one or more heteroatoms. Therefore, the heterocyclic group is a superordinate concept including a heteroaryl group.

More specifically, the substituted or unsubstituted C6 to C30 aryl group and / or the substituted or unsubstituted C2 to C30 heterocyclic group may be substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthra 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 pyrenyl 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 thiazolyl group, a substituted or unsubstituted pyrazolyl group, A substituted or unsubstituted thiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted thiadiazolyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted thiazolyl group, Substituted or unsubstituted pyrazinyl groups, substituted or unsubstituted thiazinyl groups, substituted or unsubstituted benzofuranyl groups, substituted or unsubstituted benzothiophenyl groups, substituted or unsubstituted benzimidazolyl groups, substituted A substituted or unsubstituted quinolinyl group, a substituted or unsubstituted quinolinyl 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, Substituted or unsubstituted pyrazinyl groups, substituted or unsubstituted pyrazinyl groups, substituted or unsubstituted benzoxazinyl groups, substituted or unsubstituted benzothiazyl groups, substituted or unsubstituted acridinyl groups, substituted or unsubstituted phenazinyl groups, Substituted or unsubstituted dibenzothiocarbonyl groups, substituted or unsubstituted dibenzothiocarbonyl groups, substituted or unsubstituted dibenzothiocarbonyl groups, substituted or unsubstituted dibenzothiocarbonyl groups, substituted or unsubstituted dibenzothiocarbonyl groups, A phenyl 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 to inject electrons formed in the cathode into the light emitting layer, move electrons formed in the light emitting layer 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 SnO2 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, LiO2 / Al, LiF / Ca, LiF / Al, and BaF2 / 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.

2, the organic layer 30 may further include a hole injection layer 37 between the hole transport layer 31 and the anode 10, and may include an electron injection layer 37 between the electron transport layer 34 and the cathode 20. [ And may further include an injection layer 36.

The hole injection layer 37 deposited between the hole transport layer 31 and the anode 10 not only improves the interface characteristics between the ITO used as the anode and the organic material used as the hole transport layer 31, It is applied on the top of uneven ITO to soften the surface of ITO. For example, in order to control the difference between the work function level of ITO that can be used as an anode and the HOMO level of the hole transport layer 31, the hole injection layer 37 has a function of the ITO function and the HOMO level of the hole transport layer 31 As a substance having a medium value, a substance having a particularly suitable conductivity is selected. As a constituent material of the positive hole injection layer 37, N4, N4'-diphenyl-N4, N4'-bis (9-phenyl-9H-carbazol- Diamine (N4, N4'-diphenyl-N4, N4'-bis (9-phenyl-9H-carbazol-3-yl) biphenyl-4,4'-diamine) may be used. (CuPc), N, N'-dinaphthyl-N, N'-phenyl- (1,1'-diphenylphosphonium), and the like can be used together with the conventional materials constituting the hole injection layer 37. [ 4,4'-diamine, NPD), 4,4 ', 4 "-tris [methylphenyl (phenyl) amino] triphenyl amine (m- (phenylamino) triphenyl amine (1-TNATA), 4,4 ', 4 "-tris [2-naphthyl (4-diphenylaminophenyl) phenylamino] benzene (p-DPA-TDAB) and the like, as well as aromatic amines such as 4,4'- Poly (3,4-ethylenedioxythiophene) -poly (styrnesulfonate) (PEDOT) which is a polythiophene derivative as a conductive polymer can be used as a conductive polymer. The hole injection layer 37 may be coated on top of the ITO used as the anode, for example, with a thickness of 10 to 300 ANGSTROM.

The electron injection layer 36 is a layer that is stacked on top of the electron transport layer and facilitates injection of electrons from the cathode to ultimately improve power efficiency. The electron injection layer 36 may be used without any particular limitation as long as it is commonly used in the art And materials such as LiF, Liq, NaCl, CsF, Li ₂ O, and BaO can be used.

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 electron transport layer 34 is a layer for facilitating the electron transfer from the cathode 20 to the light emitting layer 32. The electron transport layer 34 is formed of an organic compound having an electron withdrawing group, , Or a mixture thereof can be used. For example, aluminum trihydroxyquinoline (Alq ₃ ), a 1,3,4-oxadiazole derivative, 2- (4-biphenyl-5-phenyl-1,3,4-oxadiazole (4-biphenylyl) -5-phenyl-1,3,4-oxadiazole, PBD), a quinoxaline derivative such as 1,3,4-tris [(3-phenyl-6-trifluoromethyl) (4-tris [(3-penyl-6-trifluoromethyl) quino-xaline-2-yl] benzene, TPQ), triazole derivatives and triazine derivatives, Yl) phenyl) quinoline (8- (4- (4- (naphthalen-3-yl) -1,3,5-triazin- 2-yl) -6- (naphthalen-3-yl) -1,3,5-triazin-2-yl) phenyl) quinoline.

The electron transporting layer may be used alone or in combination with the electron transporting layer material as the organometallic compound represented by the following formula (c).

(C)

In the above formula (c)

Y is a moiety selected from C, N, O and S, which is directly bonded to M to form a single bond, and any moiety selected from C, N, O and S is a moiety coordinating to M And is a ligand chelated by coordination bond with the single bond,

Wherein M is an alkali metal, an alkaline earth metal, an aluminum (Al), or a boron (B) atom, and OA is a monovalent ligand capable of single bond or coordination bond with M,

O is oxygen,

A represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 50 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted C2 to C20 Substituted or unsubstituted cycloalkyl groups having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl groups having 5 to 30 carbon atoms, and substituted or unsubstituted hetero atoms having 2 to 50 carbon atoms having O, N or S, An aryl group,

M is 1 and n is 0 when M is a metal selected from an alkali metal,

M = 1, n = 1, or m = 2 and n = 0 when M is a metal selected from alkaline earth metals,

M is from 1 to 3 when M is boron or aluminum, and n is any of from 0 to 2, and m + n = 3;

The 'substituted' in the 'substituted or unsubstituted' may be a substituent selected from the group consisting of deuterium, cyano, halogen, hydroxy, nitro, alkyl, alkoxy, alkylamino, arylamino, heteroarylamino, alkylsilyl, An aryl group, an aryl group, a heteroaryl group, germanium, phosphorus, and boron.

In the present invention, each Y may be the same or different and independently selected from the following formulas c1 to c39, but is not limited thereto.

[Chemical formula c1] [Chemical formula c2] Chemical formula c3 Chemical formula c4 Chemical formula c5 [

[Chemical formula c6] [Chemical formula c7] [Chemical formula c8] [Chemical formula c9] [Chemical formula c10]

[Chemical formula c11] [Chemical formula c12] Chemical formula c13] Chemical formula c14] Chemical formula c15]

 [Chemical formula c16] [Chemical formula c17] [Chemical formula c18] [Chemical formula c19] [Chemical formula c20]

[Chemical formula c22] Chemical formula c22 Chemical formula c24 Chemical formula c25 [

[Chemical Formula c26] Chemical Formula c27 Chemical Formula c29 Chemical Formula c30 [

[Chemical formula c32] Chemical formula c33 Chemical formula c34 Chemical formula c35 [

[Chemical formula c36] [Chemical formula c37] Chemical formula c38] Chemical formula c39]

In the above formulas c1 to c39,

R is identical or different and are each independently selected from the group consisting of hydrogen, deuterium, halogen, cyano, substituted or unsubstituted C1 to C30 alkyl groups, substituted or unsubstituted C6 to C30 aryl groups, substituted or unsubstituted C3 to C30 hetero A substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C1 to C30 alkylamino group, A substituted or unsubstituted C1 to C30 alkylsilyl group, a substituted or unsubstituted C6 to C30 arylamino group, and a substituted or unsubstituted C6 to C30 arylsilyl group, and is connected to an adjacent substituent by an alkylene or alkenylene to form a spiro ring or a fused ring A ring can be formed.

The light emitting layer 32 is an organic layer having a light emitting function, and includes a host and a dopant when a doping system is employed. At this time, the host has a function of promoting the recombination of electrons and holes mainly, and has a function of confining excitons in the light emitting layer, and the dopant has a function of efficiently emitting excitons obtained by recombination.

The light emitting layer may include a known host and a dopant.

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 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,

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 formula ( ¹ ) is 0, that is, in the structure having no linking group (L ¹ ), it may form a bending structure centering on an arylene group / heteroarylene group, have.

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

In the above general formula (Ia) or (Ib), 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,

* Is a connection point,

Wherein "at least one hydrogen is substituted with one or more substituents selected from the group consisting of deuterium, halogen, C1 to C20 alkyl groups, C3 to C20 cycloalkyl groups, C1 to C20 alkoxy groups, C3 to C20 cycloalkoxy groups, C1 to C20 alkylthio groups, An alkyl group, a C6 to C30 aryl group, a C6 to C30 aryloxy group, a C6 to C30 arylthio group, a C2 to C30 heteroaryl group, a C2 to C30 amino group, a C3 to C30 silyl group, a cyano group, a nitro group, Substituted with a carboxyl group.

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 efficiency of the organic optoelectronic device to which the composition is applied.

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 and Y ² are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group or a combination thereof,

Ar ^1a and Ar ^1b are 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 ¹⁶ 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 .

The compound represented by Formula 2 is a compound having bipolar characteristics with relatively high hole characteristics and is used in the light emitting layer together with the first compound to increase charge mobility and stability, Can be improved. Further, the charge transportability can be controlled by controlling the ratio of the compound represented by the formula (2) having the hole property to the first compound.

The second compound may be represented by at least one of the following general formulas (II-1) to (II-VIII) depending on the bonding position of the bicalbaazole.

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

[Chemical Formula 2-III] [Chemical Formula 2-IV] Chemical Formula 2-V]

[Chemical Formula 2-VI] [Chemical Formula 2-VII] [Chemical Formula 2-VIII]

In the above general formulas (II-1) to (II-VIII)

Y ¹ and Y ² , Ar ^1a and Ar ^1b , and R ¹¹ to R ¹⁶ are respectively as described above.

The second compound is a structure in which two carbazole groups having a substituent are connected to each other.

Ar ^1a and Ar ^1b of the second compound 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, A substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted benzofuranyl 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 di A benzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof.

The second compound may be represented by at least one of the following general formulas (II-IX) to (II-XI) depending on the characteristics of Ar ^1a and Ar ^1b .

[Chemical Formula 2-IX] [Chemical Formula 2-X] [Chemical Formula 2-XI]

In the above formulas 2-IX to 2-XI,

Y ¹ and Y ² , and R ¹¹ to R ¹⁶ are as defined above,

ET, ET1, and ET2 are each independently a substituent having electron characteristics, and HT, HT1 and HT2 are substituents independently of each other. The substituents " ET "," ET1 ", and " ET2 " having electron characteristics in Ar ^1a and Ar ^1b of the second compound may be substituents represented by,

(A)

In the above formula (A)

Each Z is independently N or CR ^d ,

A1 and A2, and ^Rd 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]

Further, the second compound, Ar ^1a And substituents " HT "," HT1 ", and " HT2 " having a hole property in Ar ^1b may be one of the functional groups listed in the following Group 4, for example.

[Group 4]

The second compound may be selected from compounds listed in the following Group 5, but is not limited thereto.

[Group 5]

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

Specifically, the first compound and the second compound may be included in the light emitting layer 32 as a host, and at least one of the first compounds represented by the general formulas (I-1) and (II-II) And at least one of the second compounds represented by Formulas 2-IX to 2-XI. More specifically, it may include a first compound represented by Formula 1-I and a second compound represented by Formula 2-XI.

In addition, the first compound and the second compound may be contained at a weight ratio of, for example, about 1:10 to 10: 1, and specifically 2: 8 to 8: 2, 3: 7 to 7: : 4, and 5: 5 by weight. 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 relatively good hole property.

The hole transporting auxiliary layer 33 includes the third compound to reduce the HOMO energy level difference between the hole transporting layer 31 and the light emitting layer 32 to control the injection characteristics of the holes to form the hole transporting auxiliary layer 33, It is possible to reduce accumulation of holes at the interface of the light emitting layer 32 and to reduce quenching in which the excitons are destroyed by the polaron at the interface. As a result, the deterioration phenomenon of the element is reduced and the element is stabilized, thereby improving the efficiency and lifetime.

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

(3)

In Formula 3,

L ² to L ⁷ are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted heteroarylene group or a combination thereof,

n4 to n9 each independently represents an integer of 0 to 3,

R ¹⁷ to R ²² each independently represent hydrogen, deuterium, halogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, A substituted or unsubstituted C1 to C20 alkylthio group, a substituted or unsubstituted C6 to C30 aralkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C6 C30 aryloxy group, a substituted or unsubstituted C6 to C30 arylthio group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted C2 to C30 amino group, a substituted or unsubstituted C3 to C30 silyl group , A cyano group, a nitro group, a hydroxyl group or a carboxyl group, or a combination thereof,

R ¹⁷ to R ²² are each independently present, or R ¹⁷ and R ¹⁸ , R ¹⁹ and R ²⁰ , and R ²¹ and R ²² may be connected to each other to form a fused ring.

The third compound may be represented by, for example, the following formulas (III-1) to (III-III) depending on whether the substituents R ¹⁷ to R ²² are fused or not.

[Formula 3-I] [Formula 3-II]

[Formula 3-III]

In the above formulas (3-1) to (3-1), L ² to L ⁷ , n 4 to n ⁹ , and R ¹⁷ to R ²² are as described above.

The third compound may be, for example, at least one of the following formulas (3a) to (3k).

[Formula 3]

[Chemical Formula 3c]

[Formula 3e] [Formula 3f]

[Chemical Formula 3g] [Chemical Formula 3h]

[Formula 3i] [Formula 3j]

[Chemical Formula 3k]

In the above formulas (3a) to (3k), R ¹⁷ to R ²² , L ² to L ⁷ , and n 4 to n ⁹ are as described above,

X ¹ to X ³ are each independently O, S, or CR ^b R ^c ,

X ³ are each independently O or S,

R ²³ , R ²⁴ , R ^b and R ^c are each independently selected from the group consisting of hydrogen, deuterium, halogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, C20 alkoxy group, a substituted or unsubstituted C3 to C20 cycloalkoxy group, a substituted or unsubstituted C1 to C20 alkylthio group, a substituted or unsubstituted C6 to C30 aralkyl group, a substituted or unsubstituted C6 to C30 aryl group , A substituted or unsubstituted C6 to C30 aryloxy group, a substituted or unsubstituted C6 to C30 arylthio group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C2 to C30 amino group, A substituted or unsubstituted C3 to C30 silyl group, a cyano group, a nitro group, a hydroxyl group or a carboxyl group,

Ar ² to Ar ⁷ each independently represent a substituted or unsubstituted C6 to C30 aryl group.

Specifically, R ¹⁷ to R ²² in the above formula (3) specifically include a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrylene group, A substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group, A substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted benzyl group, Substituted dibenzothiophenyl groups, combinations thereof,

More specifically, a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted substituted or unsubstituted dibenzofuranyl groups, substituted or unsubstituted dibenzofuranyl groups, substituted or unsubstituted dibenzofuranyl groups, substituted or unsubstituted dibenzofuranyl groups, substituted or unsubstituted dibenzofuranyl groups, substituted or unsubstituted dibenzofuranyl groups, A benzothiophenyl group, or a combination thereof.

The Ar ² to Ar ⁷ specifically represent a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, a substituted or unsubstituted naphthyl group, a substituted Or a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenyl group, or a combination thereof Lt; / RTI >

More specifically, a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted quaterphenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl A substituted or unsubstituted phenanthrene group, a substituted or unsubstituted triphenylene group, or a combination thereof.

The L ² to L ⁷ may specifically be a phenylenyl group, a biphenylenyl group, a naphthalenyl group, or a combination thereof,

For example, one of the substituted or unsubstituted groups listed in Group 6 below.

[Group 6]

In the above group 6,

* Is a connection point,

The term "substituted" as used herein means that at least one hydrogen is replaced by a substituent selected from the group consisting of deuterium, a halogen group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, a substituted or unsubstituted C1 to C40 silyl group, Means a C30 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 C20 alkoxy group, a fluoro group, a C1 to C10 trifluoroalkyl group or a cyano group do.

The third compound may be selected from, for example, compounds listed in the following Group 7, but is not limited thereto.

[Group 7]

[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]

[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] [F-29] [F-30]

[F-31] [F-32] [F-33]

[F-34] [F-35] [F-36]

[F-37] [F-38] [F-39]

[F-40] [F-41] [F-42]

[F-43] [F-44] [F-45]

[F-46] [F-47] [F-48]

[F-49] [F-50] [F-51]

[F-52] [F-53] [F-54]

[F-55] [F-56] [F-57]

[F-58] [F-59] [F-60]

[F-61] [F-62] [F-63]

[F-64] [F-65] [F-66]

[F-67] [F-68] [F-69]

[F-70] [F-71] [F-72]

[F-73] [F-74] [F-75]

[F-76] [F-77] [F-78]

[F-79] [F-80] [F-81]

[F-82] [F-83] [F-84]

[F-85] [F-86] [F-87]

[F-88] [F-89] [F-90]

[F-91] [F-92] [F-93]

[F-94] [F-95] [F-96]

[F-97] [F-98] [F-99]

[F-100] [F-101] [F-102]

[F-103] [F-104] [F-105]

[F-106] [F-107] [F-108]

[F-109] [F-110] [F-111]

[F-112] [F-113] [F-114]

[F-115] [F-116] [F-117]

[F-118] [F-119] [F-120]

[F-121] [F-122] [F-123]

[F-124] [F-125] [F-126]

[F-127] [F-128] [F-129]

[F-130] [F-131] [F-132]

[F-133] [F-134] [F-135]

[F-136] [F-137] [F-138]

[F-139] [F-140] [F-141]

[F-142] [F-143] [F-144]

[F-145] [F-146] [F-147]

[F-148] [F-149] [F-150]

[F-151] [F-152] [F-153]

[F-154] [F-155] [F-156]

[F-157] [F-158] [F-159]

[F-160] [F-161] [F-162] [F-163]

[F-164] [F-165] [F-166] [F-167]

[F-168] [F-169] [F-170] [F-171]

[F-172] [F-173] [F-174] [F-175]

[F-176] [F-177] [F-178] [F-179]

[F-180] [F-181] [F-182] [F-183]

[F-184] [F-185] [F-186] [F-187]

[F-188] [F-189] [F-190] [F-191]

[F-192] [F-193] [F-194] [F-195]

[F-196] [F-197] [F-198] [F-199]

[F-200] [F-201] [F-202]

[F-203] [F-204] [F-205]

[F-206] [F-207] [F-208]

[F-209] [F-210] [F-211]

[F-212] [F-213] [F-214]

[F-215] [F-216] [F-217]

[F-218] [F-219] [F-220] [F-221]

[F-222] [F-223] [F-224]

[F-225] [F-226] [F-227]

[F-228] [F-229] [F-230] [F-231]

[F-232] [F-233] [F-234]

[F-235] [F-236] [F-237]

[F-238] [F-239] [F-240]

[F-241] [F-242] [F-243]

　

　

[F-244] [F-245] [F-246]

[F-247] [F-248] [F-249]

[F-250] [F-251] [F-252]

[F-253] [F-254] [F-255]

[F-256] [F-257] [F-258]

[F-259] [F-260] [F-261]

[F-262] [F-263] [F-264]

[F-265] [F-266] [F-267]

[F-268] [F-269] [F-270]

[F-271] [F-272] [F-273]

[F-274] [F-275] [F-276]

[F-277] [F-278] [F-279]

[F-280] [F-281] [F-282]

[F-283] [F-284] [F-285]

[F-286] [F-287] [F-288]

[F-289] [F-290] [F-291]

[F-292]

[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]

An organic optoelectronic device according to an embodiment of the present invention includes a light emitting layer that simultaneously includes a first compound having a strong electron characteristic and a second compound having a strong hole characteristic,

A hole transporting auxiliary layer including a third compound having a good hole transporting property capable of controlling injection characteristics of holes by reducing a HOMO energy level difference between the hole transporting layer 31 and the light emitting layer 32 may be included at the same time.

By using them together, it is possible to reduce the accumulation of holes at the interface between the hole transporting auxiliary layer 33 and the light emitting layer 32, thereby reducing quenching in which the excitons are destroyed by the polaron at the interface. As a result, the deterioration phenomenon of the element is reduced and the element is stabilized, thereby improving the efficiency and lifetime.

Specifically, a light-emitting layer comprising at least one of the first compound represented by Formula 1-I or Formula 1-II and a second compound represented by Formula 2-IX to 2-XI, and

A hole transporting auxiliary layer containing at least one of the third compounds represented by the general formulas (III-1) to (III-III), for example, the compound represented by the general formula (III-I) may be used together.

In one embodiment of the present invention, the light emitting layer comprises a first compound represented by Formula 1-I and a second compound represented by Formula 2-XI, wherein the hole transporting auxiliary layer is represented by Formula 3 Lt; RTI ID = 0.0 > III-I. ≪ / RTI >

More specifically, a light-emitting layer comprising at least one of the first compound represented by the above Chemical Formulas 1c to 1t and a second compound represented by Chemical Formula 2-IX to 2-XI, A hole transporting auxiliary layer containing at least one of the third compounds to be expressed may be used together.

More specifically, a light-emitting layer comprising at least one of a first compound represented by Chemical Formula 1c, 1d, 1g, and 1h and a second compound represented by Chemical Formula 2-IX to Chemical Formula 2-XI, , 3b, 3c, 3d, 3g, 3h and a third compound represented by the general formula (3j) may be used together with the hole transporting auxiliary layer.

In one embodiment of the present invention, the light emitting layer comprises a first compound represented by Formula 1-I and a second compound represented by Formula 2-XI, wherein the hole transporting layer, And a third compound represented by the following general formulas (3a) to (3e).

For example, at least one of the first compound represented by formula (1h), the second compound represented by formula (2-XI), and the third compound represented by formula (3a) and (3b) may be used together.

The hole transporting auxiliary layer 35 can be applied to the hole transporting layer in a thickness of 0.1 nm to 20.0 nm by a vapor deposition or inkjet process and can be applied to the hole transporting layer in the range of, for example, 0.2 nm to 10.0 nm, 0.3 nm to 5 nm, 0.3 nm to 2 nm, 1.0 nm thickness or the like.

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

Synthetic example  1: Synthesis of intermediate I-1

[Reaction Scheme 1]

After dissolving 100 g (326 mmol) of 2-bromotriphenylene (TCI) in 1 L of dimethylformamide (DMF) in a nitrogen atmosphere, bis (pinacolato) ) diboron, Aldrich), and 2.66 g (390 mmol) of (1,1'-bis (diphenylphosphine) ferrocene) dichloropalladium (II) (3.26 mmol) and potassium acetate (80 g, 815 mmol) were 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 . The thus-obtained residue was separated and purified by column chromatography to obtain 113 g (98%) of compound I-1.

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

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

Synthetic example  2: Synthesis of intermediate I-2

[Reaction Scheme 2]

32.7 g (107 mmol) of 2-bromotriphenylene (TCI) was dissolved in 0.3 L of tetrahydrofuran (THF) in a nitrogen atmosphere, and 3-chlorophenylboronic acid boronic acid (TCI) (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 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%

Synthetic example  3: Synthesis of Intermediate I-3

[Reaction Scheme 3]

Synthesis and purification were carried out in the same manner as in the synthesis of intermediate I-1 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%

Synthetic example  4: Synthesis of intermediate I-4

[Reaction Scheme 4]

Bromo-2-iodobenzene (Aldrich) was prepared by dissolving 100 g (282 mmol) of the above compound I-1 in 1 L of tetrahydrofuran (THF) in a nitrogen atmosphere, 3.29 g (2.82 mmol) of tetrakis (triphenylphosphine) palladium and 95.9 g (339 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 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%

Synthetic example  5: Synthesis of intermediate I-5

[Reaction Scheme 5]

Synthesis and purification were conducted in the same manner as in the synthesis of Intermediate I-1 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%

Synthetic example  6: Synthesis of Intermediate I-6

[Reaction Scheme 6]

Synthesis and purification were carried out in the same manner as in the synthesis of Intermediate I-4 to obtain 42.6 g (80%) of the compound I-6.

HRMS (70 eV, EI +): m / z calcd for C30H19Br: 458.0670, found: 458

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

Synthetic example  7: Synthesis of Intermediate I-7

[Reaction Scheme 7]

Synthesis and purification were conducted in the same manner as in the synthesis of Intermediate I-1 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%

Synthetic example  8: Synthesis of Compound A-33

[Reaction Scheme 8]

20 g (39.5 mmol) of the compound I-7 was dissolved in 0.2 L of tetrahydrofuran (THF) in a nitrogen atmosphere, 2-chloro-4,6-diphenyl-1,3,5-triazine 10.6 g (39.5 mmol) of tetrakis (triphenylphosphine) palladium (0.46 g, 0.4 mmol) in tetrahydrofuran Lt; / RTI > 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 column chromatography to obtain 17.9 g (74%) of the above compound A-33.

HRMS (70 eV, EI +): m / z calcd for C45H29N3: 611.2361, found: 611

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

Synthesis of second compound

Synthetic example  9: Synthesis of Compound B-10

[Reaction Scheme 9]

Step 1: Synthesis of Compound A

A suspension of 140.4 g (674 mmol, Aldrich) of 2-benzalacetophenone, 199.04 g (808.77 mmol) of pyridine salt compound and 415.6 g (5391 mmol) of ammonium acetate was suspended in methanol (1720 ml) and refluxed at 110 ° C for 2 hours . After the reaction, the product was precipitated in distilled water to form a solid, and the resulting solid was filtered to obtain 106 g (64%) of Compound A.

Step 2: Synthesis of Compound B

100 g (405.67 mmol) of the compound (A), 172.74 g (1217 mmol) of P ₂ O ₅ and 196.17 g (608.5 mmol, Aldrich) of Tetra n -butylammonium bromide (TBAB) were all added, suspended in chlorobenzene, And the mixture was refluxed and stirred at 140 DEG C for 14 hours. After the reaction, the solvent was removed, and the organic layer extracted with dichloromethane and distilled water was filtered to remove 150 ml of the obtained organic layer. Methanol was then poured to form a precipitate, and the resulting solid matter was filtered to obtain 89 g (71% Respectively.

Step 3: Synthesis of Compound J

10 g (34.83 mmol) of 9-phenyl-9H-carbazol-3-yl boronic acid, -TCI, 3-bromocarbazole, ), 14.74 g (104.49 mmol) of potassium carbonate and 0.80 g (0.7 mmmol) of tetrakis- (triphenylphosphine) palladium (0) were suspended in 140 ml of toluene and 50 ml of distilled water, Lt; / RTI > The mixture is then extracted with dichloromethane and distilled water, and the organic layer is subjected to silica gel filtration. After completion of the reaction, the reaction product is poured into methanol to obtain a solid product. The solid product is then dissolved in chlorobenzene, and activated carbon and anhydrous magnesium sulfate are added thereto and stirred. The solution was filtered and then recrystallized from chlorobenzene and methanol to obtain 22.6 g (68%) of Compound J.

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

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

Step 4: Synthesis of Compound B-10

22.42 g (54.88 mmol) of the compound represented by the compound J, 2-bromo-4,6-diphenylpyridine, 20.43 g (65.85 mmol) of compound B, After dissolving 7.92 g (82.32 mmol) of sodium in 400 ml of toluene, 1.65 g (1.65 mmol) of palladium dibenzylideneamine and 1.78 g (4.39 mmol) of tertiary butyl are added dropwise. After the completion of the reaction, methanol was poured into the reaction product to filter out the resulting solids, and the solids were again dissolved in chlorobenzene, and activated carbon and anhydrous magnesium sulfate were added thereto, followed by stirring, and the solution was filtered and then washed with chlorobenzene and methanol And recrystallized to obtain 28.10 g (80%) of the 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%

Synthetic example  10: Synthesis of Compound B-31

[Reaction Scheme 10]

10 g (34.83 mmol) of 9-phenyl-9H-carbazol-3-yl boronic acid, -TCI and 3-bromo-9-phenylcarbazole (0.7 mmol) of tetrakis- (triphenylphosphine) palladium (0) were dissolved in 140 ml of toluene (10 ml) and the mixture was stirred at room temperature for 3 hours. , And suspended in distilled water (50 ml), followed by reflux stirring 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 13.8 g (92%) of Compound B-31.

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

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

Synthetic example  11: Synthesis of compound B-43

[Reaction Scheme 11]

Step 1: Synthesis of compound K

20 g (90%) of Compound K was obtained in the same manner as in the synthesis of Compound B-10.

Step 2: Synthesis of Compound L

20 g (62.6 mmol) of the compound K was suspended in DMF (200 ml), 12.93 g (72.67 mmol, Aldrich) of N-bromosuccinimide (NBS) was added little by little and the mixture was refluxed with stirring for 12 hours. After adding distilled water and terminating the reaction, the organic layer obtained by extraction with dichloromethane 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 22.4 g (90%) of compound L.

Step 3: Synthesis of Compound N

In the same manner as in the synthesis of intermediate I-1, 22.5 g (90%) of compound N was obtained by purification.

Step 4: Synthesis of Compound B-43

Compound N, 10 g (34.83 mmol), 9- [1,1'-biphenyl-4-yl] -3-bromo-9H-carbazole (9- [ (0.7 mmol) of tetrakis- (triphenylphosphine) palladium (0) were added to a solution of toluene 140 (0.1 mmol) in toluene ml and distilled water (50 ml), and the mixture was refluxed and stirred for 12 hours. Subsequently, recrystallization from dichloromethane and n-hexane gave 18.7 g (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

Synthetic example  12: Synthesis of intermediate M-1

[Reaction Scheme 12]

The reaction was carried out in the same manner as in the synthesis of Intermediate I-4, except that the reaction solvent was toluene and refluxed for 12 hours and then purified to obtain 27 g (89%) of Intermediate M-1.

LC-Mass (theory: 322.00 g / mol, measured: M + = 322.09 g / mol, M + 2 = 324.04 g / mol)

Synthetic example  13: Synthesis of intermediate M-2

[Reaction Scheme 13]

Synthesis and purification were carried out in the same manner as in the synthesis of Intermediate M-1 to obtain 29 g (91%) of Intermediate M-2.

LC-Mass (theoretical value: 337.98 g / mol, measured: M + = 338.04 g / mol, M + 2 = 340.11 g / mol)

Synthetic example  14: Synthesis of intermediate M-3

[Reaction Scheme 14]

Synthesis and purification were conducted in the same manner as in the synthesis of Intermediate M-1 to obtain 23.9 g (91%) of Intermediate M-3.

LC-Mass (theoretical value: 278.05 g / mol, measured: M + = 278.12 g / mol, M + 2 = 280.13 g / mol)

Synthetic example  15: Synthesis of intermediate M-4

[Reaction Scheme 15]

Synthesis and purification were conducted in the same manner as in the synthesis of Intermediate M-1 to obtain 25.6 g (92%) of Intermediate M-4.

LC-Mass (294.03 g / mol, M + = 294.16 g / mol, M + 2 = 296.13 g / mol)

Synthetic example  16: Synthesis of intermediate M-5

[Reaction Scheme 16]

10 g (30.9 mmol) of intermediate M-1, 6.3 g (37.08 mmol, Aldrich) of 4-aminobiphenyl and 5.35 g (55.6 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 completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water. The organic layer was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (7: 3 by volume) to obtain 9.92 g (78%) of Intermediate M-5 as a target compound.

LC-Mass (theory: 411.16 g / mol, measured: M + = 411.21 g / mol)

Synthetic example  17: Synthesis of intermediate M-6

[Reaction Scheme 17]

6.3 g (37.08 mmol, Aldrich) and 5.35 g (55.6 mmol) of sodium di-t-butoxide were added to 9.1 g (30.9 mmol) of the intermediate M-4, 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, and the mixture was stirred under reflux for 4 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water. The organic layer was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (7: 3 by volume) to obtain 10.6 g (yield 80%) of intermediate compound M-6 as a white solid.

m / z calcd for C30H21NS: 427.14, found: 427.19

Synthetic example  18: Synthesis of intermediate M-7

[Reaction Scheme 18]

9.1 g (30.9 mmol) of the intermediate M-4, 5.3 g (37.08 mmol, Aldrich) of 1-aminonaphthalene and 5.35 g (55.6 mmol) of sodium di-t-butoxide were added and dissolved in 155 ml of toluene. 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 completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water. The organic layer was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (7: 3 by volume) to give 10 g (81% yield) of intermediate M-7 as a white solid.

m / z calcd for C28H19NS: 401.12, found: 401.15

Synthetic example  19: Synthesis of intermediate M-8

[Reaction Scheme 19]

31.9 g (64.7 mmol) of the intermediate M-2, 1.74 g (29.4 mmol, Aldrich) of acetamide and 17.3 g (117.6 mmol) of potassium carbonate were added and dissolved in 130 ml of xylene. 1.12 g (5.88 mmol) of copper (I) iodide and 1.04 g (11.8 mmol) of N, N-dimethylethylenediamine were added in this order and the mixture was refluxed under nitrogen atmosphere for 48 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 with n-hexane / ethyl acetate (7: 3 by volume) to obtain 14 g (yield 93%) of the target compound M-8.

m / z calcd for C30H21NO: 575.14, found: 575.31

Synthetic example  20: Synthesis of intermediate M-9

[Reaction Scheme 20]

13 g (25.2 mmol) of Intermediate M-8 and 4.2 g (75.6 mmol) of potassium hydroxide were added to a round bottom flask, and 80 ml of tetrahydrofuran and 80 ml of ethanol were added to dissolve. And the mixture was refluxed under nitrogen atmosphere for 12 hours. After completion of the reaction, the reaction mixture was concentrated under reduced pressure, and then extracted with dichloromethane and distilled water. The organic layer was dried with magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (7: 3 by volume) to give 12.1 g (yield 90%) of the target compound M-9.

m / z calcd for C36H23NS2: 533.13, found: 533.26

Synthetic example  21: Synthesis of intermediate M-10

[Reaction Scheme 21]

25 g (92.47 mmol, Aldrich) of 1,3-dibromo-5-chlorobenzene, 31.3 g (184.9 mmol, TCI) of diphenylamine and 26.7 g (277.41 mmol) of sodium di- And 463 ml of toluene was added to dissolve it. 0.266 g (0.462 mmol) of Pd (dba) 2 and 0.187 g (0.924 mmol) of tri-tertiary-butylphosphine were added in this order, and the mixture was stirred under reflux for 4 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water. The organic layer was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (9: 1 by volume) to give 34.7 g (84% yield) of intermediate M-10 as a white solid.

m / z calcd for C30H23ClN2: 446.15, found: 446.23

Synthetic example  22: Synthesis of intermediate M-11

[Reaction Scheme 22]

A round bottom flask was charged with 25 g (92.47 mmol, Aldrich) of 1,3-dibromo-5-chlorobenzene, 33.9 g (184.9 mmol, Aldrich) of 3-methyl- 277.41 mmol) was added and dissolved in 463 ml of toluene. 0.266 g (0.462 mmol) of Pd (dba) 2 and 0.187 g (0.924 mmol) of tri-tertiary-butylphosphine were added in this order, and the mixture was stirred under reflux for 4 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water. The organic layer was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (9: 1 by volume) to obtain 37.3 g (yield: 85%) of intermediate compound M-11 as a white solid.

m / z calcd for C32H27ClN2: 474.19, found: 474.28

Synthetic example  23: Synthesis of intermediate M-12

[Reaction Scheme 23]

A round bottom flask was charged with 25 g (92.47 mmol, Aldrich) of 1,3-dibromo-5-chlorobenzene and 45.4 g (184.9 mmol, TCI) of biphenyl- (277.41 mmol) were added and dissolved in 463 ml of toluene. 0.266 g (0.462 mmol) of Pd (dba) 2 and 0.187 g (0.924 mmol) of tri-tertiary-butylphosphine were added in this order, and the mixture was stirred under reflux for 4 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water. The organic layer was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (8: 2 by volume) to give 44.9 g (81% yield) of intermediate M-12 as a white solid.

m / z calcd for C42H31ClN2: 598.22, found: 598.37

Synthetic example  24: Synthesis of intermediate M-13

[Reaction Scheme 24]

A round bottom flask was charged with 9.5 g (36.1 mmol, Shanghai Shaoyuan Product list) of 4-bromodibenzothiophene, 7.33 g (43.32 mmol, Aldrich) of 4- aminobiphenyl and 5.2 g (54.15 mmol) And 250 ml of toluene was added to dissolve the solution. 0.21 g (0.36 mmol) of Pd (dba) 2 and 0.18 g (0.72 mmol) of tri-tertiary-butylphosphine were added in this order, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water. The organic layer was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (7: 3 by volume) to give 10.3 g (81% yield) of intermediate M-13 as a white solid.

m / z calcd for C24H17NS: 351.11, found: 351.38

Synthetic example  25: Synthesis of intermediate M-14

[Reaction Scheme 25]

(92.47 mmol, Aldrich), 30.9 g (184.9 mmol, Aldrich) of carbazole and 26.7 g (277.41 mmol) of sodium di-t-butoxide were added to a round bottom flask, Were added to dissolve. 0.266 g (0.462 mmol) of Pd (dba) 2 and 0.187 g (0.924 mmol) of tri-tertiary-butylphosphine were added in this order, and the mixture was stirred under reflux for 4 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water. The organic layer was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (8: 2 by volume) to give 33.2 g (81% yield) of intermediate M-14 as a white solid.

m / z calcd for C30H19ClN2: 442.12, found: 442.36

Synthetic example  26: Synthesis of intermediate M-15

[Reaction Scheme 26]

(92.47 mmol, Aldrich), 15.5 g (92.47 mmol, Aldrich) of carbazole and 13.4 g (138.7 mmol) of sodium di-t-butoxide were placed in a round bottom flask, and 463 ml And dissolved. 0.133 g (0.231 mmol) of Pd (dba) 2 and 0.094 g (0.462 mmol) of tri-tertiary-butylphosphine were added in this order, and the mixture was stirred under reflux for 4 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water. The organic layer was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (9: 1 by volume) to give 24.0 g (83% yield) of intermediate M-15 as a white solid.

m / z calcd for C18H11Cl2N: 311.03, found: 311.17

Synthetic example  27: Synthesis of intermediate M-16

[Reaction Scheme 27]

28.9 g (92.47 mmol) of M-15, 22.7 g (92.47 mmol, TCI) of biphenyl-4-yl-phenylamine and 13.4 g (138.7 mmol) of sodium di-t-butoxide were added to a round bottom flask, and 463 ml . 0.133 g (0.231 mmol) of Pd (dba) _{2 and} 0.094 g (0.462 mmol) of tri-tertiary-butylphosphine were added in this order, 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 and distilled water. The organic layer was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (8: 2 by volume) to obtain 38.1 g (yield 79%) of intermediate compound M-16 as a white solid.

m / z calcd for C36H25ClN2: 520.17, found: 520.36

Synthetic example  28: Synthesis of intermediate M-17

[Reaction Scheme 28]

10.5 g (30.9 mmol) of intermediate M-2, 6.3 g (37.08 mmol, Aldrich) of 4-aminobiphenyl and 5.35 g (55.6 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, and the mixture was stirred under reflux for 4 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water. The organic layer was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (7: 3 by volume) to obtain 9.91 g (yield 75%) of intermediate compound M-17 as a white solid.

m / z calcd for C30H21NS: 427.14, found: 427.29

Synthetic example  29: Synthesis of intermediate M-18

[Reaction Scheme 29]

A round bottom flask was charged with 7.6 g (30.9 mmol, Aldrich) of intermediate 2-bromodibenzofurane, 6.3 g (37.08 mmol, Aldrich) of 4- aminobiphenyl and 5.35 g (55.6 mmol) of sodium di- And dissolved. 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 stirred under reflux for 4 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water. The organic layer was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (7: 3 by volume) to obtain 8.1 g (yield 78%) of intermediate compound M-18 as a white solid.

m / z calcd for C24H17NO: 335.13, found: 335.42

Synthetic example  30: Synthesis of intermediate M-19

[Reaction Scheme 30]

A round bottom flask was charged with 8.1 g (30.9 mmol, Aldrich) of intermediate 2-bromodibenzothiophene, 5.3 g (37.08 mmol, Aldrich) of 2-aminonaphthalene and 5.35 g (55.6 mmol) of sodium di- And dissolved. 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 stirred under reflux for 4 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water. The organic layer was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (7: 3 by volume) to obtain 7.9 g (yield 79%) of intermediate compound M-19 as a white solid.

m / z calcd for C22H15NS: 325.09, found: 325.33

Synthetic example  31: Synthesis of intermediate M-20

[Reaction Scheme 31]

8.6 g (30.9 mmol) of Intermediate M-3, 5.3 g (37.08 mmol, Aldrich) of 1-aminonaphthalene and 5.35 g (55.6 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 completion of the reaction, the reaction mixture was extracted with ethyl acetate and distilled water. The organic layer was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (7: 3 by volume) to obtain 9.5 g (yield 80%) of intermediate compound M-20 as a white solid.

m / z calcd for C28H19NO: 385.15, found: 385.27

General Formulas 1 to 3: Specific Synthesis of Third Compound

The compounds E-1 to E-18, F-1 to F-292, and G-1 to G-48 can be produced according to the synthesis methods of the following general formulas 1 to 3.

General formula 1: Synthesis of compounds E-1 to E-18

[Formula 1-1]

[Formula 1-2]

General Formula 2: Synthesis of Compounds F-1 to F-292

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

Synthesis of Compound 3: Compounds G-1 to G-48

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

Representative synthesis methods of the specific compounds according to one embodiment of the present invention, and yields and LC-Mass values therefor are shown in Table 1 below.

Synthetic method The final synthetic reaction intermediate Final product Measures
MS [M +] < Halogen compound Arylamine Compound structure number In general formula
2-1

F-38 989.42 In general formula
2-2

F-251 1125.51 In general formula
2-3

F-209 1063.49 In general formula
2-4

F-203 1037.58 In general formula
3-1

G-8 945.62 In general formula
3-2

G-17 909.63 In general formula
3-3

　

　 G-40 893.57

Synthetic example  32: Synthesis of Compound E-16

[Reaction Scheme 32]

A round bottom flask was charged with 9.5 g (30.18 mmol, Aldrich) of 1,3,5-tribromobenzene, 22.21 g (90.53 mmol, TCI) of biphenyl-4-yl- 45.27 mmol) was added, and 300 ml of toluene was added to dissolve. Thereto, 0.174 g (0.302 mmol) of Pd (dba) 2 and 0.146 g (0.604 mmol) of tri-tertiary-butylphosphine were added in this order, and the mixture was refluxed under nitrogen atmosphere for 12 hours. After completion of the reaction, the reaction mixture was extracted with toluene and distilled water, and the organic layer was dried with magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (8: 2 by volume) to give 21.5 g (yield 90%) of the target compound E-16 as a white solid.

m / z calcd for C60H45N3: 807.36, found: 807.41

Synthetic example  33: Synthesis of Compound E-7

[Reaction Scheme 33]

10 g (22.37 mmol) of intermediate M-10, 7.2 g (22.37 mmol, TCI) of bisbiphenyl-4-ylamine and 3.2 g (33.56 mmol) of sodium di-t-butoxide were added to a round bottom flask and 250 ml of toluene was added . 0.129 g (0.224 mmol) of Pd (dba) 2 and 0.091 g (0.448 mmol) of tri-tertiary-butylphosphine were added in this order, 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 toluene and distilled water, and the organic layer was dried with magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (8: 2 by volume) to give 14.6 g (yield 89%) of the target compound E-7 as a white solid.

m / z calcd for C54 H41 N3: 731.33, found: 731.38

Synthetic example  34: Synthesis of Compound F-34

[Reaction Scheme 34]

10 g (22.37 mmol) of Intermediate M-10, 9.2 g (22.37 mmol) of Intermediate M-5 and 3.2 g (33.56 mmol) of sodium di-t-butoxide were added to a round bottom flask and dissolved in 250 ml of toluene. 0.129 g (0.224 mmol) of Pd (dba) 2 and 0.091 g (0.448 mmol) of tri-tertiary-butylphosphine were added in this order, 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 toluene and distilled water, and the organic layer was dried with magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (8: 2 by volume) to give 16.9 g (yield 92%) of the target compound F-34 as a white solid.

m / z calcd for C60H43N3O: 821.34, found: 821.46

Synthetic example  35: Synthesis of Compound F-104

[Reaction Scheme 35]

13.4 g (22.37 mmol) of intermediate M-12, 9.6 g (22.37 mmol) of intermediate M-6 and 3.2 g (33.56 mmol) of sodium di-t-butoxide were added to a round bottom flask and 250 ml of toluene was added to dissolve. 0.129 g (0.224 mmol) of Pd (dba) 2 and 0.091 g (0.448 mmol) of tri-tertiary-butylphosphine were added in this order, 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 toluene and distilled water, and the organic layer was dried with magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (8: 2 by volume) to give 20.6 g (yield 93%) of the target compound F-104 as a white solid.

m / z calcd for C72H51N3S: 989.38, found: 989.45

Synthetic example  36: Synthesis of Compound F-136

10.3 g (23.04 mmol) of intermediate M-10, 8.91 g (25.35 mmol) of intermediate M-13 and 3.32 g (34.57 mmol) of sodium di-t-butoxide were added to a round bottom flask and 250 ml of toluene was added to dissolve. After 0.13 g (0.23 mmol) of Pd (dba) 2 and 0.11 g (0.461 mmol) of tri-tertiary-butylphosphine were added in this order, the mixture was stirred under reflux for 12 hours under a nitrogen atmosphere. After completion of the reaction, the reaction mixture was extracted with toluene and distilled water, and the organic layer was dried with magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (7: 3 by volume) to give 19.8 g (90% yield) of the target compound F-136 as a white solid.

Synthetic example  37: Synthesis of compound F-201

10.6 g (22.37 mmol) of intermediate M-11, 11.9 g (22.37 mmol) of intermediate M-9 and 3.2 g (33.56 mmol) of sodium di-t-butoxide were added to a round bottom flask and 250 ml of toluene was added to dissolve. 0.129 g (0.224 mmol) of Pd (dba) 2 and 0.091 g (0.448 mmol) of tri-tertiary-butylphosphine were added in this order, 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 toluene and distilled water, and the organic layer was dried with magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (8: 2 by volume) to give 19.8 g (yield 91%) of the target compound F-201 as a white solid.

m / z calcd for C68H49N3S2: 971.34, found: 971.51

Synthetic example  38: Synthesis of Compound F-88

10 g (22.37 mmol) of intermediate M-10, 9.0 g (22.37 mmol) of intermediate M-7 and 3.2 g (33.56 mmol) of sodium di-t-butoxide were added to a round bottom flask and 250 ml of toluene was added to dissolve. 0.129 g (0.224 mmol) of Pd (dba) 2 and 0.091 g (0.448 mmol) of tri-tertiary-butylphosphine were added in this order, 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 toluene and distilled water, and the organic layer was dried with magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (8: 2 by volume) to give 16.5 g (yield 91%) of the target compound F-88 as a white solid.

m / z calcd for C58H41N3S: 811.30, found: 811.61

Synthetic example  39: Synthesis of compound G-25

11.7 g (22.37 mmol) of intermediate M-16, 9.2 g (22.37 mmol) of intermediate M-5 and 3.2 g (33.56 mmol) of sodium di-t-butoxide were added to a round bottom flask and dissolved in 250 ml of toluene. 0.129 g (0.224 mmol) of Pd (dba) 2 and 0.091 g (0.448 mmol) of tri-tertiary-butylphosphine were added in this order, 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 toluene and distilled water, and the organic layer was dried with magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (8: 2 by volume) to give 18 g (90% yield) of the target compound G-25 as a white solid.

m / z calcd for C58H41N3S: 895.36, found: 895.48

Synthetic example  40: Synthesis of Compound G-30

9.9 g (22.37 mmol) of intermediate M-14, 9.6 g (22.37 mmol) of intermediate M-17 and 3.2 g (33.56 mmol) of sodium di-t-butoxide were added to a round bottom flask and 250 ml of toluene was added to dissolve. 0.129 g (0.224 mmol) of Pd (dba) 2 and 0.091 g (0.448 mmol) of tri-tertiary-butylphosphine were added in this order, 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 toluene and distilled water, and the organic layer was dried with magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (8: 2 by volume) to give 17.5 g (yield 94%) of the target compound G-30 as a white solid.

m / z calcd for C60H39N3S: 833.29, found: 833.42

Fabrication of organic light emitting device

Example  One

The glass substrate coated with ITO (Indium tin oxide) thin film with thickness of 1500 Å 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. A hole transporting auxiliary layer of 50 Å in thickness was formed on the hole transporting layer by vacuum evaporation of the compound E-16 obtained in Synthesis Example 32. Subsequently, Compound A-33 obtained in Synthesis Example 8 and Compound B-43 obtained in Synthesis Example 11 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 7 wt%, and a 400 Å thick light emitting layer was formed by vacuum deposition. Compound A-33 and Compound B-43 were used in a 4: 6 weight ratio.

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,

EML [A-33: B-43: D = X: X: 7%] / EML (700 Å) / B (50 Å) / C (720 Å) / hole transporting auxiliary layer 400 Å / E: Liq 300 Å / Liq 15 Å / Al 1200 Å.

(X = weight ratio)

Example  2

An organic light emitting device was fabricated in the same manner as in Example 1, except that Compound E-7 obtained in Synthesis Example 33 was used instead of Compound E-16 in the hole transporting assisting layer.

Example  3

An organic light emitting device was fabricated in the same manner as in Example 1, except that the compound F-136 obtained in Synthesis Example 36 was used instead of the compound E-16 in the hole transporting auxiliary layer.

Comparative Example  One

An organic light emitting device was fabricated in the same manner as in Example 1, except that a hole transporting auxiliary layer was not formed, and a compound C was deposited to a thickness of 1020 A as a hole transporting layer.

evaluation

Emitting efficiency and roll-off characteristics of the organic luminescent devices according to Examples 1 to 3 and Comparative Example 1 were evaluated.

The specific measurement method is as follows, and the results are shown in [Table 2].

(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% in the characteristic values of (3) above (Max value - Numerical value at 6000 cd / m 2 / Max value).

Hole transporting auxiliary layer The light- Luminous efficiency
(cd / A) Roll-off
(%) The first compound The second compound First compound: second compound
(wt / wt) Example 1 E-16 A-33 B-43 4: 6 55.1 9.7 Example 2 E-7 A-33 B-43 4: 6 58.6 9.3 Example 3 F-136 A-33 B-43 4: 6 57.7 8.4 Comparative Example 1 - A-33 B-43 4: 6 48.1 14.9

Referring to Table 2, it can be seen that the organic light emitting devices according to Examples 1 to 3 have significantly improved luminous efficiency and roll-off characteristics at the same time as compared with the organic light emitting device according to Comparative Example 1. [

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 35: Electron transport layer
36: electron injection layer 37: hole injection layer

Claims (16)

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 the following general formula (3): < EMI ID =
[Chemical Formula 1]

In Formula 1,
At least one of Z ₁ to Z ₃ is N, the remaining Z is all C,
R ¹ to R ¹⁰ 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,
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 and Y ² are each independently a single bond or a substituted or unsubstituted C6 to C30 arylene group,
Ar ^1a and Ar ^1b are a substituted or unsubstituted C6 to C30 aryl group,
R ¹¹ to R ¹⁶ 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 group, or combinations thereof ,
(3)

In Formula 3,
L ² to L ⁷ are each independently a single bond or a substituted or unsubstituted C6 to C30 arylene group,
n4 to n9 each independently represents an integer of 0 to 3,
R ¹⁷ to R ²² each independently represent hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 To C30 heterocyclic groups, or combinations thereof,
R ¹⁷ to R ²² are each independently present, or R ¹⁷ and R ¹⁸ , R ¹⁹ and R ²⁰ , and R ²¹ and R ²² are connected to each other to form a fused ring,
"Substitution" in the above Chemical Formulas 1 to 3 means that at least one hydrogen is substituted with one or more groups selected from the group consisting of deuterium, a halogen group, a hydroxyl group, an amino group, an amine group, a nitro group, a silyl group, a C1 to C30 alkyl 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 C20 alkoxy group, a C1 to C10 trifluoroalkyl group, or a cyano group. The method of claim 1,
Wherein the first compound is represented by the following formula (I-1) or (I-II): < EMI ID =
[Chemical Formula 1-I]

[Chemical Formula 1-II]

In the above general formulas (I-1) and (II-II)
At least one of Z ₁ to Z ₃ is N, the remaining Z is all C,
R ¹ to R ¹⁰ 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,
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 term "substituted" as used herein means that at least one hydrogen is substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a hydroxy group, an amino group, an amine group, a nitro group, a silyl group, a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, An aryl group, a C2 to C30 heteroaryl group, a C1 to C20 alkoxy group, a C1 to C10 trifluoroalkyl group, or a cyano group. The method of claim 1,
Wherein the first compound is at least one of the compounds listed in the following Group 2:
[Group 2]

The method of claim 1,
Wherein the second compound is represented by the following 2-XI:
[Chemical Formula 2-XI]

In the above general formula (2-XI)
Y ¹ and Y ² are each independently a single bond or a substituted or unsubstituted C6 to C30 arylene group,
R ¹¹ to R ¹⁶ 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 group, or combinations thereof ,
Wherein HT1 and HT2 are each independently selected from substituted or unsubstituted groups listed in the following Group 4:
[Group 4]

,
The term "substituted" as used herein means that at least one hydrogen is replaced by a substituent selected from the group consisting of deuterium, a halogen group, a hydroxy group, an amino group, an amine group, a nitro group, a silyl group, a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, Group, a C2 to C30 heteroaryl group, a C1 to C20 alkoxy group, a C1 to C10 trifluoroalkyl group or a cyano group,
In the above group 4, * is a connection point. The method according to claim 1,
Wherein the second compound is selected from the compounds listed in the following Group 5:
[Group 5]

. The method of claim 1,
The light-
A first compound represented by the following formula 1-I; And
An organic optoelectronic device comprising a second compound represented by the following formula (2-XI):
[Chemical Formula 1-I]

In the above formula (I-I)
At least one of Z ₁ to Z ₃ is N, the remaining Z is all C,
R ¹ to R ¹⁰ 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,
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,
[Chemical Formula 2-XI]

In the above general formula (2-XI)
Y ¹ and Y ² are each independently a single bond or a substituted or unsubstituted C6 to C30 arylene group,
R ¹¹ to R ¹⁶ 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 group, or combinations thereof ,
Each of HT1 and HT2 is independently selected from a substituted or unsubstituted group listed in the following Group 4,
[Group 4]

,
In the above group 4, * is a connection point,
The term "substituted" as used herein means that at least one hydrogen is replaced by a substituent selected from the group consisting of deuterium, a halogen group, a hydroxy group, an amino group, an amine group, a nitro group, a silyl group, a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, Group, a C2 to C30 heteroaryl group, a C1 to C20 alkoxy group, a C1 to C10 trifluoroalkyl group, or a cyano group. The method of claim 1,
Wherein the third compound is represented by at least one of the following general formulas (III-1) to (III-III):
[Formula 3-I] [Formula 3-II]

[Formula 3-III]

In the above Formulas 3-1 to 3-1,
L ⁴ to L ⁷ are each independently a single bond or a substituted or unsubstituted C6 to C30 arylene group,
n4 to n9 each independently represents an integer of 0 to 3,
R ¹⁷ to R ²² each independently represent hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 To C30 heteroaryl groups, or combinations thereof,
The term "substituted" as used herein means that at least one hydrogen is replaced by a substituent selected from the group consisting of deuterium, a halogen group, a hydroxy group, an amino group, an amine group, a nitro group, a silyl group, a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, Group, a C2 to C30 heteroaryl group, a C1 to C20 alkoxy group, a C1 to C10 trifluoroalkyl group, or a cyano group. 8. The method of claim 7,
Wherein the third compound is represented by at least one of the following Chemical Formulas 3a to 3k:
[Formula 3]

[Chemical Formula 3c]

[Formula 3e] [Formula 3f]

[Chemical Formula 3g] [Chemical Formula 3h]

[Formula 3i] [Formula 3j]

[Chemical Formula 3k]

In the above formulas (3a) to (3k)
X ¹ to X ³ are each independently O, S, or CR ^b R ^c ,
R ¹⁷ to R ²⁴ , R ^b and R ^c are each independently hydrogen, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group, a substituted or unsubstituted C 6 to C 30 aryl group , A substituted or unsubstituted C2 to C30 heteroaryl group, or a combination thereof,
Ar ² to Ar ⁷ each independently represent a substituted or unsubstituted C6 to C30 aryl group,
L ⁴ to L ⁷ each independently represent a substituted or unsubstituted C6 to C30 arylene group,
n4 to n9 each independently represents an integer of 0 to 3,
The term "substituted" as used herein means that at least one hydrogen is replaced by a substituent selected from the group consisting of deuterium, a halogen group, a hydroxy group, an amino group, an amine group, a nitro group, a silyl group, a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, Group, a C2 to C30 heteroaryl group, a C1 to C20 alkoxy group, a C1 to C10 trifluoroalkyl group, or a cyano group. The method of claim 1,
R ¹⁷ to R ²² in Formula 3 are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted naphthyl group, A substituted or unsubstituted p-terphenyl group, a substituted or unsubstituted m-terphenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group , A substituted or unsubstituted benzofuranyl group, a substituted or unsubstituted benzothiophenyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted benzothiophenyl group, A substituted dibenzothiophenyl group, or a combination thereof. The method of claim 1,
L ² to L ⁷ in Formula 3 are each independently a single bond or a substituted or unsubstituted group listed in the following Group 6:
[Group 6]

In the above group 6,
* Is a connection point,
The term "substituted" as used herein means that at least one hydrogen is replaced by a substituent selected from the group consisting of deuterium, a halogen group, a hydroxy group, an amino group, an amine group, a nitro group, a silyl group, a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, Group, a C2 to C30 heteroaryl group, a C1 to C20 alkoxy group, a C1 to C10 trifluoroalkyl group, or a cyano group. The method of claim 1,
F-201, F-203, F-209, F-251, and F- G-8, G-17, G-25, G-30 and G-40.
[E-7] [E-16]

[F-34] [F-38] [F-88]

[F-104] [F-136] [F-201]

[F-203] [F-209] [F-251]

[G-8] [G-17] [G-25]

[G-30] [G-40]

. The method of claim 1,
Wherein the light emitting layer comprises a first compound represented by Formula 1-I and a second compound represented by Formula 2-XI,
Wherein the hole transporting auxiliary layer comprises a third compound represented by the following Formula 3-1:
[Chemical Formula 1-I]

In the above formula (I-I)
At least one of Z ₁ to Z ₃ is N, the remaining Z is all C,
R ¹ to R ¹⁰ 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,
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,
[Chemical Formula 2-XI]

In the above general formula (2-XI)
Y ¹ and Y ² are each independently a single bond or a substituted or unsubstituted C6 to C30 arylene group,
R ¹¹ to R ¹⁶ 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 group, or combinations thereof ,
Each of HT1 and HT2 is independently selected from a substituted or unsubstituted group listed in the following Group 4,
[Group 4]

,
In the above group 4, * is a connection point,
[Formula 3-I]

In the above general formula (III)
n4 to n9 each independently represents an integer of 0 to 3,
R ¹⁷ to R ²² each independently represent hydrogen, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C3 to C20 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 To C30 heteroaryl groups, or combinations thereof,
The term "substituted" as used herein means that at least one hydrogen is replaced by a substituent selected from the group consisting of deuterium, a halogen group, a hydroxy group, an amino group, an amine group, a nitro group, a silyl group, a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, Group, a C2 to C30 heteroaryl group, a C1 to C20 alkoxy group, a C1 to C10 trifluoroalkyl group, or a cyano group. The method of claim 12,
Wherein the light emitting layer comprises a first compound represented by Formula 1-I and a second compound represented by Formula 2-XI,
Wherein the hole transporting auxiliary layer of Formula 3-I comprises at least one of the following compounds represented by the following Formulas 3a to 3e:
[Formula 3]

[Chemical Formula 3c]

[Formula 3e]

In the above formulas (3a) to (3e)
X ¹ to X ³ are each independently O, S, or CR ^b R ^c ,
R ¹⁷ to R ¹⁹ , R ²¹ to R ²⁴ , R ^b and R ^c are each independently hydrogen, a substituted or unsubstituted C 1 to C 20 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group, A substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group,
Ar ² to Ar ⁷ each independently represent a substituted or unsubstituted C6 to C30 aryl group,
n4 to n9 each independently represents an integer of 0 to 3,
The term "substituted" as used herein means that at least one hydrogen is replaced by a substituent selected from the group consisting of deuterium, a halogen group, a hydroxy group, an amino group, an amine group, a nitro group, a silyl group, a C1 to C30 alkyl group, a C3 to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group, Group, a C2 to C30 heteroaryl group, a C1 to C20 alkoxy group, a C1 to C10 trifluoroalkyl group, or a cyano group. 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 further comprises a phosphorescent dopant. A display device comprising the organic optoelectronic device according to any one of claims 1 to 15.

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