KR101825541B1 - Organic optoelectric device and display device - Google Patents

Abstract

A hole transporting layer positioned between the anode and the light emitting layer, a hole transporting auxiliary layer positioned between the hole transporting layer and the light emitting layer, a hole transporting layer disposed between the cathode and the light emitting layer, An electron transporting layer disposed between the electron transporting layer and the light emitting layer, wherein the electron transporting layer comprises at least one first compound represented by the following formula Wherein 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 will be.
(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.

Of these, organic light emitting diodes (OLEDs) have attracted a great deal of attention in recent years 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 one 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; a hole transporting auxiliary layer disposed between the hole transporting layer and the light emitting layer; An electron transporting layer positioned between the cathode and the light emitting layer, and an electron transporting layer positioned between the electron transporting layer and the light emitting layer, wherein the electron transporting layer comprises at least one first And at least one second compound represented by the following general formula (2), wherein the hole transporting auxiliary layer comprises at least one third compound represented by the following general formula (3).

[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,

X < ¹ > is O or S,

R ¹⁷ and R ¹⁸ 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, 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 groups, substituted or unsubstituted C6 to C30 arylthio groups, substituted or unsubstituted C2 to C30 heteroaryl groups, substituted or unsubstituted C2 to C30 amino groups, substituted or unsubstituted C3 to C30 silyl groups , A cyano group, a nitro group, a hydroxyl group or a carboxyl group, or a combination thereof,

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

L ² to L ⁴ 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 n6 are each independently an integer of 0 to 3,

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The anode 10 can be made of a conductor having a high work function to facilitate, for example, hole injection, and can be made of, for example, a metal, a metal oxide, and / or a conductive polymer. The anode 10 is made of a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold, or an alloy thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); A combination of ZnO and Al or a metal and an oxide such as 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.

An electron transporting layer 34 and an electron transporting layer 35 disposed between the electron transporting layer 34 and the light emitting layer 32. The electron transporting layer 34 is formed of a metal such as aluminum,

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.

Examples of the known host include Alq3, CBP (4,4'-N, N'-dicarbazole-biphenyl), PVK (poly (n-vinylcarbazole) (N, N-phenylbenzimidazole-2-yl) benzene), anthracene (ADN), TCTA, TPBI (1,3,5-tris ), TBADN (3-tert-butyl-9,10-di (naphth-2-yl) anthracene), mCP and OXD-7.

The dopant may be at least one of a fluorescent dopant and a phosphorescent dopant. The phosphorescent dopant may be an organic metal complex including Ir, Pt, Os, Re, Ti, Zr, Hf or a combination of two or more of them, but is not limited thereto.

Examples of known blue dopants include F ₂ Irpic, (F ₂ ppy) ₂ Ir (tmd), Ir (dfppz) ₃ , ter-fluorene, 4,4'- Reel) biphenyl (DPAVBi), 2,5,8,11- tetra - tert - butyl perylene (TBPe), DPVBi, however, and the like pyrene derivatives (KR0525408, LG Electronics Inc.), and the like.

            DPAVBi TBPe

Examples of known red dopants include, but are not limited to, PtOEP, Ir (piq) ₃ , BtpIr, and the like.

Examples of a known green _{dopant, Ir (ppy) 3 (ppy} = phenylpyridine), and the like, but _{Ir (ppy) 2 (acac)} , Ir (mpyp) 3, but is not limited to such.

When the light emitting layer includes a host and a dopant, the content of the dopant may be generally selected from the range of about 0.01 to about 15 wt% per 100 wt% of the light emitting layer, but is not limited thereto.

The thickness of the light emitting layer is about 200 ANGSTROM to about 700 ANGSTROM.

The electron transporting auxiliary layer 35 includes a first compound having a characteristic in which the electron characteristic is relatively strong and a second compound having the characteristic in which the hole characteristic is relatively strong.

The first compound is a compound having a relatively strong electronic property and can 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 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 includes a heteroaryl group containing a triphenylene group and at least one nitrogen atom. Since the first compound includes a ring containing at least one nitrogen, the structure can receive electrons when the electric field is applied, and the electron injection amount can be increased, thereby lowering the driving voltage of the organic optoelectronic device to which the first compound is applied And can also improve efficiency.

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 ¹ ) 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.

The L ¹ may be, for example, a single bond, or 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 a relatively strong hole characteristic and can be included in the electron transporting auxiliary layer together with the first compound to adjust the electron injection amount of the first compound, It is possible to prevent the accumulation of holes at the interface of the layer to improve the stability of the device. Therefore, the luminous efficiency and lifetime characteristics of the organic optoelectronic device can be remarkably improved.

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)

Z are each independently N or CR ^k,

A1 and A2, and ^Rk 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.

The electron transport assisting layer according to an embodiment of the present invention may simultaneously include a first compound having a strong electron characteristic and a second compound having a strong hole characteristic.

The efficiency and lifetime of the device can be improved by using at least one first compound represented by Formula 1 and at least one second compound represented by Formula 2 together.

Specifically, at least one of the first compound represented by the formula (1-I) or (1-II) and the second compound represented by the formula (2-1) to (2-XI) may be used together.

More specifically, at least one of the first compounds represented by the formulas (1c) to (1t) may be used together with at least one of the second compounds represented by the formulas (II-IX) to (II-XI).

More specifically, at least one of the first compounds represented by the formulas (1c), (1d), (1g) and (1h) can be used together with at least one of the second compounds represented by the formulas (II-IX) to (II-XI).

For example, the first compound represented by the formula (1h) and the second compound represented by the formula (2-XI) can be used together.

In the electron transporting auxiliary layer 35, the first compound and the second compound may be contained at a weight ratio of, for example, about 1:99 to 99: 1. Specifically, it can be contained at a weight ratio of 10:90 to 90:10, 20:80 to 80:20, 30:70 to 70:30, and 40:60 to 60:40, most specifically, 50:50.

The electron injecting ability can be controlled according to the ratio of the two compounds by being included in the above range, so that electrons can be prevented from accumulating at the interface of the emitting layer by balancing with the electron transporting ability of the emitting layer.

Further, the holes and / or excitons transferred from the light emitting layer are converted into excitons having an energy lower than the energy of the excitons of the light emitting layer due to the electron transporting auxiliary layer 35, so that the influence of the excitons of the holes and / or the light emitting layer on the electron transporting layer 34 Can be minimized.

The hole transporting auxiliary layer 33 includes a third compound having a good hole transporting property and reduces the HOMO energy level difference between the hole transporting layer 31 and the light emitting layer 32 to control the injection characteristics of the hole, It is possible to reduce the accumulation of holes at the interface between the light emitting layer 33 and the light emitting layer 32, thereby reducing the quenching phenomenon in which the excitons by the polaron disappear at the interface. As a result, the deterioration phenomenon of the device is reduced and the device 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,

X < ¹ > is O or S,

R ¹⁷ and R ¹⁸ 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, 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 groups, substituted or unsubstituted C6 to C30 arylthio groups, substituted or unsubstituted C2 to C30 heteroaryl groups, substituted or unsubstituted C2 to C30 amino groups, substituted or unsubstituted C3 to C30 silyl groups , A cyano group, a nitro group, a hydroxyl group or a carboxyl group, or a combination thereof,

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

L ² to L ⁴ 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 n6 are each independently an integer of 0 to 3,

The third compound may be represented by, for example, the following Formula 3-I or Formula 3-II according to the bonding position of the amine substituent.

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

X ¹ , R ¹⁷ , R ¹⁸ , Ar ² , Ar ³ , L ² to L ⁴ , and n ⁴ to n 6 are as described above.

The third compound may be at least one of the following general formulas (III-III) to (III-IX).

[Chemical Formula 3-III] [Chemical Formula 3-IV] Chemical Formula 3-V]

[Formula 3-VI] [Chemical Formula 3-VII] [Chemical Formula 3-VIII]

[Chemical Formula 3-IX]

X ¹ , R ¹⁷ and R ¹⁸ , L ² to L ⁴ , and n ⁴ to n 6 are as defined above,

X ² is O, S, or CR ^c R ^d ,

X ³ are each independently O or S,

Each of R ¹⁹ to R ²⁷ , R ^c and R ^{d is} independently 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 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 C 3 to C 30 silyl group, a cyano group, a nitro group, a hydroxyl group or a carboxyl group, or a combination thereof,

Ar ² and Ar ³ 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 unsubstituted phenanthrenyl group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted phenanthrenyl group, Substituted or unsubstituted dibenzothiophenyl groups, substituted or unsubstituted dibenzothiophenyl groups, substituted or unsubstituted dibenzothiophenyl groups, substituted or unsubstituted dibenzothiophenyl groups, substituted or unsubstituted dibenzothiophenyl groups, substituted or unsubstituted dibenzothiophenyl groups , Or a combination thereof,

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 phenanthrene group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, A substituted or unsubstituted dibenzothiophenyl group, or a combination thereof.

For example, one of the functional groups listed in Group 6 below.

[Group 6]

In the above group 6,

Y is O, S, CR ^f R ^g , SiR ^h R ⁱ or NR ^j ego,

* Is a connection point,

R ^e to R ^j each independently represent hydrogen, deuterium, 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 aralkyl group, A substituted or unsubstituted C 2 to C 30 aryl group, a substituted or unsubstituted C 2 to C 30 heteroaryl group, a substituted or unsubstituted C 2 to C 30 amino group, a substituted or unsubstituted C 3 to C 30 silyl group,

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

[E-11] [E-12] [E-13]

[E-16] [E-17] [E-18] [E-19]

 [E-21] [E-22] [E-23] [E-24]

[E-26] [E-27] [E-28] [E-29]

[E-31] [E-32] [E-33] [E-34]

[E-36] [E-37] [E-38] [E-39]

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

[E-46] [E-47] [E-48] [E-49]

[E-50] [E-51] [E-52] [E-53]

[E-55] [E-56] [E-57]

[E-60] [E-61] [E-62] [E-63]

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

[E-68] [E-69] [E-70] [E-71]

[E-72] [E-73] [E-74] [E-75]

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

[E-81] [E-82] [E-83] [E-84]

[E-85] [E-86] [E-87] [E-88]

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

[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-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-38] [F-39] [F-40] [F-41]

[F-42] [F-43] [F-44] [F-45]

[F-47] [F-48] [F-49] [F-50]

[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]

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

[H-6] [H-7] [H-8] [H-9]

[H-11] [H-12] [H-13] [H-14]

[H-16] [H-17] [H-18] [H-19] [H-20]

[H-21] [H-22] [H-23] [H-24]

[H-26] [H-27] [H-28] [H-29]

[H-31] [H-32] [H-33] [H-34]

[H-36] [H-37] [H-38] [H-39]

[H-41] [H-42] [H-43] [H-44]

[H-46] [H-47] [H-48] [H-49]

[H-51] [H-52] [H-53] [H-54]

[H-56] [H-57] [H-58] [H-59]

[H-61] [H-62] [H-63] [H-64]

[H-66] [H-67] [H-68] [H-69]

[H-71] [H-72] [H-73] [H-74]

[H-76] [H-77] [H-78] [H-79]

[H-81] [H-82] [H-83] [H-84]

[H-86] [H-87] [H-88] [H-89]

[H-91] [H-92] [H-93] [H-94]

An organic optoelectronic device according to an embodiment of the present invention includes an electron transporting auxiliary layer including a first compound having a strong electron characteristic and a second compound having a strong hole characteristic at the same time

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 these materials together, it is possible to improve the efficiency by adjusting the charge balance through the hole injection control ability of the hole transporting auxiliary layer and the electron injection controlling ability of the electron transporting auxiliary layer, and the hole transporting auxiliary layer and the electron transporting auxiliary layer Charge accumulation at each interface of the organic layer is prevented, deterioration of the device is reduced, the device is stabilized, and the lifetime can be improved.

Specifically, at least one of the first compound represented by the formula (I-1) or (II-II) and the second compound represented by the formula (II-2) May be used together.

More specifically, at least one of the first compounds represented by the formulas (1c) to (1t), at least one of the second compounds represented by the formulas (2-1) to (1-2) The third compound may be used together.

More specifically, at least one of the first compounds represented by Formulas 1c, 1d, 1g and 1h, at least one of the second compounds represented by Formulas 2-IX to 2-XI, and at least one of Formula 3-VII, -III, and the third compound represented by the general formula (III-IX) can be used together.

For example, a first compound represented by the formula (1h), a second compound represented by the formula (2-XI), and a third compound represented by the formula (3-VII) and (3-VIII) 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 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

After 140.4 g (674 mmol) of 2-benzalacetophenone, 199.04 g (808.77 mmol) of pyridine salt compound and 415.6 g (5391 mmol) of ammonium acetate were suspended in methanol (1720 ml), the mixture was 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) of TBAB were all added thereto and suspended in chlorobenzene and refluxed at 140 ° 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 the compound B and sodium tert- After dissolving 7.92 g (82.32 mmol) of toluene 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, and the resulting solid was filtered, and the solid matter was dissolved again in chlorobenzene, and activated charcoal and anhydrous magnesium sulfate were added thereto and stirred, and the solution was filtered and recrystallized using chlorobenzene and methanol To obtain 28.10 g (80%) of a 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) of NBS was added in small portions, 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

10 g (34.83 mmol) of compound N, 9- [l, l ' -biphenyl-4-yl] (0.7 mmol) of tetrakis- (triphenylphosphine) palladium (0) were dissolved in 140 ml of toluene, 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. 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]

Synthesis was carried out in the same manner as in the synthesis of Intermediate M-5 except that 10 g (30.9 mmol) of Intermediate M-2 and 6.3 g (37.08 mmol, TCI) of 2-amino-9,9'- , And 11 g (76%) of Intermediate M-6 was obtained.

LC-Mass (theory: 467.17 g / mol, measured: M + = 467.23 g / mol)

Synthetic example  18: Synthesis of intermediate M-7

[Reaction Scheme 18]

Synthesis and purification were carried out in the same manner as in the synthesis of Intermediate M-5, except that 10 g (30.9 mmol) of Intermediate M-4 and 6.3 g (37.08 mmol, Aldrich) 7 10.6 g (80%) was obtained.

LC-Mass (theory: 427.14 g / mol, measured: M + = 427.19 g / mol)

Synthetic example  19: Synthesis of intermediate M-8

[Reaction Scheme 19]

Synthesis and purification were carried out in the same manner as in the synthesis of Intermediate M-5, except that 10 g (30.9 mmol) of Intermediate M-2 and 6.3 g (37.08 mmol, Aldrich) 8 < / RTI > 10.5 g (80%).

LC-Mass (theory: 427.14 g / mol, measured: M + = 427.20 g / mol)

Synthetic example  20: Synthesis of compound H-1

[Reaction Scheme 20]

15 g (46.4 mmol) of intermediate M-1, 3.9 g (23.2 mmol, Aldrich) of 4-aminobiphenyl and 6.7 g (69.6 mmol) of sodium di-t-butoxide were added to a round bottom flask and 155 ml of toluene was added to dissolve . 0.53 g (0.928 mmol) of Pd (dba) 2 and 0.38 g (1.86 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 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 obtain 13.7 g (90%) of the target compound H-1.

LC-Mass (theory: 653.24 g / mol, measured: M + = 653.31 g / mol)

Synthetic example  21 to 31: Synthesis of Compound

The starting material 1 and the starting material 2 of the following [Table 1] were synthesized according to the synthesis method of Synthesis Example 20, and the yields and the LC-Mass values were as shown in Table 1 below.

Synthetic example Starting material 1 Starting material 2 product Yield (%) LC-Mass (M + H ⁺ ) 21

H-2 87%
693.32 22

H-11 88%
761.28 23

H-6 82%
761.29 24

E-53 92%
563.28 25

E-70 85%
727.31 26

F-36 93%
619.34 27

F-44 90%
553.29 28

H-16 85%
653.34 29

H-46 94%
501.21 30

H-87 91%
533.25 31

F-41 80%
743.33

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 washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, dried and transferred to a plasma cleaner, then the substrate was cleaned using oxygen plasma for 10 minutes, and 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 H-2 obtained in Synthesis Example 21. Subsequently, BH113 and BD370, which are sold by SFC, were doped with blue fluorescent light emitting host and dopant, respectively, on the hole transporting auxiliary layer to a thickness of 200 ANGSTROM to form a light emitting layer. Subsequently, Compound A-33 obtained in Synthesis Example 8 and Compound B-43 obtained in Synthesis Example 11 were vacuum deposited on the light-emitting layer to form an electron transporting auxiliary layer having a thickness of 50 Å. Compound A-33 and Compound B-43 were used in a weight ratio of 1: 1.

Subsequently, 8- (4- (4- (naphthalen-2-yl) -6- (naphthalen-3-yl) -1,3,5-triazin-2-yl) phenyl) quinoline 2-yl) phenyl) quinoline (Compound E) and Liq (2-yl) -1,3,5-triazin- 8-hydroxyquinolatolithium were simultaneously vacuum deposited at a ratio of 1: 1 to form an electron transport layer having a thickness of 310 A, and an anode was sequentially formed by vacuum deposition of Liq 15 A and Al 1200 A over the electron transport layer to fabricate an organic light emitting device.

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

A hole transporting auxiliary layer H-2 (50 Å) / EML [BH113: BD370 (95: 5 wt%)] (200 Å) / electron transporting auxiliary layer (ITO / A 700 Å / B 50 Å / (A-33: B-43 = 1: 1 (50 Å) / E: Liq = 1: 1 (300 Å) / Liq (15 Å) / Al (1200 Å).

Example  2

An organic light emitting device was fabricated in the same manner as in Example 1, except that Compound H-11 obtained in Synthesis Example 22 was used instead of Compound H-2 in the hole transporting auxiliary layer.

Reference example  One

An organic light emitting device was fabricated in the same manner as in Example 1, except that the hole transporting layer was not formed and Compound C was deposited to a thickness of 750 A to form a hole transporting layer.

Comparative Example  One

Instead of forming the hole transporting auxiliary layer, the electron transporting layer was formed by evaporating the compound C to a thickness of 750 ANGSTROM and the compound E: Liq = 1: 1 instead of the compound E: Liq = 1: 1: 1 (360 ANGSTROM) was deposited on the organic light-emitting device.

Comparative Example  2

Except that the electron transporting auxiliary layer was not formed and the compound E: Liq = 1: 1 (360 ANGSTROM) was deposited instead of the compound E: Liq = 1: 1 (310 ANGSTROM) in the electron transporting layer, The device was fabricated.

evaluation

The luminous efficiency and lifetime of the organic luminescent devices according to Example 1, Example 2, Reference Example 1, Comparative Example 1 and Comparative Example 2 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) Life measurement

The time at which the luminance (cd / m ²⁾ was maintained at 750 cd / m ² and the current efficiency (cd / A) decreased to 97% was measured and the results were obtained.

Hole transporting auxiliary layer Electron transporting auxiliary layer Luminous efficiency
(cd / A) T97
Life span (h)
@ 750 nit The first compound The second compound First compound: second compound
(wt / wt) Example 1 H-2 A-33 B-43 1: 1 7.0 60 Example 2 H-11 A-33 B-43 1: 1 7.0 50 Reference Example 1 Compound C A-33 B-43 1: 1 6.2 48 Comparative Example 1 Compound C - - - 5.9 25 Comparative Example 2 H-2 - - - 6.9 30

Referring to Table 2, the organic light emitting devices according to Examples 1 and 2 were compared with the organic light emitting devices according to Reference Example 1 and Comparative Examples 1 and 2, respectively, and it was confirmed that the luminous efficiency and lifetime characteristics were remarkably improved at the same time .

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

10: anode 20: cathode
30: organic layer 31: hole transport layer
32: light emitting layer 33: hole transporting auxiliary layer
34: Electron transport layer 35: Electron transport layer

Claims (15)

The anode and cathode,
A light emitting layer positioned between the anode and the cathode,
A hole transporting layer disposed between the anode and the light emitting layer,
A hole transporting auxiliary layer positioned between the hole transporting layer and the light emitting layer,
An electron transporting layer positioned between the cathode and the light emitting layer, and
And an electron transporting layer positioned between the electron transporting layer and the light emitting layer,
Wherein the electron transport assisting 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,
Each Z is independently N or CR ^a ,
At least two of Z are 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 C 6 to C 30 arylene group, a C 2 to C 30 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 C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heteroaryl group,
(3)

In Formula 3,
X < ¹ > is O or S,
R ¹⁷ and R ¹⁸ are each independently hydrogen, deuterium, halogen, a C1 to C20 alkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, or a cyano group,
Ar ² and Ar ³ are each independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group,
L ² to L ⁴ 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 n6 are each independently an integer of 0 to 3,
Means that at least one hydrogen is substituted by deuterium, a halogen group, a C1 to C30 alkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl 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)
Each Z is independently N or CR ^a ,
At least two of Z are 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,
Means that at least one hydrogen is substituted with deuterium, a halogen group, a C1 to C30 alkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl 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 at least one of the following general formulas (II-1) to (II-XI):
[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 are each independently a single bond, a C 6 to C 30 arylene group, a C 2 to C 30 heteroarylene group, or a combination thereof,
R ¹¹ to R ¹⁶ are each independently hydrogen, deuterium, a C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heteroaryl group,
ET, ET1 and ET2 are each independently selected from the groups listed in the following group 3,
Wherein HT, HT1, and HT2 are each independently selected from the groups listed in Group 4 below:
[Group 3]

,
[Group 4]

,
Means that at least one hydrogen is substituted with deuterium, a halogen group, a C1 to C30 alkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, or a cyano group,
In the groups 3 and 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,
Wherein the electron transporting auxiliary layer comprises:
At least one of the first compounds represented by the following general formulas (I-1) and (II-II); And
An organic optoelectronic device comprising at least one of the following compounds represented by the following general formulas (II-1) to (II-XI)
[Chemical Formula 1-I] [Chemical Formula 1-II]

In the above general formulas (I-1) and (II-II)
Each Z is independently N or CR ^a ,
At least two of Z are 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,
[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 are each independently a single bond, a C 6 to C 30 arylene group, a C 2 to C 30 heteroarylene group, or a combination thereof,
R ¹¹ to R ¹⁶ are each independently hydrogen, deuterium, a C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heteroaryl group,
ET, ET1 and ET2 are each independently selected from the groups listed in the following group 3,
HT, HT1 and HT2 are each independently selected from the groups listed in the following group 4,
[Group 3]

,
[Group 4]

,
In the groups 3 and 4, * is a connection point,
Means that at least one hydrogen is substituted with deuterium, a halogen group, a C1 to C30 alkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, or a cyano group. The method of claim 6,
Wherein the electron transporting auxiliary layer comprises:
A first compound represented by the above formula (I-I); And
And a second compound represented by Formula 2-XI. The method of claim 1,
Wherein the third compound is represented by the following general formula (III-1) or (III-II):
[Formula 3-I] [Formula 3-II]

In the general formulas (III-I) and (III-II)
X < ¹ > is O or S,
R ¹⁷ and R ¹⁸ are each independently hydrogen, deuterium, halogen, a C1 to C20 alkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, or a cyano group,
Ar ² and Ar ³ are each independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group,
L ² to L ⁴ 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 n6 each independently represent an integer of 0 to 3,
Means that at least one hydrogen is substituted with deuterium, a halogen group, a C1 to C30 alkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, or a cyano group. The method of claim 1,
Wherein the third compound is represented by at least one of the following formulas (III-III) to (I-X): < EMI ID =
[Chemical Formula 3-III] [Chemical Formula 3-IV] Chemical Formula 3-V]

[Formula 3-VI] [Chemical Formula 3-VII] [Chemical Formula 3-VIII]

[Chemical Formula 3-IX]

In the above Formulas 3-III to 3-IX,
X ¹ and X ³ are each independently O or S,
X ² is O, S, or CR ^c R ^d ,
Each of R ¹⁷ to R ²⁷ , R ^c and R ^{d is} independently hydrogen, deuterium, halogen, a C1 to C20 alkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group,
Ar ² and Ar ³ each independently represent a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted 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, a substituted or unsubstituted naphthylene group, A substituted or unsubstituted dibenzothiophenyl group, or a combination thereof,
L ² to L ⁴ 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 n6 are each independently an integer of 0 to 3,
Means that at least one hydrogen is substituted with deuterium, a halogen group, a C1 to C30 alkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, or a cyano group. The method of claim 1,
Wherein Ar ² and Ar ³ in Formula 3 are each independently selected from the groups listed in the following Group 6:
[Group 6]

In the above group 6,
Y is O, S, CR ^f R ^g , SiR ^h R ⁱ or NR ^j ,
* Is a connection point,
R ^e to R ^j each independently represent hydrogen, deuterium, a C1 to C20 alkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, or a cyano group. The method of claim 1,
Wherein the electron transporting auxiliary layer comprises at least one of the first compounds represented by the following general formulas (I-1) and (II-II); And at least one of the second compounds represented by the following general formulas (II-1) to (II-XI)
Wherein the hole transporting auxiliary layer comprises at least one of a third compound represented by the following general formulas (III-3) to (III-IX):
[Chemical Formula 1-I] [Chemical Formula 1-II]

In the above general formulas (I-1) and (II-II)
Each Z is independently N or CR ^a ,
At least two of Z are 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,
[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 are each independently a single bond, a C 6 to C 30 arylene group, a C 2 to C 30 heteroarylene group, or a combination thereof,
R ¹¹ to R ¹⁶ are each independently hydrogen, deuterium, a C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C2 to C50 heteroaryl group,
ET, ET1 and ET2 are each independently selected from the groups listed in the following group 3,
HT, HT1 and HT2 are each independently selected from the groups listed in the following group 4,
[Group 3]

,
[Group 4]

,
In the groups 3 and 4, * is a connection point,
[Chemical Formula 3-III] [Chemical Formula 3-IV] Chemical Formula 3-V]

[Formula 3-VI] [Chemical Formula 3-VII] [Chemical Formula 3-VIII]

[Chemical Formula 3-IX]

In the above Formulas 3-III to 3-IX,
X ¹ and X ³ are each independently O or S,
X ² is O, S, or CR ^c R ^d ,
Each of R ¹⁷ to R ²⁷ , R ^c and R ^{d is} independently hydrogen, deuterium, halogen, a C1 to C20 alkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group,
Ar ² and Ar ³ each independently represent a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted 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, a substituted or unsubstituted naphthylene group, A substituted or unsubstituted dibenzothiophenyl group, or a combination thereof,
L ² to L ⁴ 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 n6 are each independently an integer of 0 to 3,
Means that at least one hydrogen is substituted with deuterium, a halogen group, a C1 to C30 alkyl group, a C6 to C30 aryl group, a C2 to C30 heteroaryl group, or a cyano group. 12. The method of claim 11,
Wherein the electron transporting auxiliary 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 at least one of the third compounds represented by the general formulas (III-VII), (III-VIII) and (III-IX). The method of claim 1,
Wherein the hole transporting auxiliary layer is in contact with the hole transporting layer and the light emitting layer,
And the electron transporting auxiliary layer is in contact with the electron transporting layer and the light emitting layer, respectively. The method of claim 1,
Wherein the light emitting layer further comprises a fluorescent dopant. A display device comprising the organic opto-electronic device according to any one of claims 1 to 14.

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