WO2016068446A1

WO2016068446A1 - Organic optoelectronic diode and display device

Info

Publication number: WO2016068446A1
Application number: PCT/KR2015/007008
Authority: WO
Inventors: 조영경; 김창우; 류진현; 민수현; 정호국; 강기욱; 강동민; 류동완; 오재진; 유은선; 정성현; 한수진
Original assignee: 삼성에스디아이 주식회사
Priority date: 2014-10-28
Filing date: 2015-07-07
Publication date: 2016-05-06
Also published as: CN107109211B; KR101848347B1; KR20160049842A; CN107109211A

Abstract

Provided is an organic optoelectronic diode and a display device comprising the organic optoelectronic diode, the organic optoelectronic diode comprising: an anode and a cathode facing each other; an emission layer located between the anode and the cathode; an electron transport layer located between the cathode and the emission layer; and an auxiliary electron transport layer located between the electron transport layer and the emission layer, wherein the auxiliary electron transport layer comprises at least one type of first compound represented by chemical formula 1 below. Chemical formula 1 is the same as that described in the description.

Description

【Specification】

[Name of invention]

Organic optoelectronic devices and displays

Technical Field

An organic optoelectronic device and a display device.

Background Art

An organic optoelectric diode is a device capable of converting electrical energy and light energy.

Organic optoelectronic devices can be divided into two types according to the principle of operation. One is that an exciton formed by light energy is separated into electrons and holes, and the electrons and holes are transferred to different electrodes to generate electrical energy. Photovoltaic device, the other by supplying voltage or current to the electrode. It is a light emitting device that generates light energy from electrical energy.

Examples of the organic optoelectronic device may be an organic photoelectric device, an organic light emitting device, an organic solar cell and an organic photo conductor drum.

Among these, organic light emitting diodes (OLEDs) have recently attracted much attention as demand for flat panel displays increases. The organic light emitting device converts electrical energy into light by applying an electric current to the organic light emitting material. The organic light emitting device has a structure in which an organic layer is inserted between an anode and a cathode.

One of the biggest problems of long-life full color displays is the lifetime of blue organic light emitting devices. Therefore, a lot of research is in progress for the development of long-life blue organic light emitting device. The present invention is to provide a long-life blue organic light emitting device to solve this problem.

[Detailed Description of the Invention]

[Technical problem]

One embodiment provides an organic optoelectronic device capable of realizing high efficiency characteristics. Another embodiment provides a display device including the organic optoelectronic device. Technical Solution

According to one embodiment, the anode and the cathode facing each other, the anode and the An emission layer located between the cathode, an electron transport layer located between the cathode and the emission layer, and an electron transport layer located between the electron transport layer and the emission layer

Comprising an electron transport auxiliary layer, the electron transport auxiliary layer provides an organic optoelectronic device comprising at least one first compound represented by the following formula (1).

One]

In Chemical Formula 1,

Z is independently N, C or CR ^a ,

At least one of Z is N,

R ¹ to R ⁶ , and R ^a are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or Combination of these,

L 'to L ⁶ 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,

nl to n6 are each independently an integer of 0 to 5.

According to another embodiment, an anode and a cathode facing each other, a light emitting layer positioned between the anode and the cathode, a hole transport layer located between the anode and the light emitting layer, a hole transport auxiliary layer located between the hole transport layer and the light emitting layer And an electron transporting layer located between the cathode and the light emitting layer, and an electron transporting auxiliary layer located between the electron transporting layer and the light emitting layer, wherein the electron transporting auxiliary layer is at least one first represented by Formula 1 below. Comprising a compound, the hole transport auxiliary layer provides an organic optoelectronic device comprising at least one second compound represented by the following formula (2). [Formula 1]

In Formula 1, the definitions of Z, R 'to R ⁶ , L' to L ⁶ , and nl to _n 6 are as described above.

[Formula 2]

In Chemical Formula 2,

X ¹ is 0 or S,

R ⁷ to R ⁹ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or Unsubstituted C3 to C20 cycloalkoxy group _: substituted or unsubstituted C1 to C20 alkylthio group, substituted or unsubstituted C6 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 To C30 aryloxy group, substituted or unsubstituted C6 to C30 arylthio group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 amino group, substituted or unsubstituted C3 to C30 silyl group , Cyano group, nitro group, hydroxyl group or carboxyl group, or a combination thereof, Ar ¹ and Ar ² are each independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group,

L ⁷ to L ⁹ 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,

n7 to n9 are each independently an integer of any one of 0 to 3, and the "substituted" of Chemical Formulas 1 and 2 indicates that at least one hydrogen is deuterium, a halogen group, a hydroxy group, an amino group, a substituted or unsubstituted C1. To C30 amine group, nitro group, substituted or unsubstituted C 1 to C40 silyl group, C1 to C30 alkyl group, C3 to C30

Substituted cycloalkyl group, C2 to C30 heterocycloalkyl group, C6 to C30 aryl group, C2 to C30 heteroaryl group, C 1 to C20 alkoxy group, fluoro group, C 1 to C 10 trifluoroalkyl group or cyano group it means.

According to another embodiment, a display device including the organic optoelectronic device is provided.

Advantageous Effects

High efficiency organic optoelectronic devices can be implemented.

[Brief Description of Drawings]

1 and 2 are cross-sectional views schematically illustrating an organic optoelectronic device according to an embodiment.

10: anode 20: cathode

30: organic layer 31: hole transport layer

32: light emitting layer 33: hole transport auxiliary layer

34: electron transport layer 35: electron transport auxiliary layer

36: electron injection layer 37: hole injection layer

[Best form for implementation of the invention]

Hereinafter, embodiments of the present invention will be described in detail. However, this is presented as an example, whereby the present invention is not limited and the present invention is defined only by the scope of the claims to be described later.

As used herein, unless otherwise defined, at least one hydrogen in a substituent or compound is deuterium, halogen, hydroxy, amino, substituted or unsubstituted. CI to C30 amine group, nitro group, substituted or unsubstituted C1 to C40 silyl group, C1 to C30 alkyl group, C1 to C10 alkylsilyl group, C3 to C30 cycloalkyl group, C2 to C30 heterocycloalkyl group, C6 to C30 aryl group It means substituted with C1 to C10 trifluoroalkyl group or cyano group, such as C2 to C30 heteroaryl group, C1 to C20 alkoxy group, fluoro group, trifluoromethyl group.

In addition, the substituted halogen, hydroxy group, amino group, substituted or unsubstituted C1 to C20 amine group, nitro group, substituted or unsubstituted C3 to C40 silyl group, C1 to C30 alkyl group, C1 to C10 alkylsilyl group, C3 to C30 cycloalkyl group, C2 to C30

Two adjacent substituents of C 1 to C 10 trifluoroalkyl group or cyano group such as heterocycloalkyl group, C 6 to C 30 aryl group, C 2 to C 30 heteroaryl group, C 1 to C 20 alkoxy group, fluoro group, trifluoromethyl group It may be fused to form a ring. For example, the substituted C6 to C30 aryl group can be fused to another adjacent substituted C6 to C30 aryl group to form a substituted or unsubstituted fluorene ring.

In the present specification, "hetero" means one to three hetero atoms selected from the group consisting of Ν, Ο, S, P, and Si in one functional group, and the remainder is carbon unless otherwise defined. .

As used herein, unless otherwise defined, an "alkyl group" is aliphatic

It means a hydrocarbon group. The alkyl group may be a "saturated alkyl group" that 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

It may be a C1 to C20 alkyl group or a C1 to C10 alkyl group. For example, a C1 to C4 alkyl group means that the alkyl chain contains 1 to 4 carbon atoms, with methyl, ethyl, propyl, iso-propyl, η-butyl, iso-butyl, sec-butyl and t-butyl Selected from the group consisting of:

Specific examples of the alkyl group include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, pentyl group, nucleosil group, cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclonucleus It means a practical skill.

As used herein, an "aryl group" means a substituent in which all of the elements of the cyclic substituent have p-orbitals, and these P-orbitals form a conjugate, and are monocyclic, polycyclic or Fused ring polycyclic (i.e., of carbon atoms Ring groups with adjacent pairs of ¥ 1).

In the present specification, a "heterocyclic group" is a hetero atom selected from the group consisting of N, 0, S, P, and Si in a ring compound such as a ¾ group, a cycloalkyl group, a fused ring thereof, or a combination thereof. It means that it contains at least one, and the rest is carbon. In the case where the heterocyclic group is a fused ring, the heterocyclic group may include one or more heteroatoms for all or each ring. Thus, the heterocyclic group is a higher concept encompassing the heteroaryl group.

More specifically, a substituted or unsubstituted C6 to C30 aryl group and / or a substituted or unsubstituted C2 to C30 heterocyclic group is a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthra Senyl group, substituted or unsubstituted

Phenanthryl groups, substituted or unsubstituted naphthacenyl groups, substituted or unsubstituted pyrenyl groups, substituted or unsubstituted biphenyl groups, 'substituted or unsubstituted P-terphenyl groups, substituted or unsubstituted m-terphenyl groups, Substituted or unsubstituted chrysenyl group, substituted or unsubstituted

Triphenylenyl group, substituted or unsubstituted perylenyl group, substituted or unsubstituted indenyl group, substituted or unsubstituted furanyl group, substituted or unsubstituted thiophenyl group, substituted or unsubstituted pyryl group, substituted or unsubstituted Substituted pyrazolyl groups, substituted or unsubstituted imidazolyl groups, substituted or unsubstituted triazolyl groups, substituted or unsubstituted oxazolyl groups, substituted or unsubstituted thiazolyl groups, substituted or unsubstituted oxadiazoles Diary, Substituted or Unsubstituted

Thiadiazolyl group, substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted benzofuranyl group, Substituted or unsubstituted benzothiophenyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted indolyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted Quinazolinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted benzoxazinyl group, substituted or unsubstituted benzthiazinyl group, substituted or unsubstituted

Acridinyl group, substituted or unsubstituted phenazineyl group, substituted or unsubstituted phenothiazineyl group, substituted or unsubstituted phenoxazineyl group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted carbazolyl group, A substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl 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 characteristic refers to a characteristic capable of forming holes by donating electrons when an electric field is applied, and injecting holes formed at the anode into the light emitting layer having conductive properties along the HOMO level, and emitting layer. It refers to a property that facilitates the movement of the hole formed in the anode and the movement in the light emitting layer.

In addition, the electron characteristic refers to a characteristic in which electrons can be received when an electric field is applied, and has conductivity characteristics along the LUMO level, injecting electrons formed in the cathode into the light emitting layer, moving electrons formed in the light emitting layer to the cathode, and It means a property that facilitates movement.

Hereinafter, an organic optoelectronic device according to example embodiments is described.

The organic optoelectronic device is not particularly limited as long as the device can switch electrical energy and light energy. Examples thereof include an organic photoelectric device, an organic light emitting device, an organic solar cell, and an organic photosensitive drum.

Here, an organic light emitting device as an example of an organic optoelectronic device will be described as an example, but the present invention is not limited thereto and may be similarly applied to other organic optoelectronic devices.

In the drawings, the thickness of layers, films, panels, regions, etc., are exaggerated for clarity. Like parts are designated by like reference numerals throughout the specification. When a part of a layer, film, area, plate, etc. is said to be "on" another part, this includes not only the other part "directly" but also another part in the middle. On the contrary, when a part is "just above" another part, there is no other part in the middle.

1 and 2 are schematic cross-sectional views of an organic optoelectronic device according to an embodiment. Referring to FIG. 1, an organic optoelectronic device according to an embodiment includes an anode 10 and a cathode 20 facing each other. ， And located between anode 10 and cathode 20

And an organic layer 30.

The anode 10 may be made of a high work function conductor, for example, to facilitate hole injection, and may be made of metal, metal oxide and / or conductive polymer, for example. The anode 10 may be, for example, a metal such as nickel, platinum, vanadium, crumb, copper, zinc, gold or an alloy thereof; Zinc oxide, indium oxide, indium tin oxide (ΠΌ), Metal oxides such as indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO and A1 or Sn02 and Sb; Conductive polymers such as poly (3 ᅳ methylthiophene), poly (3,4- (ethylene-1,2-dioxy) thiophene) (polyehtylenedioxythiophene: PEDT), polypyrrole and polyaniline, and the like. It is not.

The cathode 20 may be made of a low work function conductor, for example, to facilitate electron injection, and may be made of metal, metal oxide and / or conductive polymer, for example. The cathode 20 is, for example, a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, or an alloy thereof; Multilayer structure materials such as LiF / Al, U02 / A1, LiF / Ca, LiF / Al, and BaF2 / Ca, but are not limited thereto.

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

It also includes an electron transport layer 34 and an electron transport auxiliary layer 35 positioned between the electron transport layer 34 and the light emitting layer 32.

Referring to FIG. 2, the organic layer 30 is disposed between the hole transport layer 31 and the anode 10.

It may further include a hole injection layer 37, between the electron transport layer 34 and the cathode 20

The electron injection layer 36 may be further included.

The hole injection layer 37 laminated between the hole transport layer 31 and the anode 10 not only improves the interfacial properties between ΠΌ used as the anode and the organic material used as the hole transport layer 31, but also the surface thereof. It is applied on top of the uneven Π 주는 to soften the surface of ITO. For example, the hole injection layer 37 is used to determine the work function level of ITO and the HOMO level of the hole transport layer 31 in order to control the difference between the work function level of ITO and the HOMO level of the hole transport layer 31 which can be used as an anode. As the material having a median value, a material having a particularly suitable conductivity is selected. N4, N4'-diphenyl-N4, N4'-bis (9-phenyl-9H-carbazol-3-yl) biphenyl-4,4 as a material constituting the hole injection layer 37 in the context of the present invention. '-Diamine (N4, N4'-diphenyl-N ⁴ , N4'-bis (9-phenyl-9H-carbazol- ³ -y ^

Although not limited thereto, the hole injection layer 37 may be used.

It can be used with conventional materials that make up, for example, copper

phthlalocyanine (CuPc), N, N'-dinaphthyl-N, N'-phenyl- (l, 1 '-biphenyl) -4,4'-diamine, NPD), 4,4', 4 "-tris [methylphenyl ( phenyl) amino] triphenyl amine (m-MTDATA), 4,4 ', 4 "-tris [l- naphthy 1 (phenyl) amino] triphenyl amine (l -TNATA), 4,4 ', 4 "-tris [2- naphthyl (phenyl) amino] triphenyl amine (2-TNATA), 1, 3,5-tris [N -(4-diphenylaminophenyl) phenylamino] aromatic amines such as benzene (p-DPA-TDAB) and the like, as well as 4,4'-bis | [4- {N, N-bis (3-methylphenyl) amino} phenyl]- ^

Compounds such as phenylamino] biphenyl (DNTPD), hexaazatriphenylene-hexacarbonitirile (HAT-CN), and poly (3,4-ethylenedioxythiophene) -poly (styrnesulfonate) (PEDOT), which are polythiophene derivatives as conductive polymers, may be used. The hole injection layer 37 may be coated on top of πΌ used as an anode, for example, at a thickness of 10 to 300 A.

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

The hole transport layer 31 is a layer for facilitating hole transfer from the anode 10 to the light emitting layer 32, and may be, for example, an amine compound, but is not limited thereto. The amine compound may include, for example, at least one aryl group and / or heteroaryl group. The amine compound may be represented by, for example, the following Chemical Formula a or Chemical Formula b, but is not limited thereto.

[Formula a] [Formula b]

_/ ^N _\ N-Ar ^h -N

^{Arb Arc} Ar ^{g / X} Ar ^f

In Chemical Formula a or Chemical Formula b,

Ar ^a to Ar ^g are each independently hydrogen, deuterium, substituted or unsubstituted C1 to

C20 alkyl group, substituted or unsubstituted C6 to C30 aryl group, 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, or a combination thereof,

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 electron transfer from the cathode 20 to the light emitting layer 32. The electron transport layer 34 is an organic compound having an electron withdrawing group, and a metal compound that can accept electrons well. Or combinations thereof may be used. For example, aluminum trihydroxyquinoline (Alq ₃ ), 1,3,4-oxadiazole derivative as an electron transport layer material, 2- (4-biphenylyl-5-phenyl-1,3,4-oxadia Sol (2- (4-biphenylyl) -5-phenyl-l, 3,4-oxadiazole, PBD), a quinoxaline derivative 1,3,4-tris [(3-phenyl-6-trifluoromethyl) quinox Saline-2-yl] benzene (l, 3,4-tris [(3-penyl-6-trifluoromethyl) quino-xaline-2-yl] benzene, TPQ), triazole derivatives and triazine derivatives 8- (4 - ^(4- (naphthalen-2-yl) -6- (naphthalen-3-yl) -1,3, ^{5-triazin-2-yl)} phenyl) quinoline (8- (4- (4- (naphthalen- 2-yl) -6- (naphthalen-3-yl) -l, 3,5-triazin-2-yl) phenyl) quinoline) may be used, but is not limited thereto.

In addition, in the electron transport layer, an organometallic compound represented by the following Chemical Formula c may be used alone or in combination with the electron transport layer material.

[Formula c]

In Chemical Formula c,

Y is a portion in which any one selected from C, N, 0 and S is directly bonded to M to form a single bond, and a portion selected from C, N, 0 and S forms a coordination bond to M. It includes, and is a ligand chelated by the single bond and the coordination bond,

M is an alkali metal, alkaline earth metal, aluminum (A1) or boron (B) atom, and OA is a monovalent ligand capable of single bond or coordination with M,

0 is oxygen,

A is 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 carbon group having 2 to 20 carbon atoms An alkynyl group, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl group having 5 to 30 carbon atoms, and a substituted or unsubstituted hetero atom having 2 to 50 carbon atoms having Ο, Ν or S Any one selected from heteroaryl groups,

M = l, n = 0 when M is one metal selected from alkali metals, m = l, n = l or m = 2 when M is one metal selected from alkaline earth metals , n = 0,

When M is boron or aluminum, any one of m = 1 to 3, and ^η satisfies m + n = 3 as any one of 0 to 2;

The 'substituted' in the 'substituted or unsubstituted' is deuterium, cyano group, halogen group, hydroxy group, nitro group, alkyl group, alkoxy group, alkylamino group, arylamino group, hetero arylamino group, alkylsilyl group, arylsilyl group, An aryloxy group, an aryl group, a heteroaryl group, ^' germanium, phosphorus and boron means substituted with one or more substituents selected from the group consisting of.

In the present invention, Y is the same as or different from each other, and independently from each other may be any one selected from formula cl to formula _C 39, but is not limited thereto.

[Formula c6] [Formula c7] [Formula c8] [Formula c9]

[Formula cll] [Formula cl2] [Formula cl3] [Formula cl4] [Formula ^' cl5]

[Formula cl6] [Formula cl7] [Formula cl8] [Formula cl9] [Formula c20]

[Formula c21] [Formula c2 ² ] [Formula c23] [Formula c2 ⁴ ]

[Formula 26] [Formula c27] [Formula c28] [Formula 9] [Formula c30]

[Formula c31] [Formula c3¾] [Formula c33] [Formula c34] [Formula c35]

c36] [Formula c37] [Formula c38] [Formula c39]

In Chemical Formula cl to Chemical Formula c39,

R is the same as or different from each other, and each independently hydrogen, deuterium, halogen, cyano group, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C3 to C30 hetero Aryl group, substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C1 to C30 alkylamino group, substituted or unsubstituted Selected from a substituted 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 are linked to adjacent substituents with alkylene or alkenylene to form a spirogory or fusion. May form a ring.

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 mainly has a function of promoting recombination of electrons and holes and confining excitons in a light emitting layer, and the dopant has a function of efficiently emitting excitons obtained by recombination.

The light emitting layer can include known hosts and dopants. In a known host, e.g., Alq3, CBP (4,4'-N, N'- dicarboxylic carbazole-biphenyl), PVK (poly (n- vinylcarbazole)), 9,10-di (naphthalene-_ ² - yl) anthracene (ADN), TCTA,丁1 1 (1, 3, 5- tris ^ -phenyl-benzimidazol-2-yl) benzene (l, 3,5-tris (N -phenylbenzimidazole-2-yl) benzene )), TBADN (3- _tert -butyl- ^9,10 -di (naphth- ^2- yl) anthracene), mCP, OXD- ⁷ , BH113 commercially available from SFC, and the like, but are not limited thereto. .

PVK mCP OXD-7

The dopant may be at least one of a fluorescent dopant and a phosphorescent dopant. The phosphorescent dopant may be an organometallic complex including 11 ″, 1 ^, 05,1,, ¾, 1 or a combination of two or more thereof, but is not limited thereto.

Examples of a known blue dopyeon agent _{is, F 2 I ic, (F} 2 ppy) 2 Ir (tmd), Ir (dfppz) 3, ter- fluorene ^{(fluorene), 4, 4 '} - bis (4-phenyl amino styryl) biphenyl ^{(DPAVBi), 2, 5,} 8,11- tetrahydro - _rer t- butyl perylene (TBPe), DPVBi, pyrene derivatives (KR0525408, LG ELECTRONICS INC), BD01, BD370 available on the market in SFC And the like, but is not limited thereto.

DPAVBi TBPe

(KR0525408, LG Electronics Co., Ltd.)

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

Examples of known green dopants include, but are not limited to, Ir (ppy) ₃ (ppy = phenylpyridine), Ir (ppy) ₂ (acac), Ir (mpyp) ₃ , and the like.

Ir (ppy) ₃ lr (PPV) ₂ (acac) If said light emitting layer comprises a host and a dopant, the content of dopyeon agent typically may be selected from the range of the light-emitting layer 100 weight ^_0/0 of about 0.01 to about 15 parts by weight ⁰ / per., And the like.

The light emitting layer has a thickness of about 200 A to about 700 A.

The electron transport auxiliary layer 35 includes at least one first compound represented by the following general formula (1).

In Chemical Formula 1,

Z are each independently N, C or CR ^a ,

At least one of Z is N,

L ¹ to L ⁶ 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,

nl to n6 are each independently an integer of 0 to 5.

Since the first compound includes a ring containing at least one nitrogen, the structure is susceptible to electrons when an electric field is applied, thereby increasing the amount of electron injection, thereby lowering the driving voltage of the organic optoelectronic device to which the first compound is applied. Can improve efficiency.

In one embodiment of the present invention, nl to n6 are each independently an integer of 0 to 5, n 1 + n 2 + n 3 + n 4 + n 5 + n 6> 1, and n 1 + η 2 + η 3 + η 4 + η 5 + η 6> 2 °], nl + n2 + n3 + n4 + n5 + n6> 3 ^ΰ 1, nl + n2 + n3 + n4 + n5 + n6> 4. In addition, nl + n2 + n3 + n4 + n5 + n6≤15,

nl + n2 + n3 + n4 + n5 + n6 <12, η1 + η2 + η3 + η4 + η5 + η6 <10, η 1 + η2 + η3 + η4 + η5 + η6 <8,

η 1 + η 2 + ^η 3 + ^η 4 + ^η 5 + ^η 6 <7, and ^η 1 + _η 2 + ^η 3 + _η 4 + ^η 5 + _η 6 <6.

It is particularly advantageous in terms of performance that the first compound represented by Chemical Formula 1 has at least one kink structure around the arylene group and / or the heteroarylene group. For example, the first compound may be represented by the following Chemical Formula 1-1 or 1-Π. The following chemical formulas are only examples, and are not limited to the following.

1- 1] [Formula 1- Π]

In Chemical Formulas 1-1 and 1-Π, the definitions of Z, R 'to R ⁶ , L to L', and nl to n6 are as described above.

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

L ¹ to L ⁶ of the compound ¹ are specifically a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted quarterphenylene group , A substituted or unsubstituted naphthalenylene group, and the like, and may be, for example, one of the linking groups listed below.

For example, the first compound may be represented by at least one of Formulas lm to 1-K, but is not limited thereto.

[Formula i_m] [Formula l-iv]

Formula l-vn]

In Chemical Formulas i-m to l-K,

. z is as described above,

Each W is independently N, C or CR ^b ,

R ^5a to 1 ^{5 £ 1} are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or Is a combination.

R ^5a to R ^5d are specifically hydrogen, deuterium, substituted or unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted quarterphenyl group, substituted or unsubstituted naphthalene Groups, substituted or unsubstituted pyridine groups, substituted or unsubstituted pyrimidine groups, substituted or unsubstituted triazine groups, substituted or unsubstituted quinolinyl groups, substituted or unsubstituted isoquinolinyl groups, substituted or unsubstituted Phenanthroline, substituted or unsubstituted quinazoline, and can be, for example, one selected from the substituted or unsubstituted groups listed in Group 1 below. Group i]

In group 1, * is the point of attachment Here, "substituted"'at least one hydrogen is deuterium, halogen, C1 to C20 alkyl group, C3 to C20 cycloalkyl group, C1 to C20 alkoxy group, C3 to C20 cycloalkoxy group, C1 to C20 alkylthio group, C6 to C30 aralkyl group, C6 to C30 aryl group, C6 to C30 aryloxy group, C6 to C30 arylthio group, C2 to C30 heteroaryl group, C2 to C30 amino group, C3 to C30 silyl group, cyano group, nitro group, hydroxide Mean substituted by a real group or a carboxyl group.

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

[Group 2]

-1] [A-2] [A-3]

-4] [A-5] [A-6]

A-10] [Α-Π] [A-12]

[A-13] [A-14] [A-15]

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-4] [C-5]

The electron transport auxiliary layer may include the first compound alone, or may further include at least one third compound represented by the following Chemical Formula 3 having a relatively strong hole property in addition to the first compound.

3]

In Chemical Formula 3,

L ¹⁰ to L ¹² 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, and Ar ³ and Ar ⁴ are each independently substituted Or an unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

R ¹⁰ to R ¹³ 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 a combination thereof .

Compound represented by the formula ( ₃ ) is a compound having a relatively strong hole characteristics are included in the electron transport auxiliary layer, it is possible to control the amount of electron injection of the first compound, and to accumulate holes at the interface between the light emitting layer and the electron transport auxiliary layer By improving the stability of the device by preventing it can significantly improve the luminous efficiency and life characteristics of the organic optoelectronic device.

Ar ³ and Ar ⁴ of the third compound is a substituent having a hole or an electronic property, Each independently such as substituted or unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthracenyl group, substituted or unsubstituted carba Zolyl group, substituted or unsubstituted benzofuranyl group, substituted or unsubstituted benzothiophenyl group, substituted or unsubstituted

Fluorenyl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted triphenylene group, substituted or Unsubstituted dibenzofuranyl group, substituted or unsubstituted dibenzothiophenyl group, or a combination thereof.

The third compound may be represented by any one of the following Chemical Formulas 3-1 to 3-ΠΙ according to the characteristics of Ar ³ and Aι · ⁴ .

[Formula 3-I] [Formula 3-Π]

In the above Formula 3- 1 to 3-m, L ¹⁰ to L ¹² , and R ¹⁰ to R ¹³ are as described above,

ET, ET1, and ET2 are each independently a substituent having electronic properties, and ΗΤ, ΗΤΙ and ΗΤ2 are each independently substituents having hole characteristics. Substituents? Γ ',' ΈΤΓ and “ΕΤ2” having electronic properties among Ar ³ and Ar ⁴ of the second compound are, for example It may be a substituent represented by A.

[Formula A]

In Chemical Formula A,

Z are each independently N or CR ^q ,

A1 and A2, and R ^q 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, and at least one of the VII, ΑΙ and A2 increments is N Including

a and b are each independently 0 or 1.

The substituent represented by Formula A may be, for example, one of the functional groups listed in Group 3 below.

Group 3]

In addition, the substituents' ΉΤ '' ΉΤΓ and 'ΗΤ2' having hole characteristics in Ar ³ and Ar ⁴ of the third compound may be, for example, one of the functional groups listed in Group 4 below. [Group 4]

Compound represented by the formula (2) is a compound having a relatively strong hole characteristics, it is included in the electron transport auxiliary layer with the first compound, it is possible to control the amount of electron injection of the first compound, the light emitting layer and the electron transport auxiliary It is possible to improve the stability of the device by preventing the accumulation of holes at the charging interface. Therefore, the luminous efficiency and lifespan characteristics of the organic optoelectronic device can be significantly improved.

The third compound may be selected from, for example, compounds listed in Group 5 below, but is not limited thereto.

[Group 5]

[D-l D-2] [D-3] [-4]

[D-5] [D-6] [D-7] [D-8]

D-9] [-10] [D-11] [D-12]

[D-33] [D-34] [D-35] [D-36] [D-37]

-73] [D-74] [D-75] [D-76]

One kind or two or more kinds of the third compound may be used.

The electron transport auxiliary layer including the first compound having strong electronic properties according to an embodiment of the present invention may further include a third compound having strong hole properties.

By using at least one first compound represented by the formula (1) and at least one third compound represented by the formula (3) together, the efficiency and lifespan of the device can be improved.

Specifically, at least one of the first compounds represented by Formulas i-m to l-x and at least one of the third compounds represented by Formulas 3-1 to 3-m may be used together.

For example, at least one of the first compound represented by Chemical Formula l-iv and Chemical Formula i-νπ and the third compound represented by Chemical Formula 3-m may be used together.

In the electron transport auxiliary layer 35, the first compound and the third compound may be included, for example, in a weight ratio of about 1:99 to 99: 1. Specifically, it may be included in 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, 50:50. In addition, the first compound and the third compound are increased by 1: 2, 1: 3, 1: 4, 1: 5, 1: 1, 2: 1, 3: 1, 4: 1, 5: 1, etc. Can be mixed with rain. The mixing method mixes two substances in advance

Alternatively, each compound may be deposited simultaneously in each weight ratio.

By being included in the above range it is possible to adjust the electron injection ability according to the ratio of the two compounds, it is possible to prevent the accumulation of electrons at the interface of the light emitting layer by balancing the electron transport capacity of the light emitting layer.

In addition, the holes and / or excitons from the light emitting layer are converted into excitons of lower energy than the energy of the axtones of the light emitting layer due to the electron transport auxiliary layer 35 so that the excitons of the holes and / or light emitting layers affect the electron transport layer 34. The impact can be minimized. Therefore, when the first compound having a relatively strong electronic characteristic and the third compound having a relatively strong hole characteristic are used together in the electron transport auxiliary layer, the efficiency and lifespan of the device can be improved.

The hole transport auxiliary layer 33 includes a second compound having good hole transport properties, and adjusts the hole injection characteristics by reducing the difference in the HOMO energy level between the hole transport layer 3 1 and the light emitting layer 32. Quenching of exciton due to polaron at the interface disappears by reducing the accumulation of holes at the interface between the layer 33 and the light emitting layer 32

The quenching can be reduced. Accordingly, deterioration of the device may be reduced and the device may be stabilized to improve efficiency and lifespan.

The second compound may be a compound represented by the following Chemical Formula 2.

2]

In Chemical Formula 2,

X ¹ is 0 or S

R ⁷ to R ⁹ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted

C 1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C.1 to C20 alkoxy group, substituted or unsubstituted C3 to C20 cycloalkoxy group: substituted or unsubstituted C 1 to C20 C20 alkylthio group, substituted or unsubstituted C6 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C6 to C30 arylthio group , Substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 amino group, substituted or unsubstituted C3 to C30 silyl group, cyano group, nitro group, hydroxyl group or carboxyl group, or a combination thereof ego, Ar ¹ and Ar ² are each independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

n7 to n9 are each independently an integer of any one of 0 to 3.

The second compound may be represented by, for example, the following Formula 2-I or Formula 2-P depending on the bonding position of the amine substituent.

-I [Formula 2- Π]

In Chemical Formulas 2-1 and 2-P,? ', ΙΙ ⁷ to R ⁹ , Ar ¹ , Ar ² , L ⁷ to L ⁹ , and n7 to n9 are as described above.

L ⁷ to L ⁹ of the second compound are specifically a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted quarterphenylene group , A substituted or unsubstituted naphthalenylene group, a substituted or unsubstituted fluorenylene group, a substituted or unsubstituted dibenzofuranylene group, a substituted or unsubstituted dibenzothienylene group, and the like,

For example, the Crab 2 compound may be at least one of Formula 2-ΙΠ to Formula 2-XI. [Formula 2-m] [Formula 2-IV] [Formula 2-V]

[Formula 2-VI] [Formula 2-Vn] [Formula 2-VIH]

-K] [Formula ² -Χ]

[Formula 2-XI]

In Formula 2-m to Formula 2-XI, Χ ', ΙΙ ⁷ to R ^ Ar ¹ and Ar ² , L ⁷ to L ⁹ , and n7 to n9 are the same as described above,

X ² is 0, S, or CRiR ^j ,

X ³ are each independently 0 or S,

R ^c to R ^j are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or Unsubstituted C3 to C20 cycloalkoxy group, substituted or unsubstituted C1 to C20 alkylthio group, substituted or unsubstituted C6 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 To C30 aryloxy group, substituted or unsubstituted C6 to C30 arylthio group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 amino group, substituted or unsubstituted C3 to C30 silyl group Or cyano group, nitro group, hydroxyl group or carboxyl group, or a combination thereof.

Ar ¹ and Ar ² are specifically, substituted or unsubstituted phenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted quarterphenyl group, substituted or unsubstituted naphthyl group, substituted or Unsubstituted anthracenyl group, substituted or unsubstituted phenanthrenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted

Triphenylene group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted carbazolyl group, substituted Or an unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof,

More specifically, a substituted or unsubstituted phenyl group, substituted or unsubstituted

Biphenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted quarterphenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthracenyl group, substituted or unsubstituted phenanthrenyl group, substituted or unsubstituted Pyrenyl, substituted or unsubstituted

Triphenylene group, substituted or unsubstituted fluorenyl group, substituted or unsubstituted

Dibenzofuranyl group, substituted or unsubstituted dibenzothiophenyl group, or a combination thereof.

For example, it may be one of the functional groups listed in group 6 below. Group 6]

In group 6 above

Y is 0, S, CR'R ^m , SiR "R ° or NR ^P ,

* Is the junction point,

R ^k to R ^p are each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C20 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group, a substituted or unsubstituted C 6 to C 30 aralkyl group, substituted or unsubstituted A substituted C6 to C30 aryl 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, or a combination thereof,

Wherein “substituted” means at least one hydrogen is deuterium, a halogen group, a hydroxy 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, a C 1 to C30 alkyl group, Substituted with 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 fluoro group, a C1 to C10 trifluoroalkyl group, or a cyano group it means.

The second compound may be selected from, for example, the compounds listed in Group 7 below.

800.00 / ST0ZaM / X3d 9 »890 / 9ΐΟΖ OAV

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800.00 / ST0ZaM / X3d 9 »890 / 9ΐΟΖ OAV

800.00 / ST0ZaM / X3d 9 »890 / 9ΐΟΖ OAV

800.00 / ST0ZaM / X3d 9 »890 / 9ΐΟΖ OAV

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800.00 / SlO∑aM / X3d

9 ^ ⁷ 890 / 9T0r ΟΛΧ [H-76] [H-77] [H-78] [H-79] [H-80]

[H-81] [H-82] [H-83] [H-84] [H-85]

[H-86] [H-87] [H-88] H-89 [H-90]

H-91] H-92] H-93] [H-94] [H-95]

H-96] [H-97] [H-98]

An organic optoelectronic device according to an embodiment of the present invention, by including a ring containing at least one nitrogen, electron transport comprising a first compound which can be a structure that is easy to receive electrons when the electric field is applied, the electron injection amount can be increased An auxiliary layer or an electron transport auxiliary layer simultaneously comprising a first compound having strong electronic properties and a third compound having strong hole characteristics; By reducing the difference in HOMO energy level between the hole transport layer 31 and the light emitting layer 32, a second compound having good hole transport characteristics capable of controlling the hole injection characteristics can be obtained.

It may include a hole transport auxiliary layer containing at the same time.

By using them together, efficiency can be improved by adjusting the charge balance through the hole injection control ability of the hole transport auxiliary layer and the electron injection control ability of the electron transport auxiliary. The organic layer is applied by applying the hole transport auxiliary layer and the electron transport auxiliary layer. By preventing charge from accumulating at each interface of the device, deterioration of the device can be reduced, and the device can be stabilized to improve life.

Specifically, the electron transport auxiliary layer may include a compound selected from the first compound represented by Chemical Formulas im to lx, specifically, the compound selected from the first compound represented by Chemical Formula l-iv and Chemical Formula ι-νπ. There is,

It may further include a compound selected from the third compound represented by the formula 3- 1 to 3-m.

In addition, the hole transport auxiliary layer is a compound selected from the second compound represented by Formula 2-m to Formula 2-XI, specifically, represented by Formula 2-W, Formula 241, Formula 2-X, and Formula 2-XI. It may include a compound selected from the second compound.

For example, the electron transport auxiliary layer may be represented by Formula 1 -IV and Formula 1 -W.

It may include a compound selected from one compound and a third compound represented by the above formula 3-m,

The electron transport auxiliary layer and the hole transport auxiliary layer may be represented by Chemical Formulas 1 to IV and Chemical Formula 1 to 1, respectively.

A compound selected from a first compound represented by VE and a compound selected from the second compound represented by Formula 2-W, Formula 2-VI, Formula 2-D, and Formula 2-XI, or the electron transport assist The layer may further comprise a third compound.

The hole transport auxiliary layer 33 and the electron transport auxiliary layer 35 can be applied on the hole transport layer in a thickness of 0.1 nm to 20.0 nm by a deposition or inkjet process, for example, 0.2 nm to 10.0 nm, 0.3 nm to 5 nm, 0.3 It can be applied in a thickness of nm to 2 nm, 0.4 nm to 1.0 nm and the like.

The organic layer 30 is optionally positioned between the hole injection layer 37 and / or the cathode 20 and the electron transport layer 34 located between the anode 10 and the hole transport layer 31.

It may further include an electron injection worm (36). The organic light emitting diode described above may be applied to an organic light emitting diode display. In the present invention, the organic optoelectronic device may be selected from the group consisting of an organic light emitting device, an organic photoelectric device, an organic solar cell _{: an} organic transistor, an organic photosensitive drum and an organic memory device.

[Form for implementation of invention]

The following presents specific embodiments of the present invention. However, due diligence examples described below are merely for illustrating or explaining the present invention in detail, and thus the present invention is not limited thereto. Synthesis of First Compound

Synthesis Example 1 Synthesis of Intermediate 1-1

One ]

In a nitrogen environment, the compound 2-chloro-4,6-diphenyl-l, 3,5-triazine (50 g, 187 mmol, purchased from TCI) was dissolved in 1 L of THF, followed by (3-bromophenyl) boronic acid (45 g, 224.12 mmol, TCI) and tetrakis (triphenylphosphine) palladium (2.1 g, 1.87 mmol) were added and stirred. Potassium carbonate saturated in water (64 g, 467 mmol) was added thereto, and the mixture was heated and refluxed at 80 ° C for 12 hours. After reaction was completed, water was added to the reaction solution, extracted with dichloromethane (DCM), and water was removed with anhydrous MgS04. , Filtered and concentrated under reduced pressure. The obtained residue was separated and purified through column chromatography, obtaining Compound 1-1 (69 g, 95%).

HRMS (70 eV, EI +): m / z calcd for C21 H14 BrN3: 387.0371, found: 387

Elemental Analysis: C, 65%; H, 4% Synthesis Example 2 Synthesis of Intermediate 1-2 2]

1-1 I-2

Intermediate 1-1 and 3-chlorophenyl boronic acid (TCI) were synthesized and purified in the same manner as in the synthesis of Intermediate 1-1, to obtain 51 g (95%) of Intermediate I-2.

HRMS (70 eV, EI +): m / z calcd for C 27 H 18 C 1 N 3: 419.1189, found: 419

Elemental Analysis: C, 77%; H, 4% Synthesis Example 3 Synthesis of Intermediate 1-3

3]

In a nitrogen environment, 1-2 (100 g, 238 mmol) was dissolved in 1 L of dimethylforamide (DMF), followed by bis (pinacolato) diboron (72.5 g, 285 mmol, Aldrich) and (Ι, Γ- bis (diphenylphosphine) ferrocene ) Dichloropalladium (II) (2 g, 2.38 mmol), and potassium acetate (58 g, 595 mmol) were added thereto, and the resulting mixture was heated and refluxed at 150 ^° C. for 48 hours. After completion of reaction, water was added to the reaction solution, and the mixture was filtered and dried in a vacuum oven. The obtained residue was separated and purified through column chromatography, obtaining Compound 1-3 (107 g, 88%).

HRMS (70 eV, EI +): m / z calcd for C 33 H 30 BN 3 O 2: 51 1.2431, found: 51 1

Elemental Analysis: C, 77%; H, 6% Synthesis Example 4 Synthesis of Intermediate 1-4

In a nitrogen environment, the above compound 1-3 (50 g, 98 mmol) was dissolved in 1 L of THF, followed by 1-bromo-3-iodobenzene (33 g, 1 17 mmol, Aldrich) and tetrakis (triphenylphosphine) palladium (1 g, 0.98 mmol) and stirred. Potassium carbonate saturated in water (34 g, 245 mmol) was added thereto, and the resulting mixture was heated and refluxed at 80 ^° C. for 12 hours. After the reaction was completed, water was added to the reaction solution, extracted with dichloromethane (DCM), water was removed with anhydrous MgS04, filtered, and concentrated under reduced pressure. The obtained residue was separated and purified through column chromatography, obtaining Compound 1-4 (50 g, 95%).

HRMS (70 eV, EI < + >): m / z calcd for C 30 H 27 BO 2: 539.0997, found: 539 Elemental Analysis: C, 73.34; H, 4.10

95 g (88%) of intermediates 1-5 were obtained by synthesis and purification in the same manner as in the synthesis of intermediates 1-3.

HRMS (70 eV, EI < + >): m / z calcd for C 39 H 34 BN 302: 587.2744, found: 587 Elemental Analysis: C, 80%; H, 6% Synthesis Example 6 Synthesis of Intermediate 1-10

Scheme 6

Synthesis and purification were carried out in the same manner as the synthesis of Intermediate i- ₄ , to obtain 50 g (95%) of Intermediates 1-10.

HRMS (70 eV, EI +): m / z calcd for C30H27BO2: 539.0997, found: 539

Elemental Analysis: C, 73.34; H, 4.10 Synthesis Example 7 Synthesis of Intermediate 1-11

7]

Synthesis and purification in the same manner as in the synthesis of Intermediate 1-3, Intermediate 1-1 1 95 g

(88%) ol was obtained.

HRMS (70 eV, EI +): m / z calcd for C39H34BN302: 587.2744, found: 587

Elemental Analysis: C, 80%; H, 6% Synthesis Example 8 Synthesis of Intermediate 1-27

Synthesis and purification were carried out in the same manner as the synthesis of Intermediate 1-4 to obtain 50 g (95%) of Intermediate 1-27.

HRMS (70 eV, EI +): m / z calcd for C39 H26 BrN3: 615.1310, found 616

Elemental Analysis: C, 76%; H, 4% Synthesis Example 9 Synthesis of Intermediate 1-28

[Banungsik 9]

Synthesis and purification were carried out in the same manner as the synthesis of Intermediate 1-3 to give 86 g (80%) of Intermediate 1-28.

HRMS (70 eV, EI +): m / z calcd for C45H38BN302: 663.3057, found: 663

Elemental Analysis: C, 81%; H, 6% Synthesis Example 10 Synthesis of Intermediate 1-37

10]

Synthesis and purification were carried out in the same manner as the synthesis of Intermediate 1-3 to obtain 100 g (89%) of Intermediate 1-37. Synthesis Example 11 Synthesis of Intermediate 1-38

Π]

54 g of intermediate 1-38 by synthesis and purification in the same manner as in the synthesis of Intermediate 1-4

(73%) was obtained. Synthesis Examples 12 to 16: Synthesis of Intermediates Having Pyridine Cores

Banungsik 13]

Rebellion 15]

Scheme 16]

Intermediates 1-1 to Intermediate 1-5, Intermediate 1-, except that 4-chloro-2,6-diphenylpyridine (TCI) was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine. 10, Intermediate 1-1 Synthesis and purification were carried out in the same manner as in the synthesis of 1 to 1 to intermediate 1-12 to intermediate 1-16. Synthesis Examples 17 to 21 Synthesis of Intermediates Having Pyrimidine Cores

17]

1-17

18]

19]

20]

Intermediates 1-1 to Intermediate 1, except that 2-chloro-4,6-diphenyl-1,3-pyrimidine (TCI) ar was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine. -5, Intermediate 1-10, Intermediate 1-1 Synthesis and purification in the same manner as in the intermediate 1-1 to intermediate 1-21 Obtained. Synthesis Examples 22 to 26 Synthesis of Intermediate Having Phenylene Core

1-22

Scheme 24]

Banungsik 25]

4,4 '-(5-bromo-l, 3-phenylene) dipyridine (JP2008-127326A, see Example 1 of CHEMIPROKASEI KAISHA) instead of 2-chloro-4,6-diphenyl-l, 3 ₅ 5-triazine Thing Except for the synthesis of the intermediates 1-1 to 1-5, intermediate 1-1, intermediate 1-1 1 and the synthesis in the same manner as in the synthesis to obtain the intermediate 1-22 to intermediate 1-26. Synthesis Example 27 Synthesis of Intermediate 1-39

[Banungsik 27]

1-39

Synthesis and purification were carried out in the same manner as the synthesis of Intermediate 1-4 to obtain 35 g (57%) of Intermediate 1-39. Synthesis Example 28 Synthesis of Intermediate 1-40

Banungsik 28]

Synthesis and purification were carried out in the same manner as the synthesis of Intermediate 1_4 to give 44 g (99%) of Intermediate 1-40. Synthesis Example 29 Synthesis of Intermediate 1-41

Banungsik 29]

Synthesis and purification were carried out in the same manner as the synthesis of Intermediate 1-3 to obtain 42 g (72%) of Intermediate 1-41. Synthesis Example 30 Synthesis of Intermediate Ll

[30]

30 g (162.68 mmol, 2,4,6-trichloro-1,3,5-triazine) in a 500 mL flask

Aldrich) is dissolved in 325 ml of solvent tetrahydrofuran. Cool the solvent with ice water, and then use a dropping sheet inside a nitrogen stream to

Drop 54.23 ml (162.68 mmol) of phenylmagnesium bromide slowly.

Add phenylmagnesium bromide, and after 30 minutes, add water to terminate the reaction. Tetrahydrofuran and water are separated to remove water, and then tetrahydrofuran is removed through a distillation to obtain a solid. The solid is filtered after stirring with 100 ml of methanol. Solids were stirred again with 100 ml of nucleic acid, followed by filtration to obtain Intermediate L-l (27 g, 73% yield).

calcd. C 9 H 5 C 12 N 3: C, 47.82; H, 2. 23; C1, 31.37; N, 18.59;

found: C, 47.56; H, 2. 12; CI, 31.42; N, 18.43 Synthesis Examples 31 to 32: Synthesis of Intermediate L-7, and Intermediate L-8

Intermediates L-7, and L-8ols, presented as more specific examples of the compounds of the present invention, were synthesized in the same manner as in the synthesis of Intermediates 1-39, 1-40, and 1-41 according to Synthesis Examples 27 to 29. (3 basic reactions: Suzuki reaction, Br boration reaction, C1 boration reaction)

Scheme 31

Synthesis Example 33 Synthesis of Compound A-1

Compound 1-5 (20 g, 34 mmol) was dissolved in 0.2 L of tetrahydrofuran (THF) in a nitrogen environment, and 3-bromo-l, l'-biphenyl (9.5 g, 40 mmol) was added thereto.

tetrakis (triphenylphosphine) palladium (0.39 g, 0.34 mmol) ol was added and stirred. Potassium carbonate saturated in water (12 g, 85 mmol) was added and heated at 80 ^° C for 20 hours.

It was refluxed. After the reaction was completed, water was added to the reaction solution, extracted with dichloromethane (DCM), and then water was removed with anhydrous MgS04, filtered, and concentrated under reduced pressure. The obtained residue was separated and purified through column chromatography, obtaining Compound A-1 (24 g, 70%).

HRMS (70 eV, EI +): m / z calcd for C 45 H 31 N 3: 613.2518, found: 613

Elemental Analysis: C, 88%; H, 5% Synthesis Examples 34-39: Synthesis of Compound

HRMS

Composite (70 eV,

Starting material 1 Starting material 2

EI +)

Found

34 689

Α-7

Synthesis of Second Compound

Synthesis Example 40 Synthesis of Intermediate M-1

[34]

Synthesis and purification were carried out in the same manner as in the synthesis of M-1 intermediate 1-4, to obtain intermediate M-127 g. LC-Mass (Theoretical value: 322.00 g / mol, Measured value: M + = 322.09 g / mol, M + 2 = 324.04 g / mol) Synthesis Example 41: Synthesis of Intermediate M-2

[35]

Synthesis and purification were carried out in the same manner as the synthesis of M-2 intermediate i_4 to obtain 29 g (91%) of intermediate M-2.

LC-Mass (Theoretical value: 337.98 g / mol, Measured value: M + = 338.04 g / mol, M + 2 = 340.1 1 g / mol) Synthesis Example 42: Synthesis of Intermediate M-3

[36]

Synthesis and purification in the same manner as in the synthesis of Intermediate I_2 23.9 g of Intermediate M-3

(91%) was obtained.

LC-Mass (Theoretical value: 278.05 g / mol, Measured value: M + = 278.12 g / mol, M + 2 = 280.13 g / mol) Synthesis Example 43: Synthesis of Intermediate M-4

[Banungsik 37]

Synthesis and purification in the same manner as in the synthesis of Intermediate 1-2 25.6 g of Intermediate M-4

(92%) was obtained.

LC-Mass (Theoretical value: 294.03 g / mol, Measured value: M + = 294.16 g / mol, M + 2 = 296.13 g / mol) Synthesis Example 44 Synthesis of Intermediate M-5

[Banungsik 38]

10 g (30.9 mmol) of intermediate M-l, 6.3 g (37.08 mmol) of 4-aminobiphenyl, and 5.35 g (55.6 mmol) of sodium t-butoxide were added to the back bottom flask, and 155 ml of toluene was added to dissolve it. 0.178 g (0.31 mmol) of Pd (dba) 2 and 0.125 g (0.62 mmol) of tri-tertiary-butylphosphine were sequentially added thereto, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with ethyl acetate and distilled water, and then 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-nucleic acid / dichloromethane (7: 3 volume ratio) to give 9.92 g (78%) of the intermediate compound M-5.

. LC-Mass (Theoretical value: 41 L16 g / mol, Measured value: M + = 411.21 g / mol) Synthesis Example 45: Synthesis of Intermediate M-6

[Banungsik 39]

Synthesis and purification were carried out in the same manner as the synthesis of Intermediate M-5 to obtain 11 g (76%) of Intermediate M-6.

LC-Mass (Theoretical value: 467.17 g / mol, Measured value: M + = 467.23 g / mol) Synthesis Example 46: Synthesis of Intermediate M-7

Synthesis and purification were carried out in the same manner as the synthesis of Intermediate M-5 to obtain 10.6 g (80%) of Intermediate M-7.

LC-Mass (Theoretical value: 427.14 g / mol, Measured value: M + = 427.19 g / mol) Synthesis Example 47: Synthesis of Intermediate M-8

Scheme 41

Synthesis and purification were carried out in the same manner as the synthesis of Intermediate M-5 to obtain 10.5 g (80%) of Intermediate M-8.

LC-Mass (Theoretical value: 427.14 g / mol, Measured value: M + = 427.20 g / mol) Synthesis Example 48: Synthesis of Intermediate M-9

[Banungsik 42]

Toluene, refax, 12h

20 g (94.3 mmol) of 4-dibenzofuranboronic acid and 16.2 g (94.3 mmol) of 4-bromoaniline were added to an M-9 back bottom flask, toluene (300 ml) was added to dissolve, and 19.5 g (141.5 mmol) of potassium carbonate was dissolved. 117 ml of dissolved aqueous solution was added and stirred. Tetrakistriphenylphosphinepalladium L09g (0.94 mmol) was added thereto.

The mixture was refluxed and stirred for 12 hours under a nitrogen atmosphere. After completion of reaction, use ethyl acetate After extraction, the extract was dried over magnesium sulfate and filtered, and the filtrate was decompressed.

Concentrated. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (9: 1 volume ratio) to give 17.4 g (yield 71%) of the target compound intermediate M-9 as a white solid.

LC-Mass (Theoretical value: 259.1 g / mol, Measured value: M + = 259.2 lg / mol) Synthesis Example 49: Synthesis of Intermediate M-10

Scheme 43

10 g (30.9 mmol) of intermediate M-1, 9.6 g (37.08 mmol) of intermediate M-9 and 5.35 g (55.6 mmol) of sodium t-butoxide were added to the back bottom flask, and 155 ml of toluene was added and dissolved. 0.178 g (0.31 mmol) of Pd (dba) 2 and 0.125 g ((..62 mmol) of tri-tertiary-butylphosphine were added thereto in this order, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with toluene and distilled water, and then 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 -nucleic acid / dichloromethane (7: 3 volume ratio) to give 11.2 g (yield 72%) of the target compound Intermediate M-10 as a white solid.

LC-Mass (Theoretical value: 501.17 g / mol, Measured value: M + = 50L31g / mol)

15 g (46.4 mmol) of Intermediate M-1 and 4-aminobiphenyl in a round bottom flask. 3.9 g (23.2 mmol) and 6.7 g (69.6 mmol) of sodium t-butoxide were added and 155 ml of toluene was added to dissolve it. Here, 0.53 g (0.928 mmol) of Pd (dba) 2 and tri-tertiary-butylphosphine

0.38 g (1.86 mmol) was added sequentially, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. After the completion of reaction, the mixture was extracted with toluene and distilled water, and then 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 -nucleic acid / dichloromethane (8: 2 volume ratio) to give 13.7 g (90%) of the title compound H-1.

LC-Mass (Theoretical value: 653.24 g / mol, Measured value: M + = 653.31 g / mol) Synthesis Examples 51 to 62: Synthesis of Compound

yield(%)

LC- Synthesis Example Starting Material 1 Starting Material 2 Product

Mass (M + H ⁺ )

87%

51

693.32

Η-2

88%

52 00 761.28

Hl l 82% 761.29

92% 563.28

85% 727.31

93% 725.30

H-98

800.00 / ST0ZaM / X3d 9 »890 / 9ΐΟΖ OAV (Synthesis law: US2005- 79%

817.38 0221124 Compound Ε

See synthesis method,

Where to Buy Starting Material: Η-97

TCI) Synthesis of Third Compound

Synthesis Example 63 Synthesis of Compound D-1

[Banungsik 45]

D-1

Step 1: Synthesis of Intermediate (A)

140.4 g (674 mmol) of 2-Benzalacetophenone, 199.04 g (808.77 mmol) of pyridine salt compound, 415.6 g (5391 mmol) of ammonium acetate were suspended in methane (1720 ml), followed by stirring under reflux at 1 KTC for 2 hours. After the reaction, the product is precipitated in distilled water to give a solid

Formed and the resulting solid was filtered to yield 106 g (64%) of intermediate (A).

Second Step: Synthesis of Intermediate (B)

100 g (405.67 mmol) of intermediate (A), 172.74 g (1217 mmol) of P ₂ 0 _{5, and} 196.17 g (608.5 mmol) of TBAB (Tetra-n-butylammonium bromide) were added, suspended in chlorobenzene, and then 140 ^° C. It was stirred at reflux for 14 hours at C. After the reaction, the solvent was removed, the organic layer extracted with dichloromethane and distilled water was filtered through silica gel, the obtained organic layer was removed to 150 ml, and methanol was poured to form a precipitate. The resulting solid was filtered to give 89 g (71) of an intermediate (B). %) Was obtained.

Third Step: Synthesis of Compound J

With starting material phenyl-9H-carbazol-3-yl boronic acid (9-phenyl-9H-carbazol-3-yl boronic acid)

3-bromocarbazole was purchased from TCI and synthesized in the same manner as in the synthesis of Compound A-1. After ending the reaction, pour the methane into the reaction

After filtering the solids, the solids are again dissolved in chlorobenzene and activated carbon and

Anhydrous magnesium sulfate is added and stirred. After filtering the solution, chlorobenzene and methanol Recrystallization from a compound gave 22.6 g (68%) of compound J.

HRMS (70 eV, EI +): m / z calcd for C 30 H 20 N 2: 408.16, found: 408

Elemental Analysis: C, 88%; H, 5% Step 4: Synthesis of Compound D-l

22.42 g (54.88 mmol) of the compound represented by the compound J, 20.43 g (65.85 mmol) of 2-bromo-4,6-difetylpyridine (intermediate (B)) obtained in the second step, and tertiary sodium special After dissolving 400 ml of 7.92 g (82.32 mmol) oreluene, 1.65 g (1.65 mmol) of palladium dibenzylideneamine and l / 78 g (4.39 mmol) of tertiary butyl are added dropwise. The reaction mixture was heated and stirred at 1 10 degrees under a stream of nitrogen for 12 hours. After completion of the reaction, the solid produced by pouring methanol into the reaction product was filtered, and then the solid was dissolved in chlorobenzene, and then activated carbon and anhydrous magnesium sulfate were stirred. The solution was filtered and recrystallized with chlorobenzene and methane to obtain 28.10 g (80%) of Compound D-l.

HRMS (70 eV, EI +): m / z calcd for C47H31N3: 637.25, found: 637

Elemental Analysis: C, 89%; H, 5% Synthesis Example 64 Synthesis of Compound D-23

Banungsik 46]

First Step: Synthesis of Intermediate (K)

In the same manner as in the synthesis of Compound D-1, the mixture was purified to 20 g of intermediate (K).

(90%) was obtained.

Second Step: Synthesis of Intermediate (L)

20 g (62.6 mmol) of intermediate (K) was suspended in DMF (200 ml), followed by 1193 g (72.67 NBS). mmol) was added portionwise and stirred at reflux for 12 hours. After distilled water was added and the reaction was terminated, the organic layer obtained by extraction with dichloromethane was filtered through a silica gel filter. The organic solution was then removed and silica gel column with nucleic acid: dichloromethane = 7 _: 3 (Wv) to recrystallize the product solid with dichloromethane and n-nucleic acid to give 22.4 g (90%) of intermediate (L). Third Step: Synthesis of Intermediate (N)

Purification was carried out in the same manner as the synthesis of Intermediate 1-3 to give 22.5 g (90%) of intermediate (N).

Fourth Step: Synthesis of Compound D-23

Intermediate (N) 10 g (34.83 mmol), 9- [1,1'-biphenyl-4-yl] -3-bromo-9H-carbazole (9- [l, l'-Biphenyl-4- yl] -3-bromo-9H-carbazole, TCI), 1 1.77 g (38.31 mmol) and 14.44 g (104.49 mmol) potassium carbonate, tetrakis- (triphenylphosphine) palladium (0) 0.80 g (0.7 mmmol) Was suspended in 140 ml of toluene and 50 ml of distilled water, followed by stirring under reflux for 12 hours. Then recrystallized with dichloromethane and n-nucleic acid to give 18.7g (92%) of Compound D-23.

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

Elemental Analysis: C, 91%; H, 5% Synthesis Example 65 Synthesis of Compound D-Group

47]

Starting materials 3-bromo-9-biphenylcarbazole and phenyl-9H-carbazole_3-yl boronic acid (9-phenyl-9H-carbazol-3-yl boronic acid) Purified from TCI and synthesized in the same manner as in the synthesis of Compound A-1, dichloromethane and n-nucleic acid

Recrystallization gave 13.8 g (92%) of compound D-71.

HRMS (70 eV, EI +): m / z calcd for C36H24N2: 484.19, found: 484 Elemental Analysis: C, 89%; H, 5% Synthesis Example 66 Synthesis of Compound D-72

[Banungsik 48]

Starting material 3-phenyl-3-bromo-9-biphenylcarbazole was synthesized in the same manner as the structural formula 56D of WO2010-041872 and phenyl-9H-carbazole-3 -Yl boronic acid (9-phenyl-9H-carbazol-3-yl boronic acid) was purchased from TCI, synthesized in the same manner as in the synthesis of Compound A-1, and diluted with dichloromethane and n-nucleic acid.

Recrystallization gave 18 g (89%) of compound D-72. Fabrication of Organic Light Emitting Device

Example 1

Glass substrates coated with ΠΌ (Indium tin oxide) to a thickness of 1500A were washed by distilled water ultrasonically. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol and the like was dried and then transferred to a plasma cleaner, and then the substrate was cleaned for 10 minutes using an oxygen plasma, and then the substrate was vacuumed with a vacuum depositor. Ν4, Ν4'-diphenyl-Ν4, Ν4'-bis (9-phenyl-9Η-carbazol-3-yl) biphenyl-4,4'- on the ΠΌ substrate using the prepared ΠΌ transparent electrode as the anode diamine ^{(N4, N 4 '-diphenyl- N4} , N4'-bis (9-phenyl-9H-carbazol-3-yl) biphenyl-4,4'-diamine) ( compound a) by the vacuum vapor deposition thickness of 700 a A hole injection layer is formed and 1,4,5,8,9,1 1-nuclear azatriphenylene-nuclecarbonitrile (1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile is formed on the hole injection layer. , HAT-CN) (Compound B) was deposited to a thickness of 50 A, followed by N- (biphenyl-4-yl) -9,9-dimethyl-N- (4- (9-phenyl-9H-carbazole -3 -yl) phenyl) -9H-fluorene-2-amine (N- (biphenyl-4-yl) -9,9-dimethyl-N- (4- (9- phenyl-9H-carbazol-3-yl) phenyl) -9H-fluoren-2-amine) (Compound C) was deposited to a thickness of 700 A to form a hole transport layer. Compound H-96 obtained in Synthesis Example 58 was vacuum deposited to form a hole transport auxiliary layer having a thickness of 50 A on the hole transport layer. Subsequently, a light emitting layer was formed by doping BH1 13 and BD370 sold by SFC as a blue fluorescent light emitting host and a dopant at 5wt% on the hole transport auxiliary layer to a thickness of 200 A. Subsequently, Compound A-37 obtained in Synthesis Example 37 was vacuum deposited on the light emitting layer to form an electron transport auxiliary layer having a thickness of 50 A.

Then 8- (4- (4- (naphthalen-2-yl) -6-naphthalen-3-yl) -1,3,5-triazin-2-yl) phenyl) quinoline on top of the electron transport auxiliary layer (8- (4- (4- (naphthalen-2-yl) -6- (naphthalen-3-yl) -1,3,5-triazin-2-yl) phenyl) quinoline) (Compound E) and Liq At the same time, an electron transport layer having a thickness of 310 A was formed by vacuum deposition at a ratio of 1: 1, and an organic light emitting device was manufactured by sequentially depositing Liq l 5 A and AU200A on the electron transport layer to form a cathode.

The organic light emitting device has a structure having seven organic thin film layers, specifically

ITO / A (700A) / B (5 0A) / C (700A) / hole transport assisting layer ^{[H -% (5 0A)} ]

/ EML [BH1 13: BD370 (95: 5wt%)] (200A) / electron transport auxiliary layer [A-37 (50A) / E: Liq = l: l (310A) / Liq (15A) / Al (1200A ) ≤ structure was made. Example 2

An organic light emitting diode was manufactured according to the same method as Example 1 except for using the compound H-98 obtained in Synthesis Example 56 instead of the compound H-96 for the hole transport supplement. Example 3

An organic light emitting diode was manufactured according to the same method as Example 1 except for using the compound E-70 obtained in Synthesis Example 55 instead of the compound H-96 for the hole transport auxiliary layer. Example 4

An organic light emitting device was manufactured in the same manner as in Example 1, except that the hole transport layer (compound C) was deposited to a thickness of 750 A without forming a hole transport auxiliary layer. Example 5

The same method as in Example 1, except that Compound A-7 obtained in Synthesis Example 34 and Compound 72 obtained in Synthesis Example 66 were formed by vacuum deposition at a weight ratio of 6: 4 in an electron transport aid to form a 50 A thick layer. An organic light emitting device was manufactured. Example 6

Compound H-97 obtained in Synthesis Example 62 was used for the hole transport auxiliary layer instead of Compound H-96, and Compound A-7 obtained in Synthesis Example 34 and Compound D-72 obtained in Synthesis Example 66 were used for the electron transport auxiliary layer 6: An organic light emitting diode was manufactured according to the same method as Example 1 except that a 50 A thick layer was formed by vacuum deposition at a weight ratio of 4. Example 7

Compound H-1 1 obtained in Synthesis Example 52 was used for the hole transport auxiliary layer instead of Compound H-96, and Compound A-7 obtained in Synthesis Example 34 and Compound D-72 obtained in Synthesis Example 66 were used for the electron transport auxiliary layer. An organic light emitting diode was manufactured according to the same method as Example 1 except for forming a 50A thick layer by vacuum deposition at a weight ratio of 4: 4. Example 8

Compound H-1 1 obtained in Synthesis Example 52 was used for the hole transport auxiliary layer instead of Compound H-6, and Compound A-7 obtained in Synthesis Example 34 and Compound D-72 obtained in Synthesis Example 66 were used for the electron transport auxiliary layer. An organic light emitting diode was manufactured according to the same method as Example 1 except for forming a 50 A thick layer by vacuum deposition at a weight ratio of 6: 6. Example 9

Compound H-1 1 obtained in Synthesis Example 52 was used for the hole transport auxiliary layer instead of Compound H-96, and Compound A-24 obtained in Synthesis Example 35 and Compound D-group obtained in Synthesis Example 65 were used as the electron transport auxiliary layer: An organic light emitting diode was manufactured according to the same method as Example 1 except that a 50 A thick layer was formed by vacuum deposition at a weight ratio of 1. Example 10 An organic light emitting device was manufactured in the same manner as in Example 5, except that the hole transport layer (compound C) was deposited to a thickness of 750 A without forming a hole transport auxiliary layer. Example 11

An organic light emitting device was manufactured in the same manner as in Example 8, except that the hole transport layer (compound C) was deposited to a thickness of 750 A without forming a hole transport auxiliary layer. Example 12

An organic light emitting device was manufactured in the same manner as in Example 9, except that the hole transport layer (compound C) was deposited to a thickness of 750 A without forming a hole transport auxiliary layer. Comparative Example 1

Compound is formed in the electron transport layer without forming the hole transport auxiliary layer, by depositing the hole transport layer (Compound C) to a thickness of 750 A, and without forming the electron transport auxiliary layer.

An organic light emitting diode was manufactured according to the same method as Example 1 except for depositing the compound E: Lic l: l (360 A) instead of E: Liq = l: l (310A). evaluation

The luminous efficiency and the -off characteristics of the organic light emitting diodes according to Examples 1 to 12 and Comparative Example 1 were evaluated.

Specific measurement methods are as follows, and the results are shown in Table 2.

(1) Measurement of change of current density according to voltage change

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

(2) Measurement of luminance change according to voltage change

For the organic light emitting device manufactured, while increasing the voltage from 0V to 10V The luminance at that time was measured using a luminance meter (Minolta Cs-IOOOA) to obtain a result.

(3) Measurement of luminous efficiency

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

(4) life measurement

Maintaining the luminance (cd / m2) to 750 cd / m ² and a current efficiency (cd / A) is the time to decrease to _97%, measured to obtain a result.

TABLE 1

Referring to Table 1, the organic light emitting device according to Examples 1 to 12 according to Comparative Example 1 Compared with the organic light emitting device, it can be seen that the luminous efficiency and lifespan characteristics are significantly improved at the same time. The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims

[Range of request]

[Claim 1]

Anodes and cathodes facing each other,

A light emitting layer positioned between the anode and the cathode,

An electron transport layer between the cathode and the light emitting layer, and

An electron transport auxiliary layer positioned between the electron transport layer and the light emitting layer

Including,

The electron transport auxiliary layer is an organic optoelectronic device comprising at least one first compound represented by Formula 1 below:

One]

In Chemical Formula 1,

Ζ is each independently N, C or CR ^a ,

At least one of Z is N,

nl to n6 are each independently an integer of 0 to 5,

Wherein "substituted"'at least one hydrogen is deuterium, halogen, hydroxy, amino, substituted or unsubstituted C1 to C30 amine group, nitro group, substituted or unsubstituted C1 to C40 silyl group, C1 to C30 alkyl group, C3 to C30 cycloalkyl group, C2 to C30 It means substituted with a 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.

[Claim 2]

Anode and cathode facing each other,

A light emitting layer located between the anode and the cathode,

A hole transport layer between the phase ⁷ anode and the light emitting layer,

Phase 7 hole transport auxiliary layer located between the hole transport layer and the light emitting layer,

An electron transport layer located between the phase ⁷ cathode and the light emitting layer, and

An electron transport auxiliary layer positioned between the phase ⁷ electron transport layer and the light emitting layer, and the phase ⁷ electron transport auxiliary layer includes at least one first compound represented by Formula 1 below,

The hole transport auxiliary layer is an organic optoelectronic device comprising at least one second compound represented by Formula 2 below:

In Chemical Formula 1,

Z are each independently N, C or CR ^a ,

At least one of Z is N,

R ¹ to R ⁶ , and R ^a are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group Or a combination thereof,

L ¹ to L ⁶ are each independently a single bond, a substituted or unsubstituted C6 to C30 85 arylene group, a substituted or unsubstituted heteroarylene group, or a combination thereof

nl to n6 are each independently an integer of 0 to 5,

2] .

In Chemical Formula 2,

X ¹ is 0 or S,

R ⁷ to R ⁹ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or Unsubstituted C3 to C20 cycloalkoxy group, substituted or unsubstituted C 1 to C20 alkylthio group, substituted or unsubstituted C6 to C30 ^' aralkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C6 to C30 arylthio group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 amino group, substituted or unsubstituted C3 to C30 Silyl group, cyano group, nitro group, hydroxyl group or carboxyl group, or a combination thereof,

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

n7 to n9 are each independently an integer of any one of 0 to 3, and the "substituted" of Chemical Formulas 1 and 2 is C1 to C30 in which at least one hydrogen is deuterium, a halogen group, a hydroxyl group, an amino group, or a substituted or unsubstituted group. Amine group, nitro group, substituted or unsubstituted C1 to C40 silyl group, C1 to C30 alkyl group, C3 to C30 It is substituted with a 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.

[Claim 3]

In crab 1 or crab 2,

The first compound is an organic optoelectronic device represented by the general formula 1-1 or 1-

In Chemical Formulas 1-I and 1-Π,

Z are each independently N, C or CR ^a ,

At least one of Z is N,

R 'to R ⁶ , and R ^a are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heteroaryl group, or Combination of these,

nl to n6 are each independently an integer of 0 to 5,

Wherein “substituted” means that at least one hydrogen is deuterium, a halogen group, a hydroxy 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, a C1 to C30 alkyl group, C3 Substituted with 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, a C1 to C10 trifluoroalkyl group, or a cyano group Means that. [Claim 4]

In paragraph 1 or crab 2,

The first compound is an organic optoelectronic device represented by at least one of the formula l-m to 1-X:

[Formula l-m] [Formula l-iv]

-vm] [Formula

In Chemical Formulas i-m to 1-K,

Z are each independently N or CR ^a ,

At least one of Z is N,

Each W is independently N, C or CR ^b ,

5 ^a to R ^5d , R ^a , and R ^b are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 hetero An aryl group or a combination thereof,

Wherein "substituted" means that at least one hydrogen is deuterium, a halogen group, a hydroxy 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, a C1 to 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 do.

[Claim 5]

The method of claim 1 or 2,

Wherein said first compound is at least one compound compound listed in Group 2 below:

[Group 2]

[A-1] [A-2] [A-3]

68

800.00 / £ Ϊ0ΖΗΜ / Χ3 <1

9 »890 / 9ΐΟΖ ΟΛ \

800.00 / ST0ZaM / X3d 9 »890 / 9ΐΟΖ OAV

800.00 / ST0ZaM / X3d 9 »890 / 9ΐΟΖ OAV

-V] [89-V] [/.9-V]

800.00 / ST0ZaM / X3d 9 »890 / 9ΐΟΖ OAV 93

[88-V] [8-VJ [98-V] t6

800.00 / ST0ZaM / X3d 9 »890 / 9ΐΟΖ OAV

OAVĠ

-51] [B-52] [B-53]

C-l] C-2] [C-3]

[-4] [C-5]

[Claim 6]

The method of claim 1 or 2,

The electron transport auxiliary layer is an organic optoelectronic device further comprising at least one third compound represented by the following formula (3): 3]

In Chemical Formula 3,

L ¹⁰ to L ¹² 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 ³ and Ar ⁴ are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group or a combination thereof,

R ¹⁰ to R ¹³ 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 a combination thereof ,

Wherein “substituted” means that at least one hydrogen is a hydrogen, halogen, hydroxy, amino, substituted or unsubstituted C1 to C30 amine group, nitro group, substituted or unsubstituted C 1 to C40 silyl group, C1 to C30 alkyl group Substituted with 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 fluoro group, a C1 to C10 trifluoroalkyl group, or a cyano group Means that.

[Claim 7]

In claim 6,

The additive third compound is an organic optoelectronic device represented by at least one of the following Chemical Formulas 3- 1 to 3-ΙΠ: 3-1] [Formula 3-Π]

In Chemical Formulas 3-1 to 3-ΠΙ,

R'O to R ^l3 are each independently hydrogen, deuterium, substituted or unsubstituted C1 to

A C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, a substituted or unsubstituted C50 heteroaryl group in C2, or a combination thereof,

Wherein ΕΤ, ΕΊΊ, and ΕΤ2 are each independently selected from substituted or unsubstituted groups listed in Group 3,

Wherein ΗΤ, ΗΤΙ, and ΗΤ2 are each independently selected from substituted or unsubstituted groups listed in Group 4: Group 3]

Wherein “substituted” means that at least one hydrogen is deuterium, a halogen group, a hydroxy 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, a C1 to C30 alkyl group, C3 Substituted with 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, a C1 to C10 trifluoroalkyl group, or a cyano group It means, _and

In groups 3 and 4 above, * is the point of attachment.

[Claim 8]

In crab 6,

Wherein said third compound is selected from the compounds listed in Group 5:

[Group 5]

D-l] [D-2] [D-3] [-4]

[D-5] [D-6] [D-7] [D-8]

[D-l 3] [D-l 4] [D-l 5] [D-16] [D-17]

[9 -Q] [-α] [ε ^ α]

[9ε-α] [ςε-α] [-α] [εε-α]

[9 -α] [ςζ-α] [ZQ] [zz-a]

9 »890 / 9ΐΟΖ OAV

In paragraph 6, The electron transport aid,

At least one of the first compounds represented by Formulas i-m to l-x; An organic optoelectronic device comprising at least one of the third compounds represented by the following formula 3- 1 to 3-m:

[Formula i-m] [Formula l-iv]

i-vm] [Formula lK]

In the formula i-m to 1-K,

Z are each independently N or CR ^a ,

At least one of Z is N,

W are each independently N, C or CR ^b ,

R ^5a to R ^5d , R ^a , and R ^b are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 solution Teroaryl groups or combinations thereof,

[Formula 3-1] [Formula 3-Π]

In Chemical Formulas 3-1 to 3-m,

_L io to L ¹² each independently represent a single bond, a substituted or unsubstituted C6. A C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,

Wherein ΕΤ, ΕΤΙ, and ΕΤ2 are each independently selected from substituted or unsubstituted groups listed in Group 3,

Wherein ΗΤ, ΗΤΙ, and ΗΤ2 are each independently selected from substituted or unsubstituted groups listed in Group 4:

[Group 3]

[Group 4]

* In groups 3 and 4 is a point of attachment,

Wherein "substituted" means that at least one hydrogen is deuterium, a halogen group, a hydroxy 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, a C1 to C30 alkyl group, C3 Substituted with 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, a C1 to C10 trifluuroalkyl group, or a cyano group it means.

[Claim 10]

In 19,

The electron transport auxiliary layer,

At least one of the first compounds represented by the above formula (l-iv) and (i-νπ); And ^'

An organic optoelectronic device comprising at least one of the third compound represented by the formula 3-m. ᅳ

[Claim 1 11]

In paragraph 2,

The second compound is an organic optoelectronic device represented by the following formula 2- 1 or formula 2-

In the above formula 2- 1 and 2- 2-

X ¹ is 0 or S,

R ⁷ to R ⁹ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or Unsubstituted C3 to C20 cycloalkoxy group _: substituted or unsubstituted C1 to C20 alkylthio group, substituted or unsubstituted C6 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 To C30 aryloxy group, substituted or unsubstituted C6 to C30 arylthio group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 amino group, substituted or unsubstituted C3 to C30 silyl group , Cyano group, nitro group, hydroxyl group or carboxyl group, or a combination thereof,

Ar ¹ and Ar ² are each independently a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

n7 to n9 are each independently an integer of any one of 0 to 3, wherein "substituted" is a C1 to C30 amine group or a nitro group in which at least one hydrogen is deuterium, a halogen group, a hydroxyl group, an amino group, a substituted or unsubstituted group, and , Substituted or unsubstituted C 1 to C40 silyl group, C 1 to C30 alkyl group, C3 to C30 cycloalkyl group, C2 to C30 heterocycloalkyl 7j, C6 to C30 aryl group, C2 to C30 heteroaryl group, C1 to C20 It is substituted with an alkoxy group, a fluoro group, a CI to C10 trifluoroalkyl group, or a cyano group.

[Claim 12]

In claim 2,

The second compound is an organic optoelectronic device represented by at least one of formula 2-m to formula 2-X I:

2-m] [Formula ² -iv] [Formula 2-v]

-VI] [Formula 2-νΠ] [Formula 2- 曹]

[Formula 2-Κ] [Formula 2- Χ]

In Formula 2-m to Formula 2-X I,

X ¹ and X ³ are each independently 0 or S,

X ² is 0, S, or CR ⁱ R ^j ,

R ⁷ to R ⁹ , and R ^c to R ^j are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C3 to C20 cycloalkoxy group, substituted or unsubstituted C1 to C20 alkylthio group, substituted or unsubstituted C6 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, Substituted or unsubstituted C6 to C30 aryloxy group, substituted or unsubstituted C6 to C30 arylthio group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 amino group, substituted or unsubstituted C3 to C30 silyl group, cyano group, nitro group, hydroxyl group or carboxyl group, or a combination thereof,

Ar ¹ and Ar ² are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted

Quarterphenyl groups, substituted or unsubstituted naphthyl groups, substituted or unsubstituted anthracenyl groups, substituted or unsubstituted phenanthrenyl groups, substituted or unsubstituted pyrenyl groups, substituted or unsubstituted triphenylene groups, substituted Or an unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, a substituted or unsubstituted dibenzothiophenyl group, or a combination thereof,

n7 to n9 are each independently an integer of any one of 0 to 3, wherein "substituted"'means that at least one hydrogen is deuterium, a halogen group, a hydroxy group, Amino group, substituted or unsubstituted C1 to C30 amine group, nitro group, substituted or unsubstituted C1 to C40 silyl group, C 1 to 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, a fluoro group, C1 to C10 trifluoroalkyl group or a cyano group.

【Claim 13】

. In claim 2,

Formula 2 of Ar ¹ and Ar ² are, each independently, to an organic optoelectronic one selected from substituted or unsubstituted groups listed in the group 6 elements:

[Group 6

In group 6 above,

Y is 0, S, CR'R ^m , SiR ⁿ R ° or NRP,

* Is the junction point,

R ^k to RP are each independently 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 A C6 to C30 aryl group, substituted or Unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 amino group, substituted or unsubstituted C3 to C30 silyl group, or a combination thereof,

Wherein “substituted” means that at least one hydrogen is deuterium, a halogen group, a hydroxy 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, a C1 to 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 do.

[Claim 14]

In claim 2,

The electron transport auxiliary layer, at least one of the first compound represented by the following formula i-m to formula 1-x,

The hole transport auxiliary layer, an organic optoelectronic device comprising at least one of the second compounds represented by the following formula 2-ΠΙ to Formula 2-X I:

i-m] [Formula

[Formula 1-V] [Formula 1-VI]

In Chemical Formulas i-m to 1-κ,

Z are each independently N or CR ^a ,

At least one of Z is N,

W are each independently N, C or CR ^b ,

R ^5a to R ^5d , R ^a , and R ^b are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 solution A teroaryl group or a combination thereof,

[Formula 2-ΠΙ] [Formula 2-IV] [Formula 2-V]

2- VI] [Formula 2-VH] [Formula 2-vm]

2-K] [Formula 2- X]

In Formula 2-m to Formula 2-X I,

X ¹ and X ³ are each independently 0 or S,

X ² is 0, S, or CR ⁱ R ^j ,

R ⁷ to R ⁹ , and R ^c to R ^j are each independently hydrogen, deuterium, halogen, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C3 to C20 cycloalkyl group, substituted or unsubstituted C1 To C20 alkoxy group, substituted or unsubstituted C3 to C20 Cycloalkoxy group, substituted or unsubstituted C1 to C20 alkylthio group, substituted or unsubstituted C6 to C30 aralkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C6 to C30 aryloxy group, Substituted or unsubstituted C6 to C30 arylthio group, substituted or unsubstituted C2 to C30 heteroaryl group, substituted or unsubstituted C2 to C30 amino group, substituted or unsubstituted C3 to C30 silyl group, cyano group, nitro group , A hydroxyl group or a carboxyl group, or a combination thereof,

Ar 'and Ar ² are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted

n7 to n9 are each independently an integer of any one of 0 to 3, wherein "substituted" is a C1 to C30 amine group or a nitro group in which at least one hydrogen is deuterium, a halogen group, a hydroxyl group, an amino group, a substituted or unsubstituted group, and , Substituted or unsubstituted C1 to C40 silyl group, C1 to 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, fluorine Roh group, C1 to C10 trifluoroalkyl group or cyano group means a substituted.

[Claim 15]

The method of claim 14,

The electron transport auxiliary layer, the compound 1 is represented by the formula l-iv, and the formula ι-νπ,

The hole transport auxiliary layer is an organic optoelectronic device comprising at least one of the second compound represented by Formula 2-νΠ, Formula 2-, Formula 2-C, and Formula 2-C.

[Claim 16]

The method of claim 14, The electron transport auxiliary layer, an organic optoelectronic device further comprising a third compound represented by the following formula 3-m:

3-m]

In the above formula 3-m,

Wherein said ΗΤ, ΗΤΊ, and ΗΤ2 are each independently selected from substituted or unsubstituted groups listed in Group 4:

[Group 4]

* In group 4 is a connection point,

Wherein “substituted” means at least one hydrogen is deuterium, a halogen group, a hydroxy group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, a substituted or unsubstituted C 1 to C40 silyl group, a C1 to C30 alkyl group, Substituted with 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 fluoro group, a C1 to C10 trifluoroalkyl group, or a cyano group it means.

[Claim 17]

In claim 2,

The hole transport auxiliary layer is in contact with the hole transport layer and the light emitting layer, respectively, and the electron transport auxiliary layer is in contact with the electron transport layer and the light emitting layer, respectively.

[Claim 18]

In claim 1,

The light emitting layer is an organic optoelectronic device further comprising a fluorescent dopant.

[Claim 19]

The method of claim 1 or 2,

The organic optoelectronic device is an organic optoelectronic device selected from the group consisting of an organic light emitting device, an organic photoelectric device, an organic solar cell, an organic transistor, an organic photosensitive drum and an organic memory device.

[Claim 20]

A display device comprising the organic optoelectronic device of claim 1.