WO2015182887A9

WO2015182887A9 - Organic optoelectric device and display device

Info

Publication number: WO2015182887A9
Application number: PCT/KR2015/004248
Authority: WO
Inventors: 김훈; 김창우; 유은선; 정성현; 정호국; 강기욱; 강의수; 김윤환; 류동완; 박재한; 정우석; 조평석
Original assignee: 삼성에스디아이 주식회사
Priority date: 2014-05-30
Filing date: 2015-04-28
Publication date: 2016-09-22
Also published as: WO2015182887A1

Abstract

The present invention relates to an organic optoelectric device and a display device, the organic optoelectric device comprising: an anode and a cathode which face each other; a light emission layer disposed between the anode and the cathode; a hole transport layer disposed between the anode and the light emission layer; and a hole transport auxiliary layer disposed between the hole transport layer and the light emission layer, wherein the hole transport auxiliary layer contains a first compound represented by chemical formula 1 and a second compound represented by chemical formula 2 or 3. Here, chemical formulas 1 to 3 are as described in the specification.

Description

【Specification】

[Name of invention]

Organic optoelectronic devices and displays

Technical Field

An organic optoelectronic device and a display device.

Background Art

Organic optoelectronic diodes (organic optoelectrk diode) is a device that can switch between electrical energy and light energy.

Organic photovoltaic devices can be divided into two types according to the principle of operation. One is an optoelectronic device in which an exciton formed by light energy is separated into electrons and holes, and the electrons and holes are transferred to other electrodes, respectively, to generate electrical energy. 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 attracted much attention recently 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. _.

[Detailed Description of the Invention]

[Technical problem]

One embodiment provides an organic optoelectronic device capable of simultaneously implementing high efficiency and long life characteristics.

Another embodiment provides a display device including the organic optoelectronic device.

Technical Solution

According to an embodiment, an anode and a cathode facing each other, a light emitting layer positioned between the anode and the cathode, a hole transporting layer located between the anode and the light emitting layer, and a hole transport auxiliary positioned between the hole transporting layer and the light emitting layer Including a layer, the hole transport auxiliary layer is a compound represented by Formula 1 and the following Provided is an organic optoelectronic device comprising a second compound represented by Formula 2 or represented by a combination of the following Formulas 3 and 4.

[Formula 1]

Of

\

L ²

\

Ar2

In Chemical Formula 1,

L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C2 to C30 divalent heterocyclic group, these Or a fused ring of combinations thereof,

Ar ¹ to Ar ³ are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, a combination thereof or a fusion ring thereof

At least one of Ar ¹ to Ar ³ is one of a group represented by the following formula (A), a group represented by the combination of the following formula B and the formula (C) or a combination of the following formula B and the formula (D),

[

In Chemical Formulas A to D,

X and Z are 0, S or CR ^a R ^b ,

Two adjacent * of formula B are fused with two adjacent * of formula C or D,

Unfused * of Formula B and Formula C are CR ^ l,

R ¹ to R ⁴ , R ^a to！ 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 CI 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 arylalkyl 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 heterocyclic group, substituted or unsubstituted

C2 to C30 amino group, substituted or unsubstituted C3 to C30 silyl group, halogen, cyano group nitro group, hydroxyl group, carboxyl group, a combination thereof, a fused ring of a combination thereof, or in L ¹ to L ³ of Formula 1 Is the point of connection with at least one,

R ¹ and R ² are each independently present or form a fused ring with each other,

R ³ and R ⁴ are each independently present or form a fused ring with each other,

[Formula ² ] [Formula 3] [Formula ⁴ ]

In Chemical Formulas 2 to 4,

Y ¹ , Y ^la and Y ^lb are each independently a single bond, substituted or unsubstituted C1 to C20 alkylene group, substituted or unsubstituted C2 to C20 alkenylene group, substituted or unsubstituted C6 to C30 arylene group, substituted Or an unsubstituted C2 to C30 divalent heterocyclic group, a combination thereof or a fused ring of a combination thereof,

Ar ⁴ , Ar ^4a and Ar ^4b are each independently a substituted or unsubstituted C6 to C30 avalur substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

Two adjacent * of Formula 3 are fused with two * of Formula 4, two unfused * of Formula 3 are CR ⁵ , CR ⁶ , respectively,

R ⁵ to R ¹⁰ 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 ^ C50 heterocyclic group, or a combination thereof ego,

R ⁵ and R ⁶ are each independently present or connected to each other to form a ring, R ⁷ and R ⁸ are each independently present or connected to each other to form a ring, R ⁹ and R ¹⁰ are each independently present or connected to each other to form a ring, and in R ⁵ to R ^s and Ar ⁴ of formula (2) At least one includes a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted triphenylene group, or a substituted or unsubstituted carbazolyl group,

At least one of R ⁵ to R ¹⁰ , Ar ^4a and Ar ^4b of Formula 3 or 4 includes a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted triphenylene group, or a substituted or unsubstituted carbazolyl group .

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

Advantageous Effects

High efficiency long life organic optoelectronic devices can be implemented.

[Brief Description of Drawings]

1 is a schematic cross-sectional view of an organic optoelectronic device according to an embodiment. [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, by which 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, "substituted" means that at least one hydrogen in a substituent or compound is a deuterium, halogen group, hydroxy group, amino group, substituted or unsubstituted C1 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, C3 to C30 heterocycloalkyl group, C6 to C30 aryl group, C6 to C30 heterocyclic group, C1 to C20 alkoxy group Mean substituted by a C1 to C10 trifluoroalkyl group or a cyano group, such as a, fluoro group, and trifluoromethyl group.

In addition, the substituted halogen, hydroxy, amino, 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, C3 to C30

C1 to C10 trifluoroalkyl groups such as heterocycloalkyl groups, C6 to C30 aryl groups, C6 to C30 heterocyclic groups, C1 to C20 alkoxy groups, fluoro groups, and trifluoromethyl groups Alternatively, two adjacent substituents of the cyano group may be fused to form a ring. For example, the substituted C6 to C30 aryl group may be fused to another adjacent substituted C6 to C30 aryl group to form a substituted or unsubstituted fluorene ring.

As used herein, "hetero" means at least one hetero atom 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, "aryl group" refers to a group having one or more hydrocarbon aromatic moieties and is broadly a form in which hydrocarbon aromatic moieties are connected in a single bond and non-aromatic in which the hydrocarbon aromatic moieties are fused directly or indirectly. Also included are fused rings. Aryl groups are monocyclic, polycyclic or fused

Polycyclic (ie, a ring that divides adjacent pairs of carbon atoms) functional groups. As used herein, a "heterocyclic group" is a concept comprising a heteroaryl group, in addition to carbon (C) in a ring compound such as an aryl group, a cycloalkyl group, a fused ring thereof, or a combination thereof. It means containing at least one hetero atom selected from N, 0, S, P and Si. When the heterocyclic group is a fused ring, the heterocyclic group may include one or more heteroatoms for all or each ring.

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 group, substituted or unsubstituted naphthacenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted biphenyl group, substituted or unsubstituted P-terphenyl group, substituted or unsubstituted m-terphenyl group, substituted Or an unsubstituted chrysenyl group, a substituted or unsubstituted triphenylenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted indenyl group, a substituted or unsubstituted furanyl group, a substituted or unsubstituted thiophenyl group , Substituted or unsubstituted pyryl group, substituted or unsubstituted pyrazolyl group, substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted oxazolyl group, substituted or unsubstituted Substituted thiazolyl group, substituted or unsubstituted oxadiazoleyl group, substituted or unsubstituted thiadiazoleyl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted pyrazinyl Groups, substituted or unsubstituted triazinyl groups, substituted or unsubstituted benzofuranyl groups, Substituted or unsubstituted benzothiophenyl group, substituted or unsubstituted vanzimidazolyl group, substituted or unsubstituted indolyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted Quinazolinyl groups, substituted or unsubstituted

Quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted

Benzoxazineyl 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 dibenzofuranyl group, substituted or unsubstituted dibenzothiophenyl group, substituted or unsubstituted carbazolyl group, a combination thereof, or a combination thereof It may be, but is not limited thereto.

In the present specification, a substituted or unsubstituted arylene group or a substituted or unsubstituted heteroarylene group or a substituted or unsubstituted divalent heterocyclic group is a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group as defined above. In which there are two linking groups, for example, a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalene group, a substituted or unsubstituted anthracenylene group, a substituted or unsubstituted phenanthrylene group, a substitution Or an unsubstituted naphthaceneylene group, a substituted or unsubstituted pyrenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted quarterphenylene group, a substituted or unsubstituted CREE Senylene group, substituted or unsubstituted triphenylenylene group, substituted or unsubstituted perenylene group, substituted or unsubstituted indenylene group, substituted or unsubstituted A substituted furanylene group, a substituted or unsubstituted thiophenylene group, a substituted or unsubstituted pyrylene group, a substituted or unsubstituted pyrazolylene group, a substituted or unsubstituted imidazolylene group, a substituted or unsubstituted triazolyl Benzene group, substituted or unsubstituted oxazolylene group, substituted or unsubstituted thiazolylene group, substituted or unsubstituted

Oxadiazolylene group, substituted or unsubstituted thiadiazolylene group, substituted or unsubstituted pyridinylene group, substituted or unsubstituted pyrimidinylene group, substituted or unsubstituted

Pyrazinylene group, substituted or unsubstituted triazinylene group, substituted or unsubstituted

Benzofuranylene group, substituted or unsubstituted benzothiophenylene group, substituted or unsubstituted benzimidazolylene group, substituted or unsubstituted indolylene group, substituted or unsubstituted quinolinylene group, substituted or unsubstituted Isoquinolinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted quinoxalinylene group, substituted or unsubstituted Naphthyridinylene group, substituted or unsubstituted benzoxazinylene group, substituted or unsubstituted benzthiazinylene group, substituted or unsubstituted acridinylene group, substituted or unsubstituted phenazineylene group, substituted or unsubstituted Phenothiazineylene groups, substituted or unsubstituted

Phenoxazineylene groups, substituted or unsubstituted fluorenylene groups, substituted or unsubstituted

A dibenzofuranylene group, a substituted or unsubstituted dibenzothiophenylene group, a substituted or unsubstituted carbazolene 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 movement in the light emitting layer.

In addition, the electron characteristic refers to a characteristic that can receive electrons when an electric field is applied, and has a conductivity characteristic along the LUMO level, and injects electrons formed in the cathode into the light emitting layer, moves 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, and examples thereof include organic photoelectric devices, organic light emitting devices, organic solar cells, and organic photosensitive drums.

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 "on top" of another part, this includes not only the other part "right over", but also another part in the middle. When the part is "just above", it means that there is no other part in the middle.

1 is a schematic cross-sectional view of an organic light emitting diode according to an embodiment. Referring to FIG. 1, organic light emitting diodes 300 according to an embodiment face each other. An anode 110 and a cathode 120, and an organic layer 105 positioned between the anode 1 10 and the cathode 120, wherein the organic layer 105 is a light emitting layer 130, a hole transport auxiliary layer 142. And a hole transport layer 141.

The anode 110 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 1 10 is, for example, a metal such as nickel, platinum, vanadium, chromium, copper, zinc, gold or an alloy thereof; Zinc oxide, indium oxide, indium tin oxide (ITO),

Metal oxides such as indium zinc oxide (IZO); Combinations of oxides with metals such as ZnO and A1 or Sn0 ₂ and Sb; Conductive polymers such as poly (3-methylthiophene), poly (3,4- (ethylene-1,2-dioxy) thiophene) (polyehtylenedioxythiophene: PEDOT), polypyrrole and polyaniline, and the like. It is not.

The cathode 120 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 120 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, Li0 ₂ / Al, LiF / Ca, LiF / Al, and BaF ₂ / Ca, but are not limited thereto.

The light emitting layer 130 is positioned between the anode 110 and the cathode 120, and includes at least one kind of host and at least one kind of dopant.

The dopant is a substance that is lightly mixed with the host to cause light emission. An organic compound or a metal complex such as A1, or a metal complex such as A1, or multiplexed excitation above the triplet state in the ground state Materials such as metal complexes that emit light by multiple excitation can be used. The dopant may be, for example, an inorganic, organic, or inorganic compound, and may be included in one kind or two or more kinds.

Examples of the dopant include an organometallic compound including Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, Rh, Pd, or a combination thereof. The dopant may be, for example, a compound represented by Chemical Formula z, but is not limited thereto.

[Formula Z]

L ₂ MX In the above formula Z, Μ is a metal, L and X are the same or different from each other and a ligand to form a complex with M.

M may be, for example, Ir, Pt, Os, Ti, Zr, Hf, Eu, Tb, Tm, Fe, Co, Ni, Ru, R, Pd or a combination thereof, wherein L and X are for example bidentate It may be a ligand. The hole transport layer 141 is located between the anode 1 10 and the light emitting layer 130,

Hole transport from the anode 110 to the light emitting layer 130 can be facilitated. For example, the hole transport layer 141 may include a material having a HOMO energy level between the work function of the conductor constituting the anode 1 10 and the HOMO energy level of the material constituting the light emitting layer 130. .

The hole transport auxiliary layer 142 may be positioned between the hole transport layer 141 and the light emitting layer 130 and particularly in contact with the light emitting layer 130. The hole transport auxiliary layer 142 may be positioned in contact with the light emitting layer 130 to precisely control the mobility of holes at the interface between the light emitting layer 130 and the hole transport layer 141. The hole transport auxiliary layer 142 may include a plurality of layers.

The hole transport auxiliary layer 142 may include a plurality of compounds having different energy levels. For example, the hole transport auxiliary layer 142 may include a plurality of compounds having different HOMO energy levels associated with hole mobility.

For example, one of the plurality of compounds may be a compound having a relatively high HOMO energy level and the other compound may be a compound having a relatively low HOMO energy level. Here, the high HOMO energy level means that the absolute value is large with a vacuum level of OeV 'and the low HOMO energy level means that the absolute value is small with a vacuum level of OeV'.

In addition, a compound having a relatively high HOMO energy level and a compound having a relatively low HOMO energy level are a relative concept and have a HOMO energy with a material forming the hole transport layer 141 among materials having a higher HOMO energy level than a material forming the hole transport layer 141. A material having a relatively high level difference corresponds to an electron, that is, a compound having a relatively high HOMO energy level, and a material having a relatively small difference in HOMO energy level from a material forming the hole transport layer 141 is the latter, that is, a HOMO energy level. May correspond to relatively low compounds.

As such, by including a plurality of compounds having different HOMO energy levels together, a compound having a relatively high HOMO energy level and a relatively low HOMO energy level are included. The benefits of the compounds can be used to improve efficiency and lifetime at the same time.

For example, an organic optoelectronic device using a plurality of compounds having different HOMO energy levels together increases hole mobility by reducing the difference in HOMO energy levels between the hole transport layer 141 and the light emitting layer 130, thereby increasing the hole transport layer 141 and the hole. Holes can be prevented from accumulating at the interface between the transport auxiliary layer 142 or the hole transport auxiliary layer 142 and the light emitting layer 130. Accordingly, holes and axtones are combined and extinguished at the interface of each layer. The quenching can be reduced. Accordingly, the device can be stabilized by preventing or preventing deterioration of the device, and the initial efficiency reduction can be greatly reduced compared to a device without the hole transport supplement 142, thereby improving efficiency and lifetime. As described above, the hole transport auxiliary layer 142 may include a plurality of compounds having different energy levels mixed in one layer, and may include, for example, a first compound and a second compound having different HOMO energy levels. . In addition, the first compound and the second compound may have a uniform mixing ratio along the thickness direction of the hole transport auxiliary layer.

HOMO energy level of the first compound and the second compound is

It can be expressed as 1. ^~ [Expression 1]

In Equation 1, £ is the HOMO energy level of the first compound, E ^H _p2 is the HOMO energy level of the second compound.

One of the first compound and the second compound may be a compound having a relatively high HOMO energy level, and the other of the first compound and the second compound may be a compound having a relatively low HOMO energy level. have.

The difference in HOMO energy level of the C1 compound and the second compound may be, for example, about O.OleV or more, for example about 0.02eV or more, for example about 03eV or more, for example about 0.05eV or more. In this case, HOMO energy levels of the first compound and the crab compound 2 may be represented by at least one of the following relations la to Id.

[Relationship la]

E ^H _pl -E ^H _p2 | > 0.01 eV Relational lb

E ^H _pl -E ^H _p2 | > 0.02 eV

[Relationship lc]

E ^H _pl -E ^H _p2 | > 0.03 eV

[Relationship Id]

E ^H _pl -E ^H _p2 | > 0.05 eV

The difference between the HOMO energy levels of the first compound and the crab compound 2 may be about 0.5 eV or less within the above range. By having the above range, substantial hole injection from the anode 1 10 to the light emitting layer 130 can be facilitated. The difference in HOMO energy levels of the first compound and the crab 2 compound within the range may be, for example, about 0.4 eV or less, for example, about 0.3 eV or less.

In this case, the HOMO energy levels of the first compound and the second compound may be represented by at least one of the following relations 2a to 2c.

[Relationship 2a]

E ^H _pl -E ^H _p2 | <0.5 eV

[Relationship 2b]

E ^H _pl -E ^H _p2 | <0.4 eV

[Relationship 2c]

E ^H _pl -E ^H _p2 | <0.3 eV

For example, the HOMO energy level of the first compound and the first compound may be represented by at least one of the following relations 3a to 5e.

[Relationship 3a]

0 eV <| E ^H p,-E ^H _p2 | <0.5 eV

[Relationship 3b]

0.01 eV <| E ^H _p i- E ^H _p2 | 0.5 eV

[Relationship 3c] ^' 0.02 eV <| E ^H _p i- E ^H _p2 | <0.5 eV

[Relationship 3d]

0.03 eV <| E ^H _pl -E ^H _p2 | <0.5 eV

[Relationship 3e]

0.05 eV <| E ^H _pl -E ^H _p2 | <0.5 eV [Relationship 4a]

0eV <| EE ^H _p2 | <0.4 eV

[Relationship 4b]

0.01 eV <| E ^H _pl -E ^H _p2 | <0.4 eV

[Relationship 4c]

0.02 eV <| E ^H _p , -E ^H _p2 | <0.4 eV

[Relationship 4d]

0.03 eV <| E ^H _pl -E ^H _p2 | ≤0.4 eV

[Relationship 4e]

0.05 eV <| E ^H _pl -E ^H _p2 | <0.4 eV

[Relationship 5a]

OeV <E ^H _pl -E ^H _p2 | <0.3 eV

[Relationship 5b]

0.01 eV <| E ^H _pl -E ^H _p2 | <0.3 eV

[Relationship 5c]

0.02 eV <| E ^H p, -E ^H _p2 | <0.3 eV

[Relationship 5d]

0.03 eV <| E ^H _pl -E ^H _p2 | ≤0.3 eV

[Relationship 5e]

0.05 eV <| E ^H p, -E ^H _p2 | <0.3 eV

The hole transport auxiliary layer 142 may include a plurality of layers. In this case, the Crab 1 compound and the Crab 2 compound may be included in a layer in contact with the light emitting layer 130 of the plurality of hole transport auxiliary layers 142. Can be.

The first compound and the second compound may each have a HOMO energy level of, for example, about −5.45 eV to −5.80 eV, and may satisfy the relations within the above range.

Meanwhile, the hole transport supplement 142 may be located between the light emitting layer 130 and the hole transport layer 141 to block electrons from moving from the light emitting layer 130 to the hole transport layer 141. Accordingly, by effectively trapping electrons in the light emitting layer 130, it is possible to increase axtone generation in the light emitting layer 130 and to prevent excitons from being generated at the interface between the light emitting layer 130 and the hole transport layer 141. As a result, the efficiency can be increased. For example, when the hole transport auxiliary layer 142 includes the compound 11 and the compound 2, the LUMO energy level of the compound 1 and the compound 2 may further satisfy the following relations 6 to 9. .

[Relationship 6]

E ^L _p i | <| E hostl

[Relationship 7]

| E ^L _p i | <| E ^L _dopant |

[Relationship 8]

E ^L _p2 | <| E hostl

[Relationship 9]

E ^L _p2 | <| E ^L d _opan t |

In the above relation 6 to 9,

£ ^ is the LUMO energy level of the Crab 1 compound, E ^L _p2 is the LUMO energy level of the Crab 2 compound, E ^L _h0St is the LUMO energy level of the host of the light emitting layer and E ^L _dopant is the LUMO energy level of the _dopant of the light emitting layer.

The hole transport auxiliary layer 142 may increase efficiency by effectively blocking the movement of electrons from the light emitting layer 130 by including the first compound and the second compound satisfying the above relations 6 to 9.

The first compound and the second compound may each have a LUMO energy level of, for example, about −2.10 eV to −2.50 eV, and may satisfy the relations within the above range.

On the other hand, the hole transport auxiliary layer 142 is located between the light emitting layer 130 and the hole transport layer 141 may block the movement of the axtone from the light emitting layer 130 to the hole transport layer 141 side. Accordingly, to increase the luminous efficiency in the light emitting layer 130 by effectively confining axial tonol the light emitting layer _130, and can reduce the loss of axial tone. As a result, the efficiency can be increased.

For example, when the hole transport auxiliary layer 142 includes the C 1 compound and the second compound, the triplet energy level of the U compound and the 12 compound may further satisfy, for example, the following relations 10 to 13. have. [Relationship 10]

| E ^T host | <| E ^T _p i |

[Relationship 1 1]

| E ^T host | <| E ^T _p2 |

[Relationship 12]

| E ^T dopant | <| Ε ^Τ _ρ ι |

[Relationship 13]

| E ^T dopant | <| E ^T _p2 |

In the relation 10 to 13,

Ε ^τ _ρ1 is to a triplet energy level of the first compound Ε ^τ _ρ2 is the second compound triplet energy level and the E ^T _h0St is a triplet energy level of the emissive layer host E ^T _dopant is a triplet of the light-emitting layer dopyeon root of Energy level

The hole transport auxiliary layer 142 may include the first compound and the second compound satisfying the above relations 10 to 13 to effectively block the movement of the axtone from the light emitting layer 130 to increase efficiency.

The first compound and the second compound may each have a triplet energy level of, for example, about 2.35 eV to 2.80 eV, and satisfy the relations within the above range.

The first compound and the crab compound 2 may be selected from a compound satisfying the above-described energy level, for example, the crab compound 1 may be a compound represented by the following formula (1) and the crab compound 2 is represented by the formula (2) Or a compound represented by a combination of the following Chemical Formulas 3 and 4.

[Formula 1]

ΑΓ1

Of

Ar2

In Chemical Formula 1,

L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C6 internal C30 An arylene group, a substituted or unsubstituted C3 to C30 cycloalkylene group, a substituted or unsubstituted C2 to C30 divalent heterocyclic group, a combination thereof or a fused ring of a combination thereof,

Ar ¹ to Ar ³ are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, a combination thereof or a fused ring thereof,

At least one of Ar ¹ to Ar ³ is one of a group represented by the following formula A, a group represented by the following formula B, or a combination of the following formula B and the following formula D,

[Formula A] [Formula B] [Formula C] [Formula D]

In Chemical Formulas A to D,

X and Z are 0, S or CR ^a R ^b ,

Two adjacent * of formula B are fused with two adjacent * of formula C or D,

Unfused * of Formula B and Formula C are each CR ^C ,

R ¹ to R ⁴ , R ^a to R ^c 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 C1 to C20 alkoxy group , Substituted or unsubstituted C3 to C20

Cycloalkoxy group, a substituted or unsubstituted C1 to C20 alkylthio group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or non ^"substituted C6 to C30 aryl group, a substituted or unsubstituted C6 to C30 aryloxy group , Substituted or unsubstituted C6 to C30 arylthio group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C2 to C30 amino group, substituted or unsubstituted C3 to C30 silyl group, halogen, cyano group A nitro group, a hydroxyl group, a carboxyl group, a combination thereof, a fused ring of a combination thereof, or a connection point with at least one of L ¹ to L ³ of Formula 1,

R ³ and R ⁴ are each independently present or form a fused ring with each other, [Formula 2] [Formula 3] [Formula 4]

In Chemical Formulas 2 to 4,

γ ₁ , _{γΐ 3} and y _lb are each independently a single bond, a substituted or unsubstituted ci to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or Unsubstituted C2 to C30 divalent heterocyclic group, a combination thereof or a fused ring of a combination thereof,

Ar ⁴ , Ar ^4a and Ar ^4b are each independently a substituted or unsubstituted C6 to C30 aryl group substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

R ⁵ and R ⁶ are each independently present or connected to each other to form a ring,

R ⁷ and R ⁸ are each independently present or connected to each other to form a ring, R ⁹ and R ¹⁰ are each independently present or connected to each other to form a ring, and in R ⁵ to R ⁸ and Ar ⁴ of Formula 2 At least one includes a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted triphenylene group, or a substituted or unsubstituted carbazolyl group,

Formula 3 or _. At least one of R ⁵ to R ¹⁰ , Ar ^4a and Ar ^4b of ⁴ includes a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted triphenylene group, or a substituted or unsubstituted carbazolyl group.

The compound represented by Chemical Formula 1 is an amine compound substituted with a fused ring, and may satisfy the above-described energy level. In Formula 1, Ar ¹ to Ar ³ may be the same as or different from each other, at least one of Ar ¹ to Ar ³ is a group represented by the formula A, a group consisting of a combination of the formula B and the formula c and the It may be one selected from the group consisting of a combination of formula (B) and formula (D), for example, a group represented by the formula (A) in the formula (1), a group consisting of a combination of the formula B and the formula C and / or the formula B and One group consisting of a combination of the formula (D) may be included in one to three.

For example, when the group represented by the formula (A), the group represented by the combination of the formula B and the formula C and / or the group represented by the combination of the formula B and the formula (D) is one to three, at least One X may be O or S. In Ar ¹ to Ar ³ of Chemical Formula 1, each other except for a group represented by the combination of Chemical Formula A, Chemical Formula B and Chemical Formula C and / or a group represented by the chemical formula B and Chemical Formula D, Or a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C3 to C30 heterocyclic group, a combination thereof, or a fused ring thereof.

For example, in Ar ¹ to Ar ³ except for the group represented by the combination of Formula (A), Formula (B) and Formula (C) and / or the group represented by the combination of Formula (B) and Formula (D), each of the groups may be independently It may be one of the groups listed in 1, but is not limited thereto.

Group i]

In group 1 above,

R ⁷⁵ to R ¹¹⁷ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted C1 to C30 alkoxy group, substituted or unsubstituted C6 to C30 arylalkyl group, substituted or unsubstituted C5 to C30 aryloxy group, substituted or unsubstituted C5 to C30 arylthio group, substituted or unsubstituted C1 to C30

Alkoxycarbonyl group, carboxyl group, halogen, cyano group, nitro group, hydroxy group or a combination thereof.

Formula 1 may be represented by, for example, the following Formula 1-1 to the number and type of groups represented by the combination of Formula A, Formula B and Formula C and / or groups represented by the combination of Formula B and Formula D. It may be a compound represented by any one of 1-VIII.

In Chemical Formulas 1—I to 1—VIII L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C3 to C30

A cycloalkylene group, a substituted or unsubstituted C2 to C30 divalent heterocyclic group, a combination thereof or a fused ring of a combination thereof,

Ar ² and Ar ³ are each independently a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 heterocyclic group, a combination thereof or a fusion ring thereof;

X ^a to ^ are each independently 0, S or CR ^a R ^b ,

R ^lb , R ^2a to R ^2c , R ^3a to R ^3c , R ^4a to R ^4c , R ^a and R ^b are each independently hydrogen, deuterium, 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 heterocyclic group, substituted or Unsubstituted C2 to C30 amino group, substituted or unsubstituted C3 to C30 silyl group, halogen, cyano group, nitro group, hydroxyl group, carboxyl group, a combination thereof, and a fused ring thereof.

For example, in Formulas 1-1 to 1-VIII, at least one of X ^a to X ^c may be each independently 0 or S.

The Crab 2 compound is a compound capable of satisfying the above-described energy level in relation to the first compound, and is a carbazole compound substituted with an aryl group, triphenylene group, or carbazole group.

The compound represented by Chemical Formula 2 may be, for example, one of the compounds represented by any one of the following Chemical Formulas 2-1 to 2-IV.

[Formula 2-1] [Formula 2-Π]

[Formula 2-ΙΠ] [Formula 2-IV]

In Chemical Formulas 2-1 to 2-IV,

Y ¹ to Y ³ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C6 to C30 arylene group, a divalent substitution or Unsubstituted C2 to C30 heterocyclic group, a combination thereof or a fused ring of a combination thereof,

Ar ⁴ and Ar ⁵ 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,

Ar ^4a is each independently a substituted or unsubstituted C6 to C30 aryl group,

R ⁵ to R ²⁰ are each independently hydrogen, hydrogen, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C6 to C50 aryl group, substituted or unsubstituted C2 to C50 heterocyclic group, or Combination of these.

The compound represented by the combination of Chemical Formulas 3 and 4 may be, for example, one of the compounds represented by any one of Chemical Formulas 3-1 to 3-VII.

[Formula 3-1] [Formula 3-Π]

[Formula 3-m] [Formula 3-IV]

In Chemical Formulas 3-1 to 3-VII,

Y ^la and Y ^lb are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 divalent heterocyclic group, a combination thereof or a fused ring of a combination thereof,

Ar ^4a and Ar ^4b 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 ⁵ to R ¹⁰ , R ^d and R ^e 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 heterocycle Groups or a combination thereof, R ⁵ and R ⁶ are each independently present or connected to each other to form a ring, R ⁷ and R ⁸ are each independently present or connected to each other to form a ring, R ⁹ and R ¹⁰ are each independently present or each other Connected to form a ring, R ^d and R ^e are each independently present or connected to each other to form a ring, and at least one of R ⁵ to R ¹⁰ , Ar ^4a and Ar ^4b is substituted or unsubstituted C6 to C30 aryl Groups, substituted or unsubstituted triphenylene groups, or substituted or unsubstituted carbazolyl groups.

The first compound may be, for example, one of compounds represented by the following Formulas F-1 to F-184, G-1 to G-184, H-1 to H-204, and I-1 to 1-65. It is not limited.

82 巴^, -

Ln

(69¾) ^1-

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[8Ϊ-Η] [Ll-U] [91-Η] [Π-Η]

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-Η] [6-Η] [8-Η] ίί-ΐ [9Ή]

-H] [17-Η] [e-H] [ζ-Η] [1-Η]

[9 / .1-0] [SZ.1-9] [Ρί \ -Ό] [£ Ll

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[π-ΐ [en-H] [zu

LOI-H] -Η] [SOl-H] [SOI

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.88Z8l / ST0Z OAV

-H] [t ^ ei-HJ Leei-H] [in

[ΙΠ-Η] [ΟΠ-Η] [6Π-Η] [831 -H]

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[επ-Η] [zz \ -n] [\ Z \ -H \ [on

[6Π.Η] [8Π-Η] [λΐΐ-Η] [911 -Hi

.88Z8l / ST0Z OAV

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£ 8 _l 6--

_// : _/ O _s s2M _l> d-88sl _s s _z A _V

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o έ§ ^ί έ ^Ε ε6 ^ί [寸R ^{I t} -

LV .88Z8l / ST0Z OAV

8t7 .88Z8l / ST0Z OAV

-65]

The second compound may be, for example, one of compounds represented by B-10 to B-132, C-10 to C-33, or D-10 to D-31, but is not limited thereto. An example of this is as follows.

E-l

B-13 Bi.4 E-1S _// : _/ O _s s2M _l><i -88sl _s s _z AV

s

1-31 B-32 B-33

B-34 B-3S B-37 B-3S

.88Z8l / ST0Z OAV

B-1 3 B-1D B 05

B-130 B-131

C-14 G-15 G-16

The hole transport layer 141 is not particularly limited, but may include, for example, a compound represented by the following Chemical Formula 3. [Chemistry 3]

In Chemical Formula 3,

R ^{1 18} to R ¹²¹ 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 C2 to C30 heterocyclic group, or a combination thereof Is,

R ^{1 18} and R ^{1 19} are each independently present or form a fused ring with each other, R ¹²⁰ and R ¹²¹ are each independently present or form a fused ring with each other, Ar ⁶ to Ar ⁸ are each independently substituted or unsubstituted A substituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

L ⁴ to L ⁷ are each independently a single bond, a substituted or unsubstituted C2 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkenylene group, a substituted or unsubstituted C2 to C10 alkynylene group, a substituted or unsubstituted A substituted C6 to C30 arylene group, a divalent substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof.

For example, Ar ⁶ of Formula 3 may be a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group, and Ar ⁷ and Ar ⁸ of Formula 3 may each independently be a substituted or unsubstituted phenyl group, substituted or Unsubstituted biphenyl group, substituted or unsubstituted fluorene group, substituted or unsubstituted bisfluorene group, substituted or unsubstituted triphenylene group, substituted or unsubstituted anthracene group, substituted or unsubstituted terphenyl group, It may be either a substituted or unsubstituted dibenzofuran group or a substituted or unsubstituted dibenzothiophenyl group. The compound represented by Chemical Formula 3 may be, for example one of the compounds represented by the following J-1 to J-144, but is not limited thereto.

[9 -ri [ζ £ -Π [-Γ]

[££-[] Z £-[] [ie-r]

-r] [6Ζ-Π [83-r]

[belt]

-n [shachet]

[6Ε-Γ] [8 £ -f] [Li- []

Ζ9 .88Z8l / ST0Z OAV

-r] r]

[£ 9- [Ζ9-Π 9-f]

09-r 6s-r -r

9s-rJ

£ 9 .88Z8l / ST0Z OAV [J-73] [J-74] [J-75]

O _88s sAV

92 ¹ § ^1- ..

[ιπ-r] [on-r] [601-f]

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

[J- 130] [J-131] [J- 132]

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

In FIG. 1, the organic layer 105 includes a hole injection layer, an electron blocking layer, an electron transport layer, an electron injection layer, and / or in addition to the above-described light emitting insect 130, the hole transport auxiliary layer 142, and the air transport layer Ml. It may further include a hole blocking layer.

After the organic light emitting device 300 forms an anode or a cathode on a substrate,

After forming the organic layer by a dry film method such as evaporation, sputtering, plasma plating and ion plating or a solution process such as inkjet printing, spin coating, slit coating, bar coating and / or dip coating, It can be produced by forming a cathode or an anode thereon.

The organic light emitting diode described above may be applied to an organic light emitting diode display.

[Form for implementation of invention]

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

Synthesis of Intermediates

Synthesis of Intermediate M-1

20 g (94.3 mmol) of 4-dibenzofuranboronic acid and 26.7 g (94.3 mmol) of 1-bromo-4-iodobenzene were added to the back bottom flask, 313 ml of toluene was added to dissolve and 19.5 g of potassium carbonate ( 117 ml of an aqueous solution of 141.5 mmol) was added and stirred. Tetrakistriphenylphosphinepalladium 1.09 g (0.94 mmol) was added thereto, followed by stirring under reflux for 12 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate, filtered and the filtrate was decompressed.

Concentrated. Silica gel column with n-nucleic acid / dichloromethane (9: l v / v)

Purification by chromatography gave 27 g (89% yield) of intermediate M-1 as a white solid.

LC-Mass (Theoretical value: 322.00 g / mol, Measured value: M + = 322.09 g / mol, M + 2 = 324.04 g / mol)

Synthesis of Intermediate M-2 Banungsik 2]

38 g (154.90 mmol) of N, 4-diphenylaniline was added to the back bottom flask, and 620 ml of dichloromethane was dissolved. 41.5 g (232.35 mmol) of N-bromosuccinimide was slowly added at room temperature and under nitrogen atmosphere. Stir at room temperature for 4 hours. After completion of reaction, the mixture was diluted with dichloromethane, filtered through a silica gel filter, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (7 _: 3 v / v) to give 31.1 g (62% yield) of intermediate M-2.

LC-Mass (Theoretical value: 323.03 g / mol, Measured value: M + = 323.12 g / mol, M + 2 = 325.1 1 g / mol) Synthesis of Intermediate M-3

Banungsik 3]

31 g (95.62 mmol) of intermediate Μ-2, 24.7 g (143.43 mmol) of naphthalen-1-yl boronic acid were added to the back bottom flask, and 400 ml of toluene was added to dissolve it. Then, 39.65 g (286.85 mmol) of potassium carbonate was dissolved. ml was added and stirred. Here

2.21 g (1.91 mmol) of tetrakistriphenylphosphinepalladium was added thereto, followed by stirring under reflux for 12 hours under a nitrogen atmosphere. After the completion of reaction, the mixture was extracted with dichloromethane and distilled water, and the extract 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 v / v) to give 31.3 g (88% yield) of intermediate M-3.

LC-Mass (Theoretical value: 371.17 g / mol, Measured value: M + = 371.1 1 g / mol)

Synthesis of Intermediate K-1 [Banungsik 4]

53.15 g (250.61 mmol) of 4-dibenzofuran boronic acid, 50 g (22 g83 mmol) of 2-bromo-5-chloro-benzaldehyde, 62.98 g (455.66 mmol) of potassium carbonate and tetra in a K-1 round bottom flask Add 7.89 g (6.84 mmol) of KEYSTRIEPHINEPINSPINPALADIUM (Pd (PPh ₃ ) ₄ ), suspend it in 1000 ml of toluene and 500 ml of distilled water, and then under nitrogen atmosphere for 12 hours.

The mixture was stirred under reflux. After completion of the reaction, the mixture was extracted with toluene, dried over magnesium sulfate, filtered through silica gel, and the filtrate was concentrated under reduced pressure. 300 ml of methanol was added to the concentrate, and the resulting solid was stirred for 1 hour and then filtered to obtain 64.64 g of an intermediate K-1 (yield 93%).

LC-Mass (theoretical value: 306. ⁷ 4g / mol, measured value: M + = 306.79g / mol)

Synthesis of Intermediate K-2

[Bungungsik 5]

64.64 g (210/73 mmol) of intermediate K-1 in an isometric bottom flask,

79.46 g (231.80 mmol) of (methoxymethyl) triphenylphosphonium chloride

It is suspended in 600 ml of tetrahydrofuran and kept ^at 0 ^° C. Subsequently, 28.38 g (252.87 mmol) of Potassium _t -butoxide was slowly added under 0 ^° C., followed by stirring at room temperature for 12 hours. After completion of reaction, 600ml of distilled water was added and extracted. The extract was concentrated, suspended in 500ml of methylene chloride, dried over magnesium sulfate, filtered with silica gel, and concentrated again. The concentrated reaction solution was dissolved in 400 ml of methylene chloride and slowly added 20 g of methanesulfonic acid, followed by stirring at room temperature for 12 hours. reaction After the completion, the resulting solid was filtered, washed with 200 ml of distilled water and 200 ml of methanol, and dried to obtain 48.4 g of an intermediate K-2 (yield 76%).

LC-Mass (Theoretical value: 302.75 g / mol, Measured value: M + = 303.84 g / mol)

Synthesis of Intermediate K-3

[Half 6]

11 g (36.33 mmol) of intermediate K-2 and 1.25 g (2.18 mmol) of Pd (dba) ₂ , KOAC 10.7 g (109.00 mmol), P (Cy) 3 2.45 g (8.72 mmol), Bis (pinacolato) 11.07 g (43.60 mmol) of diboron are suspended in 150 ml of DMF and stirred under reflux for 12 hours. After the reaction was cooled to room temperature and 300 ml of distilled water was added and stirred for 1 hour. The solid formed during the stirring was filtered, washed with methanol, dissolved in 300 ml of toluene, and dissolved in a silica gel filter. The filtrate was concentrated and recrystallized from toluene to obtain 9.05 g of intermediate K-3 (yield 63%).

Synthesis of Intermediate K-4

[7]

15.0 g (65.77 mmol) of 4-dibenzothiophene boronic acid and 20.47 g (72.35 mmol) of 1-bromo-3-iodobenzene were added to the back bottom flask, and 300 ml of toluene was added to dissolve it. 95 ml of an aqueous solution of 138.12 mmol) was added and stirred. Tetrakistriphenylphosphinepalladium (Pd (PPh ₃ ) ₄ ) 0.76 g (0.66 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with ethyl acetate, the extract was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (9: 1 volume ratio) to give 20.3 g (91% yield) of intermediate K-4 as a white solid.

Synthesis of Intermediate K-5

[Reaction 8]

21 g (64.7 mmol) of intermediate M-1, 1.74 g (29.4 mmol) of acetamide, and 17.3 g (1 17. mmol) of potassium carbonate were added to a round bottom flask, and 130 ml of xylene was added to dissolve it.

1.12 g (5.88 mmol) of copper iodide and 1.04 g (1 1.8 mmol) of Ν, Ν-dimethylethylenediamine were sequentially added thereto, followed by stirring under reflux for 48 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 / ethyl acetate (5: 5 volume ratio) to give 15 g of intermediate K-5 (yield 94%).

Synthesis of Intermediate K-5-1

[9]

13.7 g (25.2 mmol) of intermediate K-5 and 4.2 g (75.6 mmol) of potassium hydroxide were added to a round bottom flask, and 80 ml of tetrahydrofuran (THF) and 80 mL of ethanol were dissolved. The mixture is stirred under reflux for 12 hours under a nitrogen atmosphere. After completion of reaction, the reaction mixture was concentrated under reduced pressure, extracted with dichloromethane 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 1.4 g (90% yield) of intermediate K-5-1. Synthesis of Intermediate K-6 [10]

20 g (476.41 mmol) of N- (4-Bromophenyl) -N, N-bis (l, r-biphenyl-4-yl) arnine and 1.03 g (1.26 mmol) of Pd (dppf) C12 in a K-6 isometric flask 12.8 g (50.38 mmol) of Bis (pinacolato) diboron and 12.36 g (125.94 mmol) of Potassium Acetate were suspended in 210 ml of toluene and stirred under reflux for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filtrate was concentrated by silica gel filter. Recrystallization from acetone afforded 17 g of intermediate K-6 (yield 77%).

Synthesis of Intermediate K-7

[U]

20 g (49.96 mmol) of N- (4-bromophenyl) -N-phenylbiphenyl-4-amine, 1.22 g (1.50 mmol) of Pd (dppf) C12, 15.22 g (59.95 mmol) of Bis (pinacolato) diboron ),

14.71 g (149.88 mmol) of Potassium Acetate is suspended in 250 ml of toluene and stirred under reflux for 12 hours. After completion of reaction, the mixture was cooled to room temperature, filtered, and the filtrate was concentrated by silica gel filter. Recrystallization from acetone afforded 18 g of intermediate K-7 (yield 81%). Synthesis of Intermediate K-8 [Banungsik 12]

Κ-8 deunggeun N- (biphenyl- ³ -yl) bottom flask biphenyl-4-amine 22.96 g ( 71 · 4 3 mmol) and _{Pd (dba) 2 1.23 g (} 2.14 mmol), P (t-Bu) 3 0.43 g (2.14 mmol) and 10.29 g (107.15 mmol) of NaO (t-Bu) are suspended in 500 ml of toluene and stirred at 60 ^° C for 12 hours. After the completion of the reaction, distilled water was added, stirred for 30 minutes, and extracted.

Columning with (nucleic acid / dichloromethane = 9: 1 (v / v)) afforded 24 g of intermediate K-8 (yield 78%). Synthesis of Intermediate K-9

In a round bottom flask, 14.5 g (40.94 mmol) of triphenylene boronic acid, 1.08 g (45.03 mmol) of 3-bromo-9H-carbazole 1, 1.32 g (81.88 mmol) of potassium carbonate, tetrakis- (triphenylforce Pin) Pall (0) (Pd (PPh ₃ ) ₄ ) 1.42 g (1.23 mmmol)

180 ml of tetrahydrofuran (THF) was suspended in 75 ml of distilled water, followed by stirring under reflux for 12 hours. Subsequently, the mixture was extracted with dichloromethane and distilled water, and the organic layer was filtered with silica gel. The organic solution was then removed and the product solid was recrystallized from dichloromethane and n-nucleic acid to give 14.66 g (91% yield) of intermediate K-9.

Synthesis of Intermediate K-10

16.0 g (49.66 mmol) of phenylcarbazolyl bromide, 11.53 g (.62 mmol) of carbazolylboronic acid and 20.59 g (148.98 mmol) of potassium carbonate, tetrakis- (triphenyl) 1.72 g (1.49 mmol) of phosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) was suspended in 150 ml of toluene and 65 ml of distilled water, followed by stirring under reflux for 12 hours. Then extracted with dichloromethane and distilled water and the organic layer is filtered on silica gel. The organic solution was then removed and the product solid was recrystallized from dichloromethane and n-nucleic acid to give 18.26 g (90% yield) of intermediate K-10.

Synthesis of Intermediate K-11

[

3,6-Dibromo-9H-carbazole 19.2 g (59.08 mmol), [U'-biphenyrH-ylboronicacidSS S g (129.97 mmol) and 20.41 g (147.69 mmol) potassium carbonate, tetrakis ^ Triphenylphosphine;！ palladium ^^^！ ^ ！！ ^^^?！ ^ ^ Was suspended in 300 ml of toluene and 100 ml of distilled water, followed by stirring under reflux for 12 hours. Then extracted with dichloromethane and distilled water and the organic layer is filtered on silica gel. The organic solution was then removed and the product solid was recrystallized from dichloromethane and n-nucleic acid to give 122.29 g (80% yield) of intermediate K-1.

Synthesis of Intermediate K-12 [

19.2 g (59.08 mmol) of 3,6-dibromozin 9Η-carbazole, 25.73 g (129.97 mmol) of [Ι, Γ- biphenyl] -3-yl boronic acid and 20.41 g of potassium carbonate ( 147.69 mmol) and 2.05 g (1.77 mmol) of tetrakis- (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) were suspended in 100 ml of 300 ml of diluent and stirred under reflux for 12 hours. Then extracted with dichloromethane and distilled water and the organic layer is filtered on silica gel. The organic solution was then removed and the product solid was recrystallized from dichloromethane and n-nucleic acid to give 21.73 g (78% yield) of intermediate K-12.

Synthesis of Final Compound

Synthesis Example 1 Synthesis of Compound 1-61

17]

1-61

15 g (46.4 mmol) of Intermediate M-1, 4.9 g (23.2 mmol) of 9,9-dimethyl-PH pulloene-2-amine, 6.7 g (NaOt-Bu) of sodium t-butoxide (69.6) in a back bottom flask mmol) was added and dissolved in 160 ml of toluene. 0.85 g (0.928 mmol) of Pd (dba) ₂ and 0.45 g (1.86 mmol) of tri-tertiary-butylphosphine (P (t-Bu) ₃ ) 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 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 27.4 g of compound I-61 (yield 85%). LC-Mass (Theoretical value: 693.27 g / mol, Measured value: M + = 693.51 g / mol)

Synthesis Example 2 Synthesis of Compound C-10

18]

10 g (34.83 mmol) of phenylcarbazolyl boronic acid and 1.77 g (38.31 mmol) of 2-bromotriphenylene were added to the back bottom flask, and 140 ml of toluene was added to dissolve it, followed by 14.44 g (104.49 mmol) of potassium carbonate. 87 ml of the dissolved aqueous solution were added and stirred.

Tetrakistriphenylphosphinepalladium (Pd (PPh ₃ ) 4) 0.80 g (0.7 mmol) was added thereto, and the mixture was stirred under reflux for 12 hours under a nitrogen atmosphere. After completion of reaction, the mixture was extracted with dichloromethane and distilled water, and the extract was dried over magnesium sulfate and filtered, and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with _n -nucleic acid / dichloromethane (7: 3 volume ratio) to give 14.4 g (88% yield) of compound C-10.

LC-Mass (Theoretical value: 469.18 g / mol, Measured value: M + = 469.10 g / mol)

Synthesis Example 3 Synthesis of Compound 1-57

20.9 g (73.42 mmol) of Compound A, 30 g (80.76 mmol) of Intermediate M-3, sodium t-blockoxide l (). 58 g (110.13 mmol) were added to a Γ-57 back bottom flask, and 700 ml of toluene was added thereto. Dissolved. 0.67 g (0.734 mmol) of Pd (dba) ₂ and 0.45 g (2.20 mmol) of tri-tertiary-butylphosphine were sequentially added thereto, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. After the reaction was completed, the mixture was extracted with toluene and distilled water, and then the organic layer was dried over magnesium sulfate and filtered. 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 39.4 g (yield 82%) of compound 1-57.

LC-Mass (Theoretical value: 653.27 g / mol, Measured value: M + = 653.33 g / mol)

Synthesis Example 4 Synthesis of Compound B-43

[Banungsik 20]

12.33 g (30.95 mmol) of biphenylcarbazolyl bromide, 12.37 g (34.05 mmol) of biphenylcarbazolylboronic acid and 12.83 g (92.86 mmol) of potassium carbonate, tetrakis- ( 1.07 g (0.93 mmmol) of triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) was suspended in 120 ml of toluene and 50 ml of distilled water, followed by stirring under reflux for 12 hours. Subsequently, the mixture was extracted with dichloromethane and distilled water, and the organic layer was filtered with silica gel. The organic solution was then removed and the product solid was recrystallized from dichloromethane and n-nucleic acid to give 18.7 g (92% yield) of compound B-43.

LC-Mass (Theoretical value: 636.26 g / mol, Measured value: M + = 636 g / mol)

Synthesis Example 5 Synthesis of Compound B-114

80 g (547.23 mmol) of α-tetrarone and 129.46 g (895.30 mmol) of phenylhydrazine hydrochloride were added to a small amount of acetic acid, and the mixture was stirred under reflux under nitrogen stream for 24 hours in 1800 ml of ethanol. After completion of reaction, the reaction product was cooled to room temperature, and the formed product was filtered, basified with a small amount of NaHC03 solution, and recrystallized with ethanol to obtain 73.0 g of intermediate A (yield: 60%).

Then 74.0 g (337.47 mmol) of Intermediate A and 116.17 g (427.46 mmol) of tetrachloro 1,4-benzoquinone were stirred at 1200 mL of xylene under reflux for 4 hours under nitrogen stream. After completion of reaction, an aqueous NaOH (10%) solution was added, extracted with dichloromethane, and the organic layer was filtered with silica gel. The organic solution was removed and the silica gel column with nucleic acid: dichloromethane = 7: 3 (v / v), and the product solid was recrystallized from dichloromethane and nucleic acid to give 31.0 g of intermediate B (yield: 42%).

31.0 g (142.68 mmol) of intermediate B, 33.60 g (214.02 mmol) of bromobenzene, 285.36 g (27.42 mmol) of NaO (t-Bu) and 7.84 g (8.56 mmmol) of Pd2 (dba) 3 were suspended in 500 mL of toluene. 41.54 mL (85.61 mmol) of P (t-Bu) 3 was added thereto, and the mixture was stirred under reflux for 24 hours under a nitrogen stream. Extract with dichloromethane and distilled water and filter the organic layer with silica gel. The organic solution was removed, and silica gel column was extracted with hexane: dichloromethane = 7 _: 3 (v / v). The product solid was recrystallized from dichloromethane and normal nucleic acid to give 39.0 g (yield: 95%) of intermediate C.

Then 39.0 g (132.94 mmol) of intermediate C and 26.03 g (146.24 mmol) of NBS were added.

It was suspended in 460 mL of chloroform and stirred under reflux for 4 hours under nitrogen stream. The mixture was extracted with dichloromethane and distilled water, and the organic layer was filtered through silica gel. The organic solution was removed and recrystallized with dichloromethane and ethanol to obtain an intermediate D 45.51 g (yield: 92%).

22.5 g (60.44 mmol) of Intermediate D, 19.95 g (78.57 mmol) of bispinacoratodiborone, PdCl ₂ (dppf) (0.99 g, 1.20 mmol) and OAc (17.79 g, 181.32 mmol) were suspended in 210 ml of toluene. After stirring under reflux for 24 hours at reflux. Extract with dichloromethane and distilled water and filter the organic layer with silica gel. The organic solution was removed and the silica gel column with nucleic acid: dichloromethane = 7: 3 (Wv) and the product solid was recrystallized from dichloromethane and normal nucleic acid to give 17.0 g of intermediate E (yield: 67%).

Intermediate E 10.7 g (25.52 mmol), 6.19 g (30.62 mmol) 2-bromonitrobenzene and 7.05 g (51.04 mmol) K2C03, 0.59 g (0.51 mmmol) of Pd (PPh ₃ ) ₄ 150 ml of toluene, distilled water 75 It was suspended in ml and stirred under reflux for 24 hours under a nitrogen stream. After completion of the reaction, the reaction mixture was extracted with dichloromethane, filtered with silica gel, and distilled under reduced pressure, followed by silica column with nucleic acid: dichloromethane = 7: 3 (v / v), followed by dichloromethane.

Recrystallization from normal nucleic acid afforded 8.1 g of intermediate F (yield: 77%).

Subsequently, 8.1 g (19.54 mmol) of intermediate F and 17.0 mL (97.72 mmol) of triethyl phosphite were stirred at reflux for 4 hours under a stream of nitrogen. After completion of reaction, the reaction solvent was removed, and silica column with nucleic acid: dichloromethane = 7: 3 (v / v) gave 6.2 g (yield: 83%) of intermediate G.

Then 6.2 g (16.21 mmol) of intermediate G, 6.01 g (19.45 mmol) of Bromo-3,5-terphenyl, 4.67 g (48.63 mmol) of NaO (t-Bu), 0.59 g (0.65 mmmol) of Pd2 (dba) 3 were added. Toluene was suspended in 500 mL, 0.39 mL (1.62 mmol) of P (t-Bu) 3 was added thereto, and the mixture was stirred under reflux for 24 hours under a nitrogen stream. Extract with dichloromethane and distilled water and filter the organic layer with silica gel. The organic solution was removed and silica gel column with nucleic acid: dichloromethane = 7: 3 (Wv) to recrystallize the product solid with dichloromethane and normal nucleic acid to give 8.6 g (yield: 87%) of compound B-114. LC-Mass (Theoretical value: 74g / mol for 61, Measured value: M + l = 61 1g / mol)

Synthesis Example 6 Synthesis of Compound B-115

[Ref 22].

15.5 g (38.92 mmol) of biphenylcarbazolyl bromide, 12.29 g (42.81 mmol) of biphenylcarbazolylboronic acid and 16.14 g (1 16.75 mmol) of potassium carbonate, tetrakis-

(Triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ ) L3 ⁵ g (1.17 mmmol) olole was suspended in 150 ml of diluent and 70 ml of distilled water, followed by stirring under reflux for 12 hours. next

Extract with dichloromethane and distilled water and filter the organic layer with silica gel. The organic solution was then removed and the product solid was recrystallized from dichloromethane and _n -nucleic acid to give 19.42 g of compound B-1 15 (yield 89%).

LC-Mass (Theoretical value: 560.69 g / mol, Measured value: M + = 560.22 g / mol)

Synthesis Example 7 Synthesis of Compound B-116

[Banungsik 23]

Biphenykarbazolyl bromide 13. lg (32.89 mmol), 13.14 g (36.18 mmol) m-biphenylcarbazolylboronic acid and 13.64 g (98.676 mmol) potassium tetracarbonate in a round bottom flask Kiss- (triphenylphosphine) palm (0) (Pd (PPh ₃ ) ₄ ) L14 g (0.99 mmmol) to 130 ml of toluene, It was suspended in 55 ml of distilled water and stirred under reflux for 12 hours. next

Extract with dichloromethane and distilled water and filter the organic layer with silica gel. The organic solution was then removed and the product solid was recrystallized from dichloromethane and n-nucleic acid to give 19.27 g of compound B-1 16 (yield 92%).

LC-Mass (Theoretical value: 636.26 g / mol, Measured value: M + = 636.11 g / mol)

Synthesis Example 8 Synthesis of Compound B-117

11.2 g (27.42 mmol) of Intermediate K-10 and 8.86 g (27.42 mmol) of Intermediate M-1, 0.25 g (0.274 mmol) of Pd2 (dba) 3, and 0.133 g (0.274 mmol) of P (t-Bu) 3 in the isometric flask ), 3.95 g (41.13 mmol) of NaO (t-Bu) is suspended in 300 ml of toluene and stirred at 60 ^° C. for 12 hours. After the completion of reaction, distilled water was added, stirred for 30 minutes, and extracted. Only the organic layer was columned with a silica gel column (nucleic acid / dichloromethane = 9: 1 (v / v)) to obtain 19.5 g of a compound B-117 (yield 88%).

LC-Mass (Theoretical value: 650.76 g / mol, Measured value: M + = 650.71 g / mol)

Synthesis Example 9 Synthesis of Compound B-118

12.0 g (29.38 mmol) of Intermediate K-10, 9.97 g (29.38 mmol) of Intermediate K-4, 0.27 g (0.294 mmol) of Pd2 (dba) 3, 0.143 g (0.588 mmol) of P (t-Bu) 3 ), 4.24 g (44.06 mmol) of NaO (t-Bu) is suspended in 310 ml of toluene and stirred at 60 ^° C for 12 hours. After the completion of reaction, distilled water was added, stirred for 30 minutes, and extracted. Only the organic layer was columned with a silica gel column (nucleic acid / dichloromethane = 9: 1 (v / v)) to obtain 17.63 g of a compound B-118 (yield 90%).

LC-Mass (Theoretical value: 666.83 g / mol, Measured value: M + = 666.7 g / mol)

Synthesis Example 10 Synthesis of Compound C-23

Scheme 26]

C-23

14.6 g (37.1 mmol) of Intermediate K-9 and 12.62 g (40.82 mmol) of 5'-bromo-l, l ': 3', l "-terphenyl in a round bottom flask, 1.70 g (1.86 mmol) of Pd2 (dba) 3 3.53 g (7.42 mmol) of P (t-Bu) 3 and 7.132 g (74.21 mmol) of NaO (t-Bu) were suspended in 280 ml of toluene and stirred for 12 hours at 6 (C. After completion of reaction, distilled water Was added, the mixture was stirred for 30 minutes, and extracted. Only the organic layer was columned with a silica gel column (nucleic acid / dichloromethane = 9 _: 1 (v / v)) to obtain 16.15 g of a compound C-23 (yield 70%).

LC-Mass (Theoretical value: 621.77 g / mol, Measured value: M + = 62L71 g / mol)

Synthesis Example 11 Synthesis of Compound D-30

D-30

Intermediate -11 20.0 g (42.41 mmol) and 4-iodo-l, l'-biphenyl (Aldrich) 11.88 g (42.41 mmol), Pd2 (dba) 3 0.388 g (0.424 mmol), P (t) -Bu) 3 0.206 g (0.848 mmol), 6.11 g (63.61 mmol) of NaO (t-Bu) are suspended in 420 ml of toluene, followed by 60 ^° C. Stir for 12 hours. After the completion of the reaction, distilled water was added, stirred for 30 minutes, and extracted. Only the organic layer was columned with a silica gel column (nucleic acid / dichloromethane = 9: 1 (v / v)) to obtain 23.02 g of a compound D-30 (yield 87%).

LC-Mass (Theoretical value: 623.78 g / mol, Measured value: M + = 623.25 g / mol)

Synthesis Example 12 Synthesis of Compound D-31

D-31

20.0 g (42.41 mmol) and 4-iodo-l, l'-biphenyl (purchased by Aldrich) and 11.88 g (42.41 mmol), Pd2 (dba) 3 0.388 g (0.424 mmol), P 0.206 g (0.848 mmol) of (t-Bu) 3, 6.11 g (63.61 mmol) of NaO (t-Bu) are suspended in 420 ml of toluene and stirred at 60 ^° C for 12 hours. After the completion of reaction, distilled water was added, stirred for 30 minutes, and extracted. Only the organic layer was columned with a silica gel column (nucleic acid / dichloromethane = 9: 1 (v / v)) to obtain 22.49 g of a compound D-31 (yield 85%).

LC-Mass (Theoretical value: 623.78 g / mol, Measured value: M + = 623.21 g / mol)

Synthesis Example 13: Synthesis of Compound H-204

H-204

17.9 g (63.07 mmol) of 1- (4-bromophenyl) naphthalene, 6.0 g (28.67 mmol) of 2-amino-9,9-dimethyl-9H-fluorene, 8.3 g of sodium t-butoxide in a back bottom flask 86.01 mmol) was added and 200 ml of toluene was added to dissolve it. 0.165 g (0.287 mmol) of Pd (dba) ₂ and 0.145 g (0.72 mmol) of tri-tertiary-butylphosphine (P (t-Bu) ₃ ) were added sequentially, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. . After reaction, extract with toluene and distilled water The organic layer was dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-nucleic acid / dichloromethane (7: 3 volume ratio) to give a light beige solid, 15.3 g. (Yield 87%) was obtained.

LC-Mass (Theoretical value: 613.28g / mol, Measured value: M + = 61 16g / mol)

Synthesis Example 14 Synthesis of Compound 1-62

9.6 g (30.9 mmol) of 4-bromotorphenyl, 15.4 g (30.8 mmol) of Intermediate K-5-1, and 5.35 g (55.6 mmol) of sodium t-butoxide were added and dissolved in 155 ml of toluene. 0.178 g (0.31 mmol) of Pd (dba) ₂ and 0.125 g (0.62 mmol) of tri-tertiary-butylphosphine (P (t-Bu) ₃ ) were added sequentially, followed by stirring under reflux for 4 hours under a nitrogen atmosphere. . After completion of the 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 20.5 g (yield 91%) of compound 1-62 as a white solid.

LC-Mass (Theoretical value: 729.27 g / mol, Measured value: M + = 729.12 g / mol)

Synthesis Example 15 Synthesis of Compound 1-63

15 g (49.55 mmol) of intermediate K-2 and 27.2 g (52.02) of intermediate K-6 in an isometric bottom flask. mmol) and 32.3 g (99.09 mmol) of cesium carbonate (Cs ₂ C0 ₃ ) were added thereto, and 250 ml of 1,4-dioxane was added to dissolve it. 0.85 g (1.49 mmol) of Pd (dba) ₂ and 0.7 g (3.47 mmol) of _tri -t-butylphosphine (P (t-Bu) ₃ ) were sequentially added thereto, followed by stirring under reflux for 12 hours under a nitrogen atmosphere. After the reaction was completed, the phase was cooled to silver and stirred for 30 minutes by adding distilled water, and the resulting solid was filtered and washed with 200 ml of distilled water and methanol. The solid was dissolved in 300 ml of dichlorobenzene (DCB), filtered through silica gel, and stirred for 1 hour by adding 300 ml of methane. The resulting solid was filtered and washed with 200 ml of acetone to give 17.2 g of compound 1-63 (yield 52%).

LC-Mass (Theoretical value: 663.8 g / mol, Measured value: M + = 663.4 g / mol)

Synthesis Example 16: Synthesis of Compound 1-64

10 g (33.03 mmol) of intermediate Κ-2, 14.77 g (33.03 mmol) of intermediate K-7 and 21.52 g (66.06 mmol) of cesium carbonate (C¾C0 ₃ ) were added to the back bottom flask, and 200 ml of 1,4-dioxane was added. Dissolved. 0.57 g (99 mmol) of Pd (dba) ₂ and 0.4 g (1.98 mmol) of _tri -t-butylphosphine (P (t-Bu) ₃ ) were added sequentially, followed by stirring under reflux for 12 hours under a nitrogen atmosphere. Let's do it. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added, stirred for 30 minutes, and the resulting solid was filtered and washed with 200 ml of distilled water and methanol. The solid was dissolved in 300 ml of toluene (DCB), filtered through silica gel, and recrystallized with acetone to obtain 10.9 g of a compound 1-64 (yield 56%).

LC-Mass (Theoretical value: 587.7 g / mol, Measured value: M + = 587.4 g / mol)

Synthesis Example 17 Synthesis of Compound 1-65

9.27 g (23.51 mmol) of Intermediate K-3, 10.16 g (23.51 mmol) of Intermediate K-8 and 15.32 g (47.02 mmol) of Cesium Carbonate (Cs ₂ C0 ₃ ) were added to the back bottom flask and 150 ml of 1,4-dioxane was added. It was added and dissolved. 0.41 g (0.71 mmol) of Pd (dba) ₂ and 0.33 g (1.65 mmol) of _tri -t-butylphosphine (P (t-Bu) ₃ ) were sequentially added thereto, followed by stirring under reflux for 12 hours under a nitrogen atmosphere. After completion of reaction, the mixture was cooled to room temperature, distilled water was added, stirred for 30 minutes, the resulting solid was filtered, and distilled water and methane were washed with 200 ml each. The solid was dissolved in 300 ml of toluene (DCB), followed by adsorption with silica gel to obtain 8.1 g (yield 52%) of compound 1-65.

LC-Mass (Theoretical value: 663.8 g / mol, Measured value: M + = 663.2 g / mol) Evaluation 1

The energy levels of the main compounds obtained in the synthesis examples were measured.

HOMO energy level is diluted to a concentration of lxl (T ⁵ M) of each compound in CHC1 ₃ , using a Shimadzu UV-350 Spectrometer (Shimadzu UV-350 Spectrometer), after measuring the UV absorption spectrum at room temperature, the absorption Calculations were made using the optical band gap (Eg) from the edge of the spectrum _(e dg _e ).

LUMO energy level is Cyclic voltammetry (CV) (electrolyte: 0.1 M BU ₄ NCIO4 I solvent: CH ₂ C1 ₂ I electrode: 3 electrode system (working electrode: GC, reference electrode: Ag / AgCl, auxiliary electrode: Pt)) After obtaining the potential (V) -current (A) graph of each compound, the LUMO energy level of each compound was calculated from the reduction onset of the graph.

The T1 energy level is a mixture of MTHF and each compound (dissolved 1 mg of each compound in 3 cc of MTHF) in a quartz cell, followed by liquid nitrogen (77K) and a photoluminescence measuring instrument. Photoluminescence spectra were measured and compared with normal room temperature photoluminescence spectra to calculate only peaks observed only at low temperatures.

The results are shown in Table 1.

TABLE 1

Fabrication of Organic Light Emitting Diode

Example 1

Indium tin oxide (A) 1500 A thin glass substrate coated with a thin film was washed with distilled water ultrasonically. After the washing using distilled water was transferred to the substrate with isopropyl alcohol or acetone, and then after the ultrasonic cleaning of the methane in a solvent such as dried was transferred to a plasma cleaner by using the following oxygen plasma cleaning the substrate 5 minutes _vacuum, deposition . N-([l, l'-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (9-phenyl-9H-carbazol) was prepared on the ΠΌ substrate using the prepared ΠΌ transparent electrode as an anode. -3-yl) phenyl) -9H-fluoren-2-amine was vacuum deposited to form a hole transport layer having a thickness of 1400A. 1-61 obtained in Synthesis Example 1 and C-10 obtained in Synthesis Example 2 were simultaneously deposited on the hole transport layer in a ratio of 1: 1 to form a hole transport auxiliary layer having a thickness of 50 A. SFC BH1 13 was used as a host on the hole transport auxiliary layer and a doped BD370 of 5 wt% was used as a dopant to form a light emitting layer having a thickness of 250 A by vacuum deposition. Of ^{8- (4- (4, 6-} di (naphthalen-2-yl) -l, 3,5-triazin-2-yl) phenyl) quinoline in the emission layer by vacuum deposition to form an electron transport layer of 250A thickness . The organic light emitting device was manufactured by sequentially depositing LiF lOA and A1 1000A on the electron transport layer to form a cathode. Example 2

An organic light emitting device was manufactured in the same manner as in Example 1, except that 1-61 obtained in Synthesis Example 1 and C-10 obtained in Synthesis Example 2 were used at a ratio of 3: 7 (wt / wt). Example 3

An organic light emitting diode was manufactured according to the same method as Example 1 except for using the ratio of 1-61 obtained in Synthesis Example 1 and 7: 3 (wt / wt) of C-10ol obtained in Synthesis Example 2. Example 4

An organic light emitting diode was manufactured according to the same method as Example 1 except for using B-1 17 obtained in Synthesis Example 8 instead of C-10 obtained in Synthesis Example 2.

Example 5

. An organic light emitting diode was manufactured according to the same method as Example 1 except for using B-1 15 obtained in Synthesis Example 6 instead of C-10 obtained in Synthesis Example 2.

Example 6

An organic light emitting diode was manufactured according to the same method as Example 1 except for using H-204 obtained in Synthesis Example 13 instead of 1-61 obtained in Synthesis Example 1.

Example 7

An organic light emitting diode was manufactured according to the same method as Example 1 except for using 1-64 obtained in Synthesis Example 16 instead of 1-61 obtained in Synthesis Example 1.

Example 8

An organic light emitting diode was manufactured according to the same method as Example 1 except for using D-30 obtained in Synthesis Example 11 instead of C-10 obtained in Synthesis Example 2.

Example 9

An organic light emitting diode was manufactured according to the same method as Example 1 except for using B-43 obtained in Synthesis Example 4 instead of C-10 obtained in Synthesis Example 2.

Example 10

An organic light emitting diode was manufactured according to the same method as Example 1 except for using D-31 obtained in Synthesis Example 12 instead of C-10 obtained in Synthesis Example 2.

Example 11

An organic light emitting diode was manufactured according to the same method as Example 1 except for using B-1 14 obtained in Synthesis Example 5 instead of C-10 obtained in Synthesis Example 2. Example 12

An organic light emitting diode was manufactured according to the same method as Example 1 except for using 1-62 obtained in Synthesis Example 14 instead of 1-61 obtained in Synthesis Example 1 and B-1 16 obtained in Synthesis Example 7 instead of C-10. It was.

Example 13

Instead of 1-61 obtained in Synthesis Example 1, using 1-62 obtained in Synthesis Example 14,

Instead of C-10 obtained in 2, use B-1 16 obtained in Synthesis Example 7 and replace 1-62 and B-1 16.

In the same manner as in Example 1 except for using a ratio of 7: 3 (wt / wt)

An organic light emitting device was manufactured.

Example 14

Instead of 1-61 obtained in Synthesis Example 1, using 1-63 obtained in Synthesis Example 15,

An organic light emitting diode was manufactured according to the same method as Example 1 except for using B-1 18 obtained in Synthesis Example 9 instead of C-10 obtained in 2.

Example 15

Instead of C-10 obtained in 2, use B-1 18 obtained in Synthesis Example 9 and replace 1-63 and B-1 18.

3: In the same manner as in Example 1 except that it was used in a ratio of l (wt / wt)

An organic light emitting device was manufactured.

Example 16

Synthesis Example 1-64 obtained in Synthesis Example 16 was used instead of 1-61 in Synthesis Example 1.

An organic light emitting diode was manufactured according to the same method as Example 1 except for using C-23 obtained in Synthesis Example 10 instead of C-10 obtained in 2.

Example 17

In the same manner as in Example 1, except that 1-64 obtained in Synthesis Example 16 was used instead of 1-61 obtained in Synthesis Example 1, and B-1 16 obtained in Synthesis Example 7 was used instead of C-10 obtained in Synthesis Example 2. An organic light emitting device was manufactured.

Example 18

The same procedure as in Example 1 was repeated except that 1-65 obtained in Synthesis Example 17 was used instead of 1-61 obtained in Synthesis Example 1, and B-43 obtained in Synthesis Example 4 was used instead of C-10 obtained in Synthesis Example 2. A light emitting device was prepared. Comparative Example 1

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the hole transport auxiliary layer was not formed.

Comparative Example 2

I- obtained in Synthesis Example 1 instead of 1-61 obtained in Synthesis Example 1 and C-10 obtained in Synthesis Example 2

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the hole transport auxiliary layer was formed of 610,000.

Comparative Example 3

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the hole transport auxiliary layer was formed using only C-10 obtained in Synthesis Example 2 instead of 1-61 obtained in Synthesis Example 1 and C-10 obtained in Synthesis Example 2. .

Comparative Example 4

An organic light-emitting device was manufactured in the same manner as in Example 4, except that the hole transport auxiliary layer was formed using only B-1 17 obtained in Synthesis Example 8 instead of B-1 17 obtained in Synthesis Example 1 and B-1 17 obtained in Synthesis Example 8. Prepared.

Comparative Example 5

An organic light-emitting device was manufactured in the same manner as in Example 12, except that the hole transport auxiliary layer was formed using only 1-62 obtained in Synthesis Example 14 instead of 1-62 obtained in Synthesis Example 14 and B-1 16 obtained in Synthesis Example 7. It was.

Comparative Example 6

An organic light emitting diode was manufactured according to the same method as Example 6 except for forming a hole transport auxiliary layer using only H-204 obtained in Synthesis Example 13 instead of H-204 obtained in Synthesis Example 13 and C-10 obtained in Synthesis Example 2. .

Comparative Example 7

An organic light-emitting device was manufactured in the same manner as in Example 14, except that the hole transport auxiliary layer was formed using only 1-63 obtained in Synthesis Example 15 instead of 1-63 obtained in Synthesis Example 15 and B-1 18 obtained in Synthesis Example 9. It was.

Comparative Example 8

The same procedure as in Example 14 except that the hole transport auxiliary layer was formed using only B-1 18 obtained in Synthesis Example 9 instead of 1-63 obtained in Synthesis Example 15 and B-1 18 obtained in Synthesis Example 9. An organic light emitting device was manufactured by the method.

Comparative Example 9

An organic light emitting device was manufactured in the same manner as in Example 7, except that the hole transport auxiliary layer was formed using only 1-64 obtained in Synthesis Example 16 instead of 1-64 obtained in Synthesis Example 16 and C-10 obtained in Synthesis Example 2. .

Comparative Example 10

An organic light emitting device was manufactured in the same manner as in Example 18, except that the hole transport auxiliary layer was formed using only 1-65 obtained in Synthesis Example 17 instead of 1-65 obtained in Synthesis Example 17 and B-43 obtained in Synthesis Example 4. . Evaluation 2

Driving voltage and efficiency characteristics of the organic light emitting diode according to the Examples and the corresponding comparative examples were evaluated.

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

(1) Measurement of driving voltage

For the manufactured organic light emitting device, the voltage was measured at the same luminance (750 cd / m 2) by using a current-voltmeter (Keithley 2400) while increasing the voltage from 0V to 10V.

(2) Measurement of change in current density in response to voltage changes

For the organic light emitting device manufactured, 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.

(3) Measurement of luminance change by voltage change

The resulting organic light emitting device was measured using a luminance meter (Minolta Cs-1000 A) while increasing the voltage from 0V to 10V to obtain a result.

(4) 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 (2) and (3).

[3 votes]

£ 6 .88Z8l / ST0Z OAV Referring to Table 2, the organic light emitting diode according to the embodiments is driven in comparison with the organic light emitting diode according to each comparative example including the organic light emitting diode according to Comparative Example 1 and a single compound without using the hole transport auxiliary layer It can be seen that the voltage and efficiency characteristics are greatly improved. Evaluation 3

The lifespan characteristics of the organic light emitting diode according to the examples and the corresponding comparative examples were evaluated.

The life characteristics were evaluated from the measurement by keeping the luminance (cd / m 2) at 6000 cd / m 2 and decreasing the current efficiency (cd / A) to 97%.

The results are shown in Table 3.

TABLE 3

Service life (T97,

(wt / wt) h)

Example 1 I-61: C-10 (5: 5) 50

Example 2 1-61: C-10 (3: 7) 49

Example 3 I-61: C-10 (7: 3) 48

Example 4 I-61: B-117 (5: 5) 62

Example 5 I-61: B-115 (5: 5) 60

Example 6 H-204: C-10 (5: 5) 71

Example 7 I-64: C-10 (5: 5) 64

Example 8 I-61: D-30 (5: 5) 78

Example 9 I-61: B-43 (5: 5) 65

Example 10 I-61: D-31 (5: 5) 69

Example 12 I-62: B-116 (5: 5) 58

Example 14 I-63: B-118 (5: 5) 60

Comparative Example 2 1-61 38

Comparative Example 3 C-10 1 Comparative Example 4 B-1 17 10

Comparative Example 5 1-62 50

Comparative Example 6 H-204 43

Comparative Example 8 B-1 18 42 Referring to Table 3, it can be seen that the organic light emitting diode according to the embodiments has a greatly improved lifespan characteristics compared to the organic light emitting diode according to each of the comparative examples including a single compound. . 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, the embodiments described above are to be understood in all respects as illustrative and not restrictive.

[Explanation of code]

300: organic light emitting device

1 10: anode

120: cathode

130: light emitting layer

141: hole transport layer

142: hole transport auxiliary layer

Claims

[Range of request]

[Claim 1]

Anode and cathode facing each other,

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

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

A hole transport auxiliary layer positioned between the hole transport layer and the light emitting layer

Including

The hole transport auxiliary layer

A first compound represented by Formula 1, and

A second compound represented by the following formula (2) or a combination of the following formulas (3) and (4)

Organic optoelectronic device containing all.

[Formula 1]

Ari

Ar ³ b ¹

^ L3 /

\

L ²

\

Ar 2

In Chemical Formula 1,

At least one of Ar ¹ to Ar ³ is one of a group represented by the following formula (A), a group represented by the combination of the following formula B and the formula (C) or a combination of the following formula B and the formula (D), [A Formula B] [Formula C]

In Chemical Formulas A to D,

X and Z are 0, S or CR ^a R ^b ,

Two adjacent * of Formula B are fused with two adjacent * of Formula c or Formula D,

Unfused * in Formula B and Formula C are each CR ^C ,

Cycloalkoxy group, substituted or unsubstituted C1 to C20 alkylthio group, substituted or unsubstituted C6 to C30 arylalkyl 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 heterocyclic group, substituted or unsubstituted C2 to C30 amino group, substituted or unsubstituted C3 to C30 silyl group, halogen, cyano group nitro A group, a hydroxyl group, a carboxyl group, a combination thereof, a fused ring of a combination thereof, or a linking point with at least one of L ¹ to L ³ of Formula 1,

R ¹ and R ² each independently exist or form a fused ring with each other. R ³ and R ⁴ each independently exist or form a fused ring with each other,

[Formula 2] [Formula 3] [Formula 4]

In Chemical Formulas 2 to 4,

Y ¹ , Y ^la and Y ^lb are each independently a single bond, substituted or unsubstituted C1 to C20 alkylene group, substituted or unsubstituted C2 to C20 alkenylene group, substituted or unsubstituted

A C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 divalent heterocyclic group, a combination thereof or a fused ring of a combination thereof,

Ar ⁴ , Ar ^4a and Ar ^4b 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,

Two adjacent * of Formula 3 are fused with two * of Formula 4,

Two unfused * of Formula 3 are CR ⁵ , CR ⁰ , respectively,

R ⁵ to R ¹⁰ are each independently hydrogen, deuterium, substituted or unsubstituted C1 to

C20 alkyl group, substituted or unsubstituted C6 to C50 aryl group, substituted or unsubstituted C2 to

C50 heterocyclic group or a combination thereof,

R ⁵ and R ⁶ are each independently present or connected to each other to form a ring, R ⁷ and R ⁸ are each independently present or connected to each other to form a ring, R ⁹ and R ¹⁰ are each independently present or each other Are linked to form a ring, and at least one of R ⁵ to R ⁸ and Ar ⁴ of Formula 2 is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted triphenylene group, or a substituted or unsubstituted carbazolyl group Including

At least one of R ⁵ to R ¹⁰ , Ar ^4a and Ar ^4b of Formula 3 or 4 includes a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted triphenylene group, or a substituted or unsubstituted carbazolyl group. .

[Claim 2]

In U-port,

Ar ¹ to Ar ³ of Formula 1 are each independently a group listed in Group 1, a group represented by Formula A or a combination of Formula B and Formula C,

At least one of Ar ¹ to Ar ³ is an organic optoelectronic device group consisting of a group represented by the formula (A) or a combination of the formula (B) and the formula (C). Group i]

In group 1 above,

R ⁷⁵ to R ¹¹⁷ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted Substituted C1 to C30 alkoxy group, substituted or unsubstituted C6 to C30 arylalkyl group, substituted or unsubstituted C5 to C30 aryloxy group, substituted or unsubstituted C5 to C30 arylthio group, substituted or unsubstituted C1 to C30

[Claim 3]

In claim 1,

The C1 compound is an organic optoelectronic device represented by any one of the following Formula 1-1 to 1-νΠΙ:

L ¹ to L ³ are each independently a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C3 to C30

X ^a to ^ are each independently 0, S or CR ^a R ^b ,

R ^lb , R ^2a to R ^2c , R ^3a to R ^3e , R ^4a to R ^4c , R ^a and R ^b are each independently hydrogen, deuterium, 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 heterocyclic group, substituted or Unsubstituted C2 to C30 amino group, substituted or unsubstituted C3 to C30 silyl group, halogen _. , Cyano group, nitro group, hydroxyl group, carboxyl group, a combination thereof, and a fused ring of a combination thereof.

[Claim 4]

In claim 3,

At least one of X ^a to X ^c is each independently 0 or S, an organic optoelectronic device. [Claim 5]

In claim 1,

The second compound is an organic optoelectronic device represented by any one of the following formulas 2-1 to 2-IV:

[Formula 2-1] [Formula 2-II]

[Formula 2-ΙΠ] [Formula 2-IV]

In Chemical Formulas 2-1 to 2-IV,

Υ ¹ to Υ ³ are each independently a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C6 to C30 arylene group, a divalent substituted or Unsubstituted C2 to C30 heterocyclic group, a combination thereof or a fused ring of a combination thereof,

R ⁵ to R ²⁰ are each independently hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C50 aryl group, substituted _. Or an unsubstituted C2 to C50 heterocyclic group or a combination thereof.

[Claim 6]

In paragraph 1,

The second compound is an organic optoelectronic device represented by any one of the following formulas 3-1 to 3-VII:

[Formula 3-1] [Formula 3-II]

[Formula 3-III]

In Chemical Formulas 3-1 to 3-VII,

[Claim 7]

In paragraph 1,

The first compound is an organic optoelectronic device of any one of the compounds listed in Group 2. [Group 2]

[-32] [F-35] [F-36] [F-39] [F-40]

[【寸 £ 【卜一-

[1-61] [1-62] [1- [1-64]

-65]

[Claim 8]

In claim 1,

The second compound is one of the compounds listed in Group 3 below.

[Group 3]

B-10 Β-1δ 8— SO 8—22

§-24 B-3i

[Claim 9]

In claim 1,

The hole transport auxiliary layer is in contact with the light emitting layer.

[Claim 10]

(F) in paragraph 1,

The hole transport auxiliary layer includes a plurality of layers,

And the first compound and the second compound are included in a layer in contact with the light emitting layer among the plurality of hole transport auxiliary layers.

[Claim 11]

In crab 1,

The difference between the HOMO energy level of the first compound and the second compound is O. OleV to 0.5eV organic optoelectronic device.

[Claim 12]

In claim 1,

The light emitting layer includes a host and a dopant,

The first compound and the second compound is an organic optoelectronic device satisfying the following relations 6 to 9:

[Relationship 6]

E ^L _p i | <| E ^L host |

[Relationship 7]

E ^L _p l | <| E ^L dopant |

[Relationship 8]

E ^L _p2 | <| E ^L host |

[Relationship 9]

E ^L _p | <| E ^L dopant | In the relation 6 to 9,

E ^L _pl is the LUMO energy level of the first compound, E ^L _p2 is the LUMO energy level of the second compound, E ^L _hSt is the LUMO energy level of the host of the light emitting layer, and ^ ^ is the LUMO energy level of the _dopant of the light emitting layer.

【Claim 13】

In claim 1,

The light emitting layer includes a host and a dopant,

The first compound and the second compound is an organic optoelectronic device that satisfies the following relations 10 to 13.

[Relationship 10]

| E ^T host | <| E ^T _p i |

[Relationship 1 1]

| E ^T hosl | <| E ^T _P 2 |

[Relationship 12]

| E ^T dopant | <| E ^T _p i |

[Relationship 13]

| E ^T dopant | <| E ^T _p2 |

In the relation 10 to 13,

E ^T _pl is a triplet energy level and Ε ^τ _ρ2 is the triplet energy level of the second compound of the first compound _E ^T _h0St is a triplet energy level of the host of the light emitting layer ^^^ is a triplet light-emitting layer of the bit dopyeon The energy level.

[Claim 14]

In claim 1,

The first compound and the second compound is an organic optoelectronic device having a uniform mixing ratio along the thickness direction of the hole transport auxiliary layer

[Claim 15]

In claim 1,

The hole transport layer is an organic optoelectronic device comprising a compound represented by the formula (3): [Chemistry 3]

In Chemical Formula 3,

R ^{1 18} to R ¹²¹ 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 C2 to C30 heterocyclic group, or a combination thereof And

R ^{1 18} and R ^{1 19} each independently exist or form a fused ring with each other, R ¹²⁰ and R ¹²¹ each independently exist or form a fused ring with each other, and Ar ⁶ to Ar ⁸ are each independently substituted or unsubstituted A substituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heterocyclic group,

L ⁴ to L ⁷ are each independently a single bond, a substituted or unsubstituted C2 to C10 alkylene group, a substituted or unsubstituted C2 to C10 alkenylene group, a substituted or unsubstituted C2 to C10 alkynylene group, a substituted or Unsubstituted C6 to C30 arylene groups, substituted or unsubstituted C2 to C30 divalent heterocyclic groups, or a combination thereof.

[Claim 16]

The method of claim 15,

Ar ⁶ of Formula 3 is a substituted or unsubstituted phenyl group, or a substituted or unsubstituted biphenyl group,

Ar ⁷ and Ar ⁸ of Formula 3 are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted fluorene group, a substituted or unsubstituted bisfluorene group, a substituted or unsubstituted An organic optoelectronic device, which is any one of a substituted triphenylene group, a substituted or unsubstituted anthracene group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted dibenzofuran group, or a substituted or unsubstituted dibenzothiophenyl group.

[Claim 17] 17. An organic optoelectronic device according to any one of claims 1 to 16.