WO2017099326A1

WO2017099326A1 - Compound for organic optoelectronic device, organic optoelectronic device, and display apparatus

Info

Publication number: WO2017099326A1
Application number: PCT/KR2016/008569
Authority: WO
Inventors: 한수진; 강동민; 이한일; 류동완; 민수현; 신창주; 유은선; 정성현; 정호국
Original assignee: 삼성에스디아이 주식회사
Priority date: 2015-12-08
Filing date: 2016-08-03
Publication date: 2017-06-15
Also published as: KR101962420B1; KR20170067473A

Abstract

Provided are: a compound for an organic optoelectronic device, represented by chemical formula I; an organic optoelectronic device to which the same is applied; and a display apparatus comprising the organic optoelectronic device. [Chemical formula I] (In chemical formula I, X is O or S.)

Description

【Specification】

[Name of invention]

Compound for organic optoelectronic devices, organic optoelectronic devices and display devices

Technical Field

A compound for organic optoelectronic devices, an organic optoelectronic device, and a display device.

Background Art

Organic optoelectronic devices are devices that can switch electrical energy and light energy.

Organic optoelectronic devices can be divided into two types according to the principle of operation. One is an optoelectronic device in which excitons formed by light energy are separated into electrons and holes, and the electrons and holes are transferred to the other electrodes, respectively, to generate electrical energy. It is a light emitting device that generates light energy from 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, and has a structure in which an organic layer is inserted between an anode and a cathode.

consist of. The organic layer may include a light emitting layer and an auxiliary layer, and the auxiliary layer may include, for example, a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, and an electron injection layer to increase efficiency and stability of the organic light emitting device. And at least one layer selected from a hole blocking layer.

The performance of the organic light emitting device is greatly influenced by the characteristics of the organic layer, and in particular, by the organic materials included in the organic layer.

In particular, in order for the organic light emitting diode to be applied to a large flat panel display, it is necessary to develop an organic material capable of increasing the mobility of holes and electrons and increasing electrochemical stability.

[Detailed Description of the Invention]

[Technical problem] It is to provide a compound capable of providing an organic optoelectronic device having high efficiency, long life and the like.

It is ^"to provide a display device including an organic optoelectronic device and the organic optoelectronic devices comprising said compound.

Technical Solution

According to one embodiment, a compound for an organic optoelectronic device represented by the following formula (I) is provided.

[Formula I]

In Formula I,

X is 0 or S,

R ¹ is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heterocyclic group, a substituted or unsubstituted C6 to C30 arylamine group, or a combination thereof,

R ² to R ⁵ are each independently hydrogen, deuterium, substituted or unsubstituted C1 to

C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C6 to C30 arylamine group, or Combination of these,

L is a single bond, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof,

Herein, "substituted" means that at least one hydrogen is deuterium, a halogen group, a hydroxyl group, a C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C2 to C30 heterocyclo Alkyl group, C6 to C30 aryl group, C2 to C30 heterocyclic group, C1 to C20 alkoxy group, C1 to C10 trifluoroalkyl group or Mean substituted by cyano group.

According to another embodiment, an organic optoelectronic device includes an anode and a cathode facing each other, and at least one organic layer positioned between the anode and the cathode, the organic layer including the compound for an organic optoelectronic device described above. do.

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

EFFECTS OF THE INVENTION The highly efficient long-life organic optoelectronic devices can be realized.

[Brief Description of Drawings]

1 and 2 are cross-sectional views illustrating organic light emitting diodes according to example embodiments.

100 and 200: organic light emitting element

105: organic layer

1 10: cathode

120: anode

130: light emitting layer

140: hole auxiliary layer

[Best form for implementation of the invention]

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

As used herein, "substituted" means that at least one hydrogen is deuterium, a halogen group, a hydroxyl group, a C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C2 to C30 It means substituted with a heterocycloalkyl group, a C6 to C30 aryl group, a C2 to C30 heterocyclic group, a C1 to C20 alkoxy group, a C1 to C10 trifluoroalkyl group or a cyano group.

In addition, the substituted halogen group, hydroxyl 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 Adjacent groups of an aryl group, a C2 to C30 heterocyclic group, a C1 to C20 alkoxy group, a C1 to C10 trifluoroalkyl group, or a cyano group Two substituents may be fused to form a ring. For example, the substituted C6 to C30 aryl group can be fused to another adjacent substituted C6 to C30 aryl group to form a substituted or unsubstituted fluorene ring.

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

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

It means a hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double bonds or triple bonds.

The alkyl group may be an alkyl group of C1 to C30. More specifically, the alkyl group

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

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

As used herein, the term "aryl (aryl) group" refers to a group of groups having at least one hydrocarbon aromatic moiety, wherein all of the elements of the hydrocarbon aromatic moiety have a P-orbital, and these P-orbitals are conjugated (conjugation). ), Including a phenyl group, a naphthyl group, and the like, and two or more hydrocarbon aromatic moieties connected through a sigma bond, such as a biphenyl group, a terphenyl group, a quarterphenyl group, and the like. Non-aromatic fused rings in which the tees are fused directly or indirectly may be included, for example, a fluorenyl group and the like.

Aryl groups are monocyclic, polycyclic or fused ring polycyclic (i.e.

Ring) groups that divide adjacent pairs of carbon atoms. For example, the aryl group means a phenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, chrysenyl group and the like.

As used herein, the term "heterocyclic group" is a higher concept including a heteroaryl group, 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 the group consisting of N, 0, S, P and Si in place of carbon (C). In the case where the heterocyclic group is a fused ring, the heterocyclic group may include one or more heteroatoms for all or each ring.

In one example, a "heteroaryl group" refers to N, O, S, P and instead of carbon (C) in the aryl group.

It means to contain at least one hetero atom selected from the group consisting of Si. Two or more heteroaryl groups may be directly connected through a sigma bond, or when the C2 to C60 heteroaryl group includes two or more rings, two or more rings may be fused to each other. When the heteroaryl group is a fused ring, each ring may contain 1 to 3 heteroatoms.

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, 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 perrylenyl 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 groups, substituted or unsubstituted benzimidazolyl groups, substituted or unsubstituted indolyl groups, substituted or unsubstituted groups Substituted quinolinyl groups, substituted or unsubstituted isoquinolinyl groups, 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 carbazole group, substituted or unsubstituted benzothiophenpyrimidinyl group, substituted or unsubstituted benzothiophenpyridyl group, substituted Or an unsubstituted benzofuran pyrimidinyl group, a substituted or unsubstituted benzofuran pyridyl group, a substituted or unsubstituted benzofuran pyrrolyl group, a substituted or unsubstituted benzothiophenpyridyl group, a substituted or unsubstituted benzothiopenty An azolyl group, a substituted or unsubstituted benzofuranthiazolyl group, a substituted or unsubstituted thiazoloquinolinyl group, a substituted or unsubstituted oxazoloquinolinyl group, or a combination thereof, but

It is not limited.

In the present specification, a single bond means carbon or a bond directly connected to each other via a hetero atom other than carbon, and specifically, L means a single bond that a substituent connected to L is directly connected to a central core. it means. That is, in the present specification, a single bond does not mean methylene or the like via carbon.

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

Hereinafter, a compound for an organic optoelectronic device according to one embodiment is described.

The compound for an organic optoelectronic device according to one embodiment is represented by the following formula (I). [Formula I]

In formula (I)

X is 0 or S,

R ¹ is a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to

C30 heterocyclic group, substituted or unsubstituted C6 to C30 arylamine group, or a combination thereof,

R ² to R ⁵ are each independently hydrogen, deuterium, substituted or unsubstituted C1 to C30 alkyl group, substituted or unsubstituted C3 to C30 cycloalkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted A C2 to C30 heterocyclic group, a substituted or unsubstituted C6 to C30 arylamine group, or a combination thereof,

Here, "substituted" means that at least one hydrogen is deuterium, halogen, C1 to C40 silyl group, C1 to C30 alkyl group, C1 to C10 alkylsilyl group, C3 to C30 cycloalkyl group, C2 to C30 heterocycloalkyl group, C6 to C30 It means an aryl group, a C2 to C30 heterocyclic group, a C1 to C20 alkoxy group, a C1 to C10 trifluoroalkyl group or a cyano group.

The core of the compound for organic optoelectronic devices represented by the formula (I)

An additional ring is fused to indolophenoxazine (indolo phenoxazine), or indolophenothiazine.

In Formula (I), by including a form in which an additional ring is fused as a core, π-conjugated as compared to a structure comprising a phenoxazine core, a phenothiazine core, an indolophenoxazine core, and an indolovinothiazine core Widen the gating, so electron or hole mobility Can be high.

In addition, by including 0 or S in X, it has a low HOMO value when compared to the structure containing C or N, which is advantageous to lower the driving voltage.

In one embodiment of the present invention to reduce the driving voltage through an additional ring extended from the indolophenoxazine core, or indolophenothiazine core, and at the same time to manufacture a long-life and high efficiency organic electroluminescent device Can be.

In one embodiment of the invention the HOMO energy level and through the substituent R ¹ and

By adjusting the LUMO energy level, the effect of desired efficiency and long life can be obtained. Specifically, the substituent R ¹ is a C6 to C30 aryl group unsubstituted or substituted

C30 aryl group; C6 to C30 arylamine group unsubstituted or substituted with C6 to C30 aryl group; A C2 to C30 heterocyclic group unsubstituted or substituted with a C6 to C30 aryl group or a C2 to C30 heterocyclic group; Or N-containing C2 to C30 except for a carbazolyl group

It may be a C6 to C30 aryl group substituted with a heterocyclic group.

Meanwhile, indolophenoxazine core, or indolophenothiazine

A core having an additional ring extended from (indolophenothiazine) has excellent light emitting ability and electron transporting ability or hole transporting ability of the core itself, but due to the plate-like structure, fairness may be reduced during the deposition process. However, fairness can be improved by including a C6 to C30 aryl group substituted or unsubstituted with a C6 to C30 aryl group in R ¹ as a substituent to modify the plate structure.

In addition, the core has excellent hole accepting ability, while the hole transporting ability is

There is an aspect that is insufficient for use in the hole transport layer. However, R ¹ to C6 to C30

A C6 to C30 arylamine group, which is unsubstituted or substituted with an aryl group, may be included as a substituent to have a hole transporting capacity of about a layered layer for use in the hole transport layer.

In addition, C2 to C30 heterocyclic group having a hole characteristic in R ¹

By substituting, a device having a stronger hole accepting ability and a hole transporting ability can be manufactured,

By substituting the C2 to C30 heterocyclic groups having electronic properties in R ¹ , a device suitable for use in a HOST defect or an electron transport layer having bipolar properties can be produced. More specifically, the C6 to C30 aryl group or C2 to C30 The C2 to C30 heterocyclic group unsubstituted or substituted with a heterocyclic group includes a C2 to C30 heterocyclic group having hole characteristics, and a C2 to C30 heterocyclic group having electronic characteristics,

The C2 to C30 heterocyclic group having the above hole characteristics is a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted group

Dibenzothiophenyl group,

The C2 to C30 heterocyclic group having the above electronic properties may be an N-containing C2 to C30 heterocyclic group except for a carbazolyl group or an N-containing C2 to C30 heterocyclic group except for a carbazolyl group unsubstituted or substituted with a C6 to C30 aryl group. .

N-containing C2 to C30 heterocyclic group except for the carbazolyl group is, for example, a substituted or unsubstituted pyridinyl group, a substituted or unsubstituted pyrimidinyl group, a substituted or unsubstituted triazinyl group, a substituted or unsubstituted quinazoli Nyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted indolyl group, substituted or Unsubstituted isoindolyl group, substituted or unsubstituted benzothiophenpyrimidinyl group, substituted or unsubstituted benzothiophenpyridyl group, substituted or unsubstituted benzofuran pyrimidinyl group, or substituted or unsubstituted benzofuran pyri It may be a dill.

In one embodiment of the present invention, the C2 to C30 heterocyclic group is a pyridyl group, pyrimidyl group, triazinyl group, benzoimidazole group, benzopyrimidyl group, benzopyridyl group, carbazolyl group, dibenzofuranyl group, dibenzoti Offenyl, fluorenyl, benzothiopyrimidinyl,

It may be selected from benzofuran pyrimidinyl group, benzothiopyridyl group or benzofuran pyridyl group.

The C6 to C30 aryl group unsubstituted or substituted with the C6 to C30 aryl group may be, for example, a phenyl group, a biphenyl group, a terphenyl group, a quarterphenyl group, a fluorenyl group, and the like, but is not limited thereto.

The C6 to C30 arylamine group unsubstituted or substituted with the C6 to C30 aryl group may be, for example, a diphenylamine group, a dibiphenylamine group, a phenylbiphenylamine group, a phenylnaphthylamine group, a dinaphthylamine group, or the like. It is not limited to this.

C6 to C30 aryl group substituted with N-containing C2 to C30 heterocyclic group except the carbazolyl group, pyridinylphenyl group, pyrimidinylphenyl group, triazinylphenyl group, Pyridinylbiphenyl group, pyrimidinylbiphenyl group, triazinylbiphenyl group,

Dipyridinylphenyl group, dipyrimidinylphenyl group, ditriazinylphenyl group, dipyridinylbiphenyl group, dipyrimidanylbiphenyl group, ditriazinylbiphenyl group, quinolinylphenyl group,

It may be an isoquinolinylphenyl group, a quinolinylbiphenyl group, an isoquinolinylbiphenyl group, etc., but is not limited thereto.

In the most specific embodiment of the present invention, R ¹ may be selected from the groups listed in the following Groups 1 to 4, but is not limited thereto.

Group 1]

[Group 2]

Group 3]

In groups 1 to 4, * is a point of attachment.

Meanwhile, in one embodiment of the present invention, L is a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted quarterphenylene group, It may be a substituted or unsubstituted naphthylene group, or a combination thereof.

For example, it may be selected from a single bond and a substituted or unsubstituted group listed in Group 5 below. Group 5]

In group 5 above,

* Is a point of attachment, where "substitution" is as described above.

The compound for an organic optoelectronic device may be selected from, for example, the compounds listed in Groups A to D, but is not limited thereto.

[Group A]

91 9ZC660 / .T0Z OAV

Hereinafter, a valuable optoelectronic device to which the compound for an organic optoelectronic device is applied will be described.

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

The organic optoelectronic device may include an anode and a cathode facing each other, at least one organic layer positioned between the anode and the cathode, and the organic layer may include the compound for an organic optoelectronic device described above.

Herein, an organic light emitting diode as an example of an organic optoelectronic device will be described with reference to the drawings.

1 and 2 are cross-sectional views illustrating an organic light emitting diode according to an embodiment. Referring to FIG. 1, an organic light emitting diode 100 according to an embodiment includes an anode 120 and a cathode 110 facing each other, and an organic layer 105 positioned between the anode 120 and the cathode 1 10. It includes. The anode 120 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 120 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: PEDT), polypyrrole and polyaniline, and the like. It is not limited.

A cathode (110) is, for example, and an electron injection can be a work function of ^■ made low conductive body so as to facilitate, for example, it may be made of a metal, metal oxide and / or conductive polymers. The negative electrode 1 10 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 organic dance 105 includes a light emitting layer 130 including the compound for an organic optoelectronic device described above.

The light emitting layer 130 may include, for example, the compound for an organic optoelectronic device alone, may include at least two kinds of the compound for the organic optoelectronic device described above, or may include the composition for the organic optoelectronic device described above. .

The compound for an organic optoelectronic device according to an embodiment of the present invention may be included, for example, as a host of the light emitting layer, and most specifically, may be included as a red host. Referring to FIG. 2, the organic light emitting diode 200 further includes a hole auxiliary layer 140 in addition to the light emitting layer 130. The hole auxiliary layer 140 may further increase hole injection and / or hole mobility between the anode 120 and the light emitting layer 130 and block electrons. The hole auxiliary layer 140 may be, for example, a hole transport layer, a hole injection layer, and / or an electron blocking layer, and may include at least one layer. The compound for an organic optoelectronic device described above may be included in the emission layer 130.

In an embodiment of the present invention, the organic light emitting device may further include an electron transport layer, an electron injection layer, a hole injection layer, and the like as the organic layer 105 in FIG. 1 or 2. The organic light emitting diodes 100 and 200 form an anode or a cathode on a substrate, and then form an organic layer by a dry film method such as evaporation, sputtering, plasma plating, and ion plating, and then thereon. It can be prepared by forming a cathode or an anode.

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.

Starting materials and reactants used in the synthesis examples and examples were purchased from Sigma-Aldrich or TCI, unless otherwise noted. Synthesis Example 1 Synthesis of Intermediate 1-1

[Banungsik 1]

Dissolve 1011- | 311∞0 & ^^ (20 109 11 101) in 101 ^^ 0.2] _^ in a nitrogen environment, then add 1-bromo-2-iodobenzene (36 g, 131 mmol)

Tris (diphenylideneacetone) dipalladium (o) (lg, 1.09 mmol), tris-tert butylphosphine (0.2 g, 1.09 mmol) and sodium tert-butoxide (0. ² g, 2 mmol) were added sequentially and 18 hours at 100 ^° C. Heated to reflux. After the reaction was completed, add water to the reaction solution

Extracted with dichloromethane (DCM) and then water was removed with anhydrous MgS0 ₄ , filtered and concentrated under reduced pressure. The obtained residue was separated and purified through flash column chromatography to obtain Intermediate 1-1 (29 g, 80%).

HRMS (70 eV, EI < + >): m / z calcd for C 18 H 12 BrNO: 337.0102, found: 337.

Elemental Analysis: C, 64%; H, 4% Synthesis Example 2 Synthesis of Intermediate 1-2 Scheme 2]

In nitrogen, Intermediate 1-1 (29 g, 68 mmol) was dissolved in 1 L of dimethylformamide (DMF), followed by Palladium (II) acetate (2.2 g, 10.2 mmol) and Benzyltriethylammonium chloride (BnEt3NCl) (15 g, 68 mmol). ) And stirred. Potassium carbonate saturated in water (23 g, 340 mmol) was added thereto, and the resulting mixture was heated and refluxed at 80 ^° C. for 12 hours. After the reaction was completed, water was added to the reaction solution, and extracted with dichloromethane (DCM), and then water was removed with anhydrous MgS0 ₄ , filtered and concentrated under reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining intermediate 1-2 (11 g, 65%).

HRMS (70 eV, EI < + >): m / z calcd for C 18 H 11 NO: 257.0841, found: 257.

Elemental Analysis: C, 84%; H, 3% Synthesis Example 3 Synthesis of Intermediate 1-3

3]

In a nitrogen environment, Intermediate 1-2 (30 g, 87 mmol) ol is dissolved in 1 L of dichloromethane and stirred at 0 ^° C. N-bromosuccinimide (NBS) (13 g, 78.3 mmol) was added thereto, followed by stirring at room temperature for 6 hours. After the reaction was completed, water was added to the reaction solution, and the mixture was filtered and dried in a vacuum oven. The residue thus obtained is flash column

Chromatographic separation and purification afforded Intermediate 1-3 (23 g, 80%).

HRMS (70 eV, EI < + >): m / z calcd for C 18 H 10 BrNO: 334.9946, found: 335.

Elemental Analysis: C, 64%; H, 3% Synthesis Example 4 Synthesis of Intermediate 1-4 4]

In nitrogen, Intermediate 1-3 (23 g, 68 mmol) was dissolved in 1 L of dimethylformamide (DMF), followed by 1 4,4,5,5-tetramethyl-2- (2-nitrophenyl) -l, 3,2- Dioxaborolane (18 g, 74.8 mmol) and tetrakis (triphenylphosphine) palladium (785 mg, 0.68 mmol) were added and stirred. 1 ^ & 33 11 ^ 130 6 (23 170 1 ^ 1) saturated in water was added and refluxed at 80 ^° C. for 12 hours. After completion of reaction, water was added to the reaction solution, extracted with dichloromethane (DCM), water was removed with anhydrous MgS0 ₄ , filtered and concentrated under reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining an intermediate 1-4 (25 g, 95%).

HRMS (70 eV, EI < + >): m / z calcd for C24H14N203: 378.1004, found: 378.

Elemental Analysis: C, 76%; H, 4% Synthesis Example 5 Synthesis of Intermediate 1-5

5]

Intermediate 1-4 (25 g, 68 mmol) was added to Triethyl phosphate (56 g, 340 mmol) in a nitrogen environment, followed by stirring. After the reaction was completed, water was added to the reaction solution, extracted with dichloromethane (DCM), water was removed with anhydrous MgS0 ₄ , filtered, and concentrated under reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining an intermediate 1-5 (16 g, 70%).

HRMS (70 eV, EI < + >): m / z calcd for C 24 H 14 N 20: 346.1106, found: 346.

Elemental Analysis: C, 83%; H, 4% Synthesis Example 6 Synthesis of Intermediate 1-6 [Bandungsik 6]

In a nitrogen environment, 4-1 01∞-1,1'-1 ^ 1 ^ 1 (20 86 11 ^ 101) was dissolved in 1 L of dimethylformamide (DMF), followed by bis (pinacolato) diboron (26 g, 103 mmol). And (1,1 '-bis (diphenylphosphine) ferrocene) dichloropalladium (II) (0.7 g, 0.86 mmol) and potassium acetate (21 g, 215 mmol) were added and heated to reflux for 5 hours at 150 ^° C. After the reaction was completed, water was added to the reaction solution, and the mixture was filtered and dried in a vacuum oven. The obtained residue was separated and purified through flash column chromatography, obtaining an intermediate I-6 (20 g, 85%).

HRMS (70 eV, EI +): m / z calcd for C18H21B02: 280.1635, found: 280

Elemental Analysis: C, 77%; H, 8% Synthesis Example iii: Synthesis of Intermediate 1-7

7]

In nitrogen, Intermediate 1-6 (20 g, 71 mmol) was dissolved in 1 L of THF, followed by 1-bromo-3 -iodobenzene (24 g, 85 mmol) and tetrakis (triphenylphosphine) palladium (0.8 mg, 0.7 mmol). ) Was added and stirred. 1 ^ & 5 ^^。 3] "1) 0 ^ 1 24.5 177 11 101) saturated in water was added and heated to reflux at 80 ^° C for 12 hours. After completion of the reaction, water was added to the reaction solution and dichloromethane (DCM) was added. The resulting residue was filtered, dried over anhydrous MgSO ₄ , filtered and concentrated under reduced pressure, and the residue thus obtained was separated and purified through flash column chromatography to obtain Intermediate 1-7 (30 g, 90%).

HRMS (70 eV, EI < + >): m / z calcd for C 18 H 13 Br: 309.1998, found 309 Elemental Analysis: C, 70%; H, 4% Synthesis Example 8 Synthesis of Intermediate 1-8

8]

In nitrogen, Intermediate 1-7 (25 g, 81 mmol) was dissolved in 1 L of dimethylformamide (DMF), followed by bis (pinacolato) diboron (25 g, 97 mmol) and (Ι, Γ- bis (diphenylphosphine) ferrocene). Dichloropalladium (II) (0.7 g, 0.81 mmol) and potassium acetate (20 g, 203 mmol) were added thereto, and the resulting mixture was heated and refluxed at 150 ^° C for 5 hours. After the reaction was completed, water was added to the reaction solution, and the mixture was filtered and dried in a vacuum oven. The obtained residue was separated and purified through flash column chromatography, obtaining an intermediate 1-8 (27 g, 93%).

HRMS (70 eV, EI +): m / z calcd for C24H25B02: 356.1948, found: 356

Elemental Analysis: C, 81%; H, 7% Synthesis Example 9 Synthesis of Intermediate 1-9

9]

In nitrogen, Intermediate 1-8 (50 g, 140 mmol) was dissolved in 1 L of THF, followed by 1-bromo-3 -iodobenzene (47 g, 168 mmol) and tetrakis (triphenylphosphine) palladium (1.6 g, 1.4 mmol). ) Was added and stirred. Potassium carbonate saturated in water (48 g, 350 mmol) was added thereto, and the resulting mixture was heated and refluxed at 80 ^° C. for 12 hours. After the reaction was completed, water was added to the reaction solution, extracted with dichloromethane (DCM), water was removed with anhydrous MgS0 ₄ , filtered, and concentrated under reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining an intermediate 1-9 (44 g, 89%).

HRMS (70 eV, EI +): m / z calcd for C24H17Br: 384.0514, found 384 Elemental Analysis:

C, 75%; H, 4% Synthesis Example 10 Synthesis of Intermediate 1-10

In nitrogen, intermediate 1-9 (20 g, 52 mmol) was dissolved in 1 L of dimethylformamide (DMF), followed by bis (pinacolato) diboron (16 g, 62.5 mmol) and (Ι, Γ- bis (diphenylphosphine) ferrocene). Dichloropalladium (II) (0.4 g, 0.52 mmol) and potassium ^ 13 130 1 ^ 101) was added and heated to reflux for 5 hours at 150 ^° C. After completion of reaction, water was added to the reaction solution, and the mixture was filtered and dried in a vacuum oven. The obtained residue was separated and purified through flash column chromatography, obtaining an intermediate 1-10 (19 g, 85%).

HRMS (70 eV, EI +): m / z calcd for C30H29BO2: 432.2261, found: 432

Elemental Analysis: C, 83%; H, 7% Synthesis Example 11: Synthesis of Intermediate 1-11

11]

In nitrogen, Intermediate 1-10 (60 g, 140 mmol) was dissolved in 1 L of THF, followed by 1-bromo-3 -iodobenzene (47 g, 168 mmol) and tetrakis (triphenylphosphine) palladium (1.6 g, 1.4 mmol). ) Was added and stirred. Potassium carbonate saturated in water (48 g, 350 mmol) was added thereto, and the resulting mixture was heated and refluxed at 80 ^° C. for 12 hours. After completion of reaction, water was added to the reaction solution, extracted with dichloromethane (DCM), water was removed with anhydrous MgS0 ₄ , filtered and concentrated under reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining an intermediate 1-1 1 (54 g, 85%).

HRMS (70 eV, EI +): m / z calcd for C 30 H 21 Br: 460.0827, found 460 Elemental Analysis:

C, 78%; H, 5% Synthesis Example 12 Synthesis of Intermediate 1-12

12]

In a nitrogen environment, 3-bromo-l, r-biphenyl (20 g, 86 mmol) was dissolved in 1 L of dimethylformamide (DMF), followed by bis (pinacolato) diboron (26 g, 103 mmol) and (Ι, Ι '- Bis (diphenylphosphine) ferrocene) dichloropalladium (II) (0.7 g, 0.86 mmol) and potassium acetate (21 g, 215 mmol) were added and heated to reflux for 5 hours at 150 ^° C. After the reaction was completed, water was added to the reaction solution, and the mixture was filtered and dried in a vacuum oven. The obtained residue was separated and purified through flash column chromatography, obtaining an intermediate 1-12 (20 g, 85%).

HRMS (70 eV, EI +): m / z calcd for C18H21B02: 280.1635, found: 280

Elemental Analysis: C, 77%; H, 8% Synthesis Example 13: Synthesis of Intermediate 1-13

In nitrogen, Intermediate 1-12 (20 g, 71 mmol) was dissolved in 1 L of THF, followed by 1-bromo-3 -iodobenzene (24 g, 85 mmol) and tetrakis (triphenylphosphine) palladium (0.8 mg, 0.7 mmol). ) Was added and stirred. 1 ^ & 3 ^^ 001 0 6 (24.5 §, 177 1 ^ 1) saturated in water was added and heated to reflux at 80 ^° C for 12 hours. After the reaction was completed, water was added to the reaction solution, and extracted with dichloromethane (DCM), and then water was removed with anhydrous MgS0 ₄ , filtered and concentrated under reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining an intermediate 1-13 (30 g, 90%).

HRMS (70 eV, EI +): m / z calcd for C18H13Br: 309.1998, found 309 Elemental Analysis: C, 70%; H, 4% Synthesis Example 14 Synthesis of Intermediate 1-14

[Banungsik 14]

In nitrogen, Intermediate 1-13 (25 g, 81 mmol) was dissolved in 1 L of dimethylformamide (DMF), followed by bis (pinacolato) diboron (25 g, 97 mmol) and (Ι, Ι '-bis (diphenylphosphine) ferrocene ) Dichloropalladium (II) (0.7 g, 0.81 mmol) and potassium acetate (20 g, 203 mmol) were added thereto, and the resulting mixture was heated and refluxed at 150 ° C for 5 hours. After completion of reaction, water was added to the reaction solution, and the mixture was filtered and dried in a vacuum oven. The obtained residue was separated and purified through flash column chromatography, obtaining an intermediate 1-14 (27 g, 93%).

HRMS (70 eV, EI +): m / z calcd for C24H25B02: 356.1948, found: 356

Elemental Analysis: C, 81%; H, 7% Synthesis Example 15 Synthesis of Intermediate 1-15

In nitrogen, Intermediate 1-14 (50 g, 140 mmol) was dissolved in 1 L of THF, followed by 1-bromo-3-iodobenzene (47 g, 168 mmol) and tetrakis (triphenylphosphine) palladium (1.6 g, 1.4 mmol). ) Was added and stirred. 1 ^ 355 111 0 ^ 130 16 (48 350 1110101) saturated in water was added thereto, and the mixture was heated and refluxed at 80 ° C. for 12 hours. After completion of the reaction, water was added to the reaction solution and extracted with dichloromethane (DCM), followed by removal of water with anhydrous MgS0 ₄ , followed by filtration and concentration under reduced pressure. The obtained residue was separated and purified through flash column chromatography, intermediate 1-15 (44 g). , 89%).

HRMS (70 eV, EI +): m / z calcd for C24H17Br: 384.0514, found 384 Elemental Analysis: C, 75%; H, 4% Synthesis Example 16: Synthesis of Intermediate 1-16

[Banungsik 16]

In nitrogen, Intermediate 1-15 (20 g, 52 mmol) was dissolved in 1 L of dimethylformamide (DMF), followed by 1 (1 ^^ 01 0) <1 0 «(16 62.5 11111101) and (1，1'- Bis (diphenylphosphine) ferrocene) dichloropalladium (II) (0.4 g, 0.52 mmol) and potassium ^ 6 (13 ^ 130 1 1 ^ 1) were added and heated to reflux for 5 hours at 150 ^° C. After completion of reaction, water was added to the reaction solution, and the mixture was filtered and dried in a vacuum oven. The obtained residue was separated and purified through flash column chromatography, obtaining an intermediate 1-16 (19 g, 85%).

HRMS (70 eV, EI +): m / z calcd for C30H29BO2: 432.2261, found: 432

Elemental Analysis: C, 83%; H, 7% Synthesis Example 17 Synthesis of Intermediate 1-17

17]

In nitrogen, Intermediate 1-16 (60 g, 140 mmol) was dissolved in 1 L of THF, followed by 1-bromo-3 -iodobenzene (47 g, 168 mmol) and 'tetrakis (triphenylphosphine) palladiiun (1.6 g, 1.4 mmol) was added and stirred. Potassium carbonate saturated in water (48 g, 350 mmol) was added thereto, and the resulting mixture was heated and refluxed at 80 ^° C. for 12 hours. After the reaction was completed, water was added to the reaction solution, extracted with dichloromethane (DCM), water was removed with anhydrous MgS0 ₄ , filtered, and concentrated under reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining an intermediate 1-17 (54 g, 85%).

HRMS (70 eV, EI < + >): m / z calcd for C 30 H 21 Br: 460.0827, found 460 Elemental Analysis: C, 78%; H, 5% Synthesis Example 18 Synthesis of Intermediate 1-18

[Banungsik 18]

In a nitrogen environment, aniline (30 g, 536 mmol) was dissolved in 1 L of tetrahydrofiiran (THF), followed by 4-bromo-1, 1'-biphenyl (125 g, 536 mmol).

Add tris (diphenylideneacetone) dipalladium (o) (5 g, 5.36 mmol) tris-tert buty lpho sphine (4.3 g, 21.44 mmol) and sodium tert-butoxide (62 g, 717 mmol) sequentially for 18 hours at 100 ^° C Heated to reflux. After the reaction was completed, add water to the reaction solution

Extracted with dichloromethane (DCM) and then water was removed with anhydrous MgS0 ₄ , filtered and concentrated under reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining a compound 1-18 (118 g, 90%).

HRMS (70 eV, EI < + >): m / z calcd for C 18 H 15 N: 245.1204, found: 245.

Elemental Analysis: C, 88%; H, 6% Synthesis Example 19 Synthesis of Intermediate 1-19

Banungsik 19]

Dissolve intermediate 1-18 (30 g, 536 mmol) in 1 L of tetrahydrofuran (THF) in a nitrogen environment.

(1 ⁵ 0 536 11 ^ 101) and

add tris (diphenylideneacetone) dipalladium (o) (5 g, 5.36 mmol) tris-tert butylphosphine (4.3 g, 21.44 mmol) and 30 ^ 1 ^ -13 0 ^ (1 62 71 ⁷ 1 ^^ 1) ^It was heated to reflux at 18 ^° C for 18 hours. After the reaction was completed, add water to the reaction solution

Extract with dichloromethane (DCM), remove moisture with anhydrous MgS0 ₄ , filter Concentrated under reduced pressure. The obtained residue was separated and purified through flash column chromatography to obtain Intermediate I-19 (118 g, 90%).

HRMS (70 eV, EI < + >): m / z calcd for C 24 H 18 BrN: 399.0623, found: 399.

Elemental Analysis: C, 72%; H, 5%. Synthesis Example 20 Synthesis of Intermediate 1-20

20]

1-20

In a nitrogen environment, ^^ (！！ ^ ^ ^！ ^ was dissolved in 1 L of THF, followed by stirring with phenyl boronic acid (53 g, 436.87 mmol) and tetrakis (triphenylphosphine) palladium (6 g, 5 mmol). Potassium carbonate saturated in water (l 50 g, 1062 mmol) was added thereto, and the mixture was heated to reflux for 12 hours at 80 ^° C. After completion of reaction, water was added to the reaction solution, and extracted with dichloromethane (DCM), followed by anhydrous MgS0 ₄ . The resulting residue was filtered, concentrated under reduced pressure, and the residue thus obtained was separated and purified through flash column chromatography, obtaining an intermediate 1-20 (106 g, 88%).

HRMS (70 eV, EI < + >): m / z calcd for C 14 H 9 C 1 N 2: 240.0454, found 240 Elemental Analysis: C, 70%; H, 4% Synthesis Example 21 Synthesis of Intermediate 1-21

In nitrogen, intermediate 1-20 (35 g, 145 mmol) was dissolved in 1 L of THF, followed by 3-Chlorophenylboronic acid (24 g, 159 mmol) and tetrakis (triphenylphosphine) palladium (1.6 g, 1.4 mmol) was added and stirred. Potassium carbonate saturated in water (50 g, 362 mmol i: was added thereto and heated to reflux for 12 hours at 80 ^° C. After completion of reaction, water was added to the reaction solution, extracted with dichloromethane (DCM), and water was removed with anhydrous MgS0 ₄ . The resulting residue was separated and purified through flash column chromatography, obtaining a compound 1-21 (106 g, 88%).

HRMS (70 eV, EI < + >): m / z calcd for C20H13C1N2: 316.0767, found 316 Elemental Analysis: C, 76%; H, synthesis of 4% final compound

Synthesis Example 22 Synthesis of Compound A-3

22]

After dissolving intermediate 1-5 (5 g, 14.4 mmol) in 1 L of tetrahydroforan (THF) in nitrogen _: Intermediate 1-1 1 (10 g, 21.6 mmol) and tris (diphenylideneacetone) dipalladium (o) (0.13) g, 0.14 mmol) tris-tert butylphosphine (0.12 g, 0.58 mmol) and sodium tert-butoxide (1.6 g, 17.28 mmol) were sequentially added and heated to reflux for 18 hours at 100 ^° C. After the reaction was completed, water was added to the reaction solution, and extracted with dichloromethane (DCM), and then water was removed with anhydrous MgS0 ₄ , filtered and concentrated under reduced pressure. The obtained residue was separated and purified through flash column chromatography to obtain a final compound A-3 (7.8 g, 75%).

HRMS (70 eV, EI < + >): m / z calcd for C 54 H 34 N 20: 726.2671, found: 726.

Elemental Analysis: C, 89%; H, 5% Synthesis Example 23 Synthesis of Compound A-4

In nitrogen, Intermediate 1-5 (5 g, 14.4 mmol) was dissolved in 1 L of tetrahydrofuran (THF), followed by Intermediate I-17 (10 g, 2L6 mmol).

tris (diphenylideneacetone) dipalladium (o) (0.13 g, 0.14 mmol) tris-tert butylphosphine (0.12 g, 0.58 mmol) and sodium tert-butoxide (l.6 g, 17.28 mmol)

It was heated to reflux at 100 X for 18 hours. After completion of reaction, water was added to the reaction solution, extracted with dichloromethane (DCM), water was removed with anhydrous MgS0 ₄ , filtered and concentrated under reduced pressure. The obtained residue was separated and purified through flash column chromatography to obtain Compound A-4 (7.6 g, 73%).

HRMS (70 eV, EI < + >): m / z calcd for C 54 H 34 N 20: 726.2671, found: 726.

Elemental Analysis: C, 89%; H, 5% 24: Synthesis of Compound B-2

After melting, it was prepared with intermediate 1-19 (8.6 g, 21.6 mmol)

tris (diphenylideneacetone) dipalladium (o) (0.13 g, 0.14 mmol) tris-tert butylphosphine (0.12 g, 0.58 mmol) and sodium tert-butoxide (l .6 g, 17.28 mmol)

It was heated to reflux for 18 hours at 100 ^° C. After completion of reaction, water was added to the reaction solution, extracted with dichloromethane (DCM), water was removed with anhydrous MgS0 ₄ , filtered and concentrated under reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining a compound B-2 (7.2 g, 76%). HRMS (70 eV, EI < + >): m / z calcd for C48H31N30: 665.2467, found: 665.

Elemental Analysis: C, 87%; H, 5% 25: Synthesis of Compound C-2

In a nitrogen environment, intermediate 1-5 (5 g, 14.4 mmol) was dissolved in 1 L of tetrahydrofuran (THF), followed by 3-bromo-9-phenyI-9H-carbazole (7 g, 2L6 imnol).

tris (diphenylideneacetone) dipalladium (o) (0.13 g, 0.14 mmol) tris-tert butylphosphine (0.12 g, 0.58 mmol) and sodium tert-butoxide (L6 g, 17. ² 8 mmol)

It was heated to reflux for 18 hours at 100 ^° C. After the reaction was completed, water was added to the reaction solution, extracted with dichloromethane (DCM), water was removed with anhydrous MgS0 ₄ , filtered, and concentrated under reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining a compound C-2 (6.2 g, 75%).

HRMS (70 eV, EI < + >): m / z calcd for C 42 H 25 N 30: 587.1998, found: 587.

Elemental Analysis: C, 86%; H, 4% Synthesis Example 26 Synthesis of Compound D-19

after Intermediate 1- ² 1 (7 21.6 1 turn 01) and tris (diphenylideneacetone) dipalladiira (o) (0.13 g, Ο, Μ mmol) tris-tert butylphosphine (0.12 g, 0.58 mmol) and sodium tert-butoxide (1.6 g, 17.28 mmol) was added sequentially and refluxed by heating at 100 ^° C. for 18 hours. After the reaction was completed, water was added to the reaction solution, extracted with dichloromethane (DCM), water was removed with anhydrous MgS0 ₄ , filtered, and concentrated under reduced pressure. The residue thus obtained is flash column

Separation and purification by chromatography gave Compound D-19 (6.8 g, 78%).

HRMS (70 eV, EI < + >): m / z calcd for C44H26N40: 626.2107, found: 626.

Elemental Analysis: C, 84%; H, 4%

In a nitrogen environment, intermediate 1-5 (5 g, 14.4 mmol) was dissolved in 1 L of tetra ydrofuran (THF), followed by intermediate 1-20 (7 g, 21.6 mmol).

add tris (diphenylideneacetone) dipalladium (o) (0.13 g, 0.14 mmol) tris-tert butylphosphine (0.12 g, 0.58 mmol) and sodium tert-butoxide (1.6 g, 17.28 mmol)

It was heated to reflux for 18 hours at 100 ^° C. After completion of reaction, water was added to the reaction solution, extracted with dichloromethane (DCM), water was removed with anhydrous MgS0 ₄ , filtered and concentrated under reduced pressure. The obtained residue was separated and purified through flash column chromatography, obtaining a compound D-20 (6.2 g, 78%).

HRMS (70 eV, EI < + >): m / z calcd for C38H22N40: 550.1794, found: 550.

Elemental Analysis: C, 83%; H, fabrication of 4% organic light emitting device

Example 1

Compound A-3 obtained in Synthesis Example 22 was used as a host, and acetylacetonatobis (2- An organic light emitting diode was manufactured using phenylquinolinato) iridium (Ir (pq) ₂ acac) as a dopant. I used ΠΌ for anode at a thickness of 1500 A and aluminum (A1) for cathode

Used to a thickness of 1000 A. Specifically, the method of manufacturing the organic light emitting device, the anode is cut into a size of 50mm X 50 mm X 0.7 mm ΠΌ glass substrate with a sheet resistance value of 15 Ω / αί in each of acetone, isopropyl alcohol and pure water For 15 minutes

After ultrasonic cleaning, UV ozone washing was used for 30 minutes.

4,4'-bis [N- [4- {N, N-bis (3-methylphenyl) amino} -phenyl]-under vacuum conditions of 650x HT ⁷ Pa and deposition rate of 0.1-0.3 nm / s on the substrate. N-pheny lamino] biphenyl [DNTPD] was vacuum deposited to form a hole injection layer having a thickness of 600 A. Then the same vacuum

Under the deposition conditions, a hole transport layer having a thickness of 300A was formed by vacuum deposition of HT-1.

Next, a light emitting layer having a thickness of 300 A was formed using compound A-3 obtained in Synthesis Example 22 under the same vacuum deposition conditions. At this time, phosphate dopant acetylacetonatobis (2-phenylquinolinato) iridium (Ir (pq) 2acac) was formed. Deposition at the same time. At this time, by adjusting the deposition rate of the phosphorescent dopant, it was deposited in the amount of the phosphorescent dopyeon agent so that 7 percent by weight when the total amount of the light-emitting layer to 100 parts by weight ^_0/0.

Using the same vacuum deposition conditions on the light emitting layer, Bis (2-methyl-8-quinolinolate) -4- (phenylphenolato) aluminum (BAlq) was deposited to have a film thickness of 50 A.

A hole blocking layer was formed. Subsequently, Tris (8-hydroxyquinolinato) aluminum (Alq3)-was deposited under the same vacuum deposition conditions to form an electron transport layer having a thickness of 250 A. An organic photoelectric device was manufactured by sequentially depositing LiF and A1 as a cathode on the electron transport layer.

The structure of the organic photoelectric device is ITO / DNTPD (60 nm) / HT-l (30 nm) / EML ( compound A-3 (93 parts by weight ^{0 /.) + Ir (pq} ) 2 acac (7 parts by weight ^_0/0) , 30 nm) / Balq (5 nm) / Alq ₃ (25 nm) / LiF (1 nm) I Al (100 nm).

Examples 2-6

Compound A-4 of Synthesis Example 23, Compound B-2 of Synthesis Example 24, Compound C-2 of Synthesis Example 25, Compound D-19 of Synthesis Example 26, Compound of Synthesis Example 27 instead of Compound A-3 of Synthesis Example 22 The organic light emitting diodes of Examples 2 to 6 were prepared in the same manner as in Example 1, except that D-20 was used.

Comparative Example 1 An organic light emitting diode was manufactured according to the same method as Example 1 except for using 4,4′-di (9H-carbazol-9-yl) biphenyl (CBP) instead of Compound A-3 of Synthesis Example 22.

The structures of DNTPD, BAlq, HT-1, CBP, and Ir (pq) ₂ acac used in the organic light emitting device are as follows.

evaluation

Current density change, luminance change, and luminous efficiency of the organic light emitting diode according to Examples 1 to 6 and Comparative Example 1 were measured.

Specific measurement methods are as follows, and the results are shown in Table 1.

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

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.

(2) Measurement of luminance change according to 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.

(3) Measurement of luminous efficiency

The current efficiency (cd / A) of the same current density (10 mA / cm ² ) was calculated using the luminance, current density and voltage measured from (1) and (2). (4) life measurement

The initial luminance (cd / m ² ) was emitted at 3000 cd / m ² , and the decrease in luminance over time was measured to obtain a result by measuring the time of decreasing to 90% of the initial luminance.

TABLE 1

Referring to Table 1, it can be seen that the organic light emitting device according to Examples 1 to 6 is significantly improved light emission efficiency and life characteristics compared to the organic light emitting device according to Comparative Example 1. The present invention is not limited to the above embodiments, but may be manufactured in various forms, and a person skilled in the art to which the present invention pertains has another specific form without changing the technical spirit or essential features of the present invention. It will be appreciated that the present invention may be practiced as. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims

[Range of request]

[Claim 11

Compound for an organic optoelectronic device represented by the formula (I)

[Formula I]

In Formula I,

X is 0 or S,

Herein, "substituted" means that at least one hydrogen is deuterium, a halogen group, a hydroxyl group, a C1 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C2 to C30 heterocycloalkyl group It means substituted with a C6 to C30 aryl group, a C2 to C30 heterocyclic group, a C1 to C20 alkoxy group, a C1 to C10 trifluoroalkyl group or a cyano group.

[Claim 2]

The method according to claim 1,

R ¹ is a C6 to C30 aryl group unsubstituted or substituted with a C6 to C30 aryl group; C6 to C30 arylamine group unsubstituted or substituted with C6 to C30 aryl group; A C2 to C30 heterocyclic group unsubstituted or substituted with a C6 to C30 aryl group or a C2 to C30 heterocyclic group; Or a C6 to C30 aryl group substituted with an N-containing C2 to C30 heterocyclic group except for a carbazolyl group.

[Claim 3]

The method of claim 2,

The C2 to C30 heterocyclic group unsubstituted or substituted with the C6 to C30 aryl group or C2 to C30 heterocyclic group, C2 to C30 heterocyclic group having a hole characteristic or C2 to C30 heterocyclic group having an electronic property,

The C2 to C30 heterocyclic group having the hole characteristics is a substituted or unsubstituted carbazolyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group,

The C2 to C30 heterocyclic group having the above electronic properties is an N-containing C2 to C30 heterocyclic group except for a carbazolyl group or an N-containing C2 to C30 heterocyclic group except for a carbazolyl group unsubstituted or substituted with a C6 to C30 aryl group. Compound for device.

【Claim 4】.

The method of claim 3, wherein

Compound for an organic optoelectronic device wherein the C2 to C30 heterocyclic group having a hole characteristic is selected from the groups listed in the following Group 1:

Group 1]

In group 1, * is the point of attachment.

[Claim 5]

The method of claim 3,

The compound for an organic optoelectronic device, wherein the C2 to C30 heterocyclic group having the electronic properties is selected from the groups listed in the following Group 2: Group 2]

In group 2 above,

* Is the connection point.

[Claim 6]

The method of claim 1,

The C2 to C30 heterocyclic group is pyridyl group, pyrimidyl group, triazinyl group, benzoimidazole group, benzopyrimidyl group, benzopyridyl group, carbazolyl group, dibenzofuranyl group, dibenzothiophenyl group, benzothiopyri The compound for organic optoelectronic devices selected from a midinyl group, a benzofuran pyrimidinyl group, a benzothiopyridyl group, or a benzofuran pyridyl group.

[Claim 7]

The method of claim 2,

The C6 to C30 aryl group unsubstituted or substituted with a C6 to C30 aryl group is selected from the groups listed in Group 3 for the organic optoelectronic device compound: Group 3]

In group 3 above,

* Is the connection point.

[Claim 8] _;

The method of claim 2,

Wherein the C6 to C30 arylamine group substituted or unsubstituted with the C6 to C30 aryl group is selected from the groups listed in Group 4 below:

Group 4]

In group 4 above

* Is the connection point.

[Claim 9]

The method according to claim 1,

L is a single bond, a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted quarterphenylene group, a substituted or unsubstituted naphthylene group, Or a combination thereof.

[Claim 10] The method of claim 1,

Wherein L is selected from a single bond and a substituted or unsubstituted or substituted or unsubstituted group listed in Group 5 below:

Group 5]

In group 5 above,

* Is the connection point,

As used herein, "substitution" is as defined in claim 1 above.

【Claim 11】

According to claim 1,

In the compounds listed in Groups A to D below. The compound for an organic optoelectronic device selected:

[Group A]

[Group D]

ε ^ -α _Z -n V -Q

3d 9 ^ 9ZC660 / .T0Z OAV

[Claim 12]

Positive and negative electrodes facing each other, and

An organic optoelectronic device comprising at least one organic layer positioned between the anode and the cathode, wherein the organic layer comprises a compound for an organic optoelectronic device according to any one of claims 1 to 11.

[Claim 13]

The method of claim 12,

The organic layer includes a light emitting layer,

The light emitting layer is an organic optoelectronic device comprising the compound for an organic optoelectronic device.

[Claim 14]

The method of claim 13,

The organic optoelectronic device compound is included as a host of the light emitting layer.

【Claim 15】

A display device comprising the organic optoelectronic device of claim 12.