WO2014104535A1

WO2014104535A1 - Compound for organic optoelectronic device, organic light-emitting diode including same, and display apparatus including said organic light-emitting diode

Info

Publication number: WO2014104535A1
Application number: PCT/KR2013/008219
Authority: WO
Inventors: 신창주; 강동민; 원종우; 이남헌; 정수영; 정호국; 채미영; 김현정; 정우석
Original assignee: 제일모직 주식회사
Priority date: 2012-12-31
Filing date: 2013-09-11
Publication date: 2014-07-03
Also published as: KR20140087996A

Abstract

The present invention relates to a compound for an organic optoelectronic device, to an organic light-emitting diode including same, and to a display apparatus including said organic light-emitting diode, and provides a compound for an organic optoelectronic device represented by chemical formula 1.

Description

【Specification】

[Name of invention]

A compound for an organic optoelectronic device, an organic light emitting device including the same, and a display device including the organic light emitting device

Technical Field

A compound for an organic optoelectronic device, an organic light emitting device including the same, and a display device including the organic light emitting device.

Background Art

An organic optoelectric device refers to a device requiring charge exchange between an electrode and an organic material using holes or electrons.

Organic optoelectronic devices can be divided into two types according to the operation principle. First, an exciton is formed in the organic layer by photons introduced into the device from an external light source, and the exciton is separated into electrons and holes, and these electrons and holes are transferred to different electrodes.

An electronic device of the type used as a current source (voltage source).

The second is an electronic device in which holes or electrons are injected into an organic semiconductor forming an interface with electrodes by applying voltage or current to two or more electrodes, and operated by the injected electrons and holes.

Examples of organic optoelectronic devices include organic optoelectronic devices, organic light emitting devices, organic solar cells, organic photo conductor drums, and organic transistor posts, all of which are used to inject or transport holes or electrons to drive the device. Injection or transport materials, or luminescent materials.

In particular, organic light emitting diodes (OLEDs) are attracting attention as the demand for flat panel displays increases.

In general, organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material.

Such an organic light emitting device converts electrical energy into light by applying an electric current to the organic light emitting material, and is generally functional between an anode and a cathode. It has a structure in which an organic layer is inserted. Where the organic layer is

In order to increase the efficiency and stability of the organic light emitting device is often composed of a multi-layer structure composed of different materials, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer.

When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer in the anode and electrons in the cathode, and the injected holes and electrons meet and recombine by recombination. High energy excitons are formed. At this time, the excitons formed move to the ground state, and light having a specific wavelength is generated. Recently, it has been known that not only fluorescent light emitting materials but also phosphorescent light emitting materials can be used as light emitting materials of organic light emitting devices. Such phosphorescent light emission is generated by inter-system transition after electrons are transferred from the ground state to the excited state. It is composed of a mechanism in which singlet excitons are non-luminescent transition into triplet excitons, and then triplet excitons are emitted to the ground state.

As described above, the material used as the organic material layer in the organic light emitting device may be classified into a light emitting material and a charge transport material, such as a hole injection material, a hole transport material, an electron transport material, an electron injection material, and the like according to a function.

In addition, the light emitting materials may be classified into blue, green, and red light emitting materials, and yellow and orange light emitting materials required to achieve better natural colors according to light emission colors.

On the other hand, when only one material is used as the light emitting material, the maximum emission wavelength is shifted to a long wavelength due to the intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the decay effect. In order to increase luminous efficiency and stability through the host / dopant system can be used as a light emitting material.

In order for the organic light emitting device to fully exhibit the above-described excellent features, the organic layer of the material, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, a host and / or dopant in the light emitting material The back should be supported by a stable and efficient material. In addition, the development of a stable and efficient organic material layer for an organic light emitting device has not been made yet, and therefore, development of new materials is continuously required. The need for such material development is

The same applies to organic optoelectronic devices.

In addition, the low molecular weight organic light emitting diode is manufactured in the form of a thin film by vacuum deposition method, so the efficiency and lifespan performance is good, and the high molecular weight organic light emitting diode uses the inkjet or spin coating method, and the initial investment cost is low. Large area has an advantage.

Both low molecular weight organic light emitting diodes and high molecular weight organic light emitting diodes are attracting attention as next-generation displays because they have advantages such as self-luminous, high speed response, wide viewing angle, ultra-thin, high definition, durability, and wide driving temperature range. In particular, compared to conventional LCD (liquid crystal display), as a self-luminous type, even in the dark or outside light, the cyan is good, and since it does not need a backlight, the thickness and weight can be reduced to 1/3 level of LCD.

In addition, because the response speed is 1000 times faster than LCD, it is possible to realize perfect video without afterimage. Therefore, it is expected to be spotlighted as an optimal display in line with the recent multimedia era, and based on these advantages, it has achieved rapid technological development of 80 times since its first development in the late 1980s _: more than 100 times of life, and recently, 40 inches. Increasingly, the size of organic light emitting diode panels is being announced rapidly.

In order to increase the size, increase in luminous efficiency and lifespan of the device

It must be accompanied. To this end, it is necessary to develop a stable and efficient organic material layer for an organic light emitting device.

[Content of invention]

[Problem to solve]

It is to provide a compound for an organic optoelectronic device capable of providing an organic optoelectronic device having characteristics such as high efficiency and long life.

An organic light emitting device including the compound for an organic optoelectronic device and a display device including the organic light emitting device are provided. [Measures of problem]

In one embodiment of the present invention, represented by the following formula (1)

Provided is a compound for an organic optoelectronic device.

[Formula 1]

In Formula 1, Ar ¹ , Ατ ² , ΐΛΐΛη1, η2 and R ¹ to R ³ are as defined in the following detailed description.

In one embodiment of the present invention, an anode, a cathode and at least one organic thin film layer interposed between the anode and the cathode

In the organic light emitting device, at least one of the organic thin film layer provides an organic light emitting device comprising the compound for the organic optoelectronic device.

In another embodiment of the present invention, a display device including the organic light emitting diode is provided.

【Effects of the Invention】

The organic optoelectronic device including the compound for an organic optoelectronic device has excellent electrochemical and thermal stability, excellent life characteristics, and low

It can have a high luminous efficiency even at the driving voltage.

[Brief Description of Drawings]

1 and 2 are cross-sectional views showing various embodiments of an organic light emitting device that may be manufactured using a compound for an organic optoelectronic device according to an embodiment of the present invention.

[Specific contents to carry out invention]

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

As used herein, unless otherwise defined, "substituted" means that at least one hydrogen in a substituent or compound is a hydrogen, halogen, hydroxy, amino, substituted or unsubstituted C1 to C30 amine group, nitro group, substituted or unsubstituted. C1, such as a ring C3 to C40 silyl group, C1 to C30 alkyl group, C1 to C10 alkylsilyl group, C3 to C30 cycloalkyl group, C6 to C30 aryl group, C1 to C20 alkoxy group, pullouro group, trifluoromethyl group, etc. To C10 tripolouroalkyl group or cyano 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 Two adjacent substituents among C1 to C10 trifluorouroalkyl groups such as a C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a fluoro group, and a trifluoromethyl group or a cyano group may be fused to form a ring. have.

As used herein, unless otherwise defined, "hetero" means containing 1 to 3 heteroatoms selected from the group consisting of N, 0, S, and P in one functional group, and the remainder is carbon.

As used herein, unless otherwise defined, an "alkyl group" means an aliphatic hydrocarbon group. The alkyl group may be any unsaturated "saturated alkyl group" which contains any double or triple bonds.

The alkyl group may be an alkyl group that is C1 to C20. More specifically, the alkyl group may be a C1 to C10 alkyl group or a C1 to C6 alkyl group. For example, a C1 to C4 alkyl group means that the alkyl chain contains 1 to 4 carbon atoms, with methyl, ethyl, propyl, iso-propyl, η-butyl, iso-butyl, sec-butyl and t-butyl Selected from the group consisting of:

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

An "aryl group" means that all the elements of the cyclic substituent have P—orbital And a substituent in which these P-orbitals form conjugates, and include monocyclic or fused ring polycyclic (ie, rings that divide adjacent pairs of carbon atoms) functional groups.

"Heteroaryl group" means containing 1 to 3 hetero atoms selected from the group consisting of N, O, S, and P in the aryl group, and the rest are carbon. When the heteroaryl group is a fused ring, each ring may include 1 to 3 heteroatoms.

In the present specification, the hole property refers to a property of having a conduction property along the HOMO level to facilitate the injection and movement of the hole formed in the anode into the light emitting layer. More specifically, it may be similar to the property of repelling electrons.

In addition, the electronic property refers to a property that has conductive properties along the LUMO level, thereby facilitating injection of electrons formed in the cathode into the light emitting layer and movement in the light emitting layer. More specifically, it may be similar to the property of attracting electrons. In one embodiment of the present invention, represented by the following formula (1)

The compound for organic optoelectronic devices can be provided.

In Formula 1, Ar ¹ and Ar ² are independently of each other, a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group, L ¹ and L ² are independently from each other, substituted Or a ^ C6 alkenylene group in C2, a substituted or unsubstituted C2 to C6 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group, or a combination thereof And nl and η2 are each independently 0 to An integer of any one of 5 and at least one of AT ¹ or Ar ² is a substituted or unsubstituted C2 to C30 heteroaryl group; At least one of L ¹ or L ² is a substituted or unsubstituted C2 to C30 heteroarylene group, R ¹ to R ³ are independently of each other, hydrogen, hydrogen, halogen, cyano, hydroxyl, amino, Substituted or unsubstituted C1 to C20 amine group, nitro group, carboxyl group, ferrocenyl group, substituted or unsubstituted C1 to C20 alkyl group, substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted C2 to C30 hetero Aryl group, substituted or unsubstituted C1 to C20 alkoxy group, substituted or unsubstituted C6 to C20 aryloxy group, substituted or unsubstituted C3 to C40 silyloxy group, substituted or unsubstituted C1 to C20 acyl group, substituted Or an unsubstituted C2 to C20 alkoxycarbonyl group, a substituted or unsubstituted C2 to C20 acyloxy group, a substituted or unsubstituted C2 to C20

Acylamino group, substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, substituted or unsubstituted C1 to C20 sulfamoylamino group, substituted or unsubstituted C1 to C20 sulfonyl group, substituted or unsubstituted C1 to C20 alkylthiol group, substituted or unsubstituted C6 to C20 arylthiyl group, substituted or unsubstituted C1 to C20

A heterocyclothiol group, a substituted or unsubstituted C1 to C20 uraide group, a substituted or unsubstituted C3 to C40 silyl group, or a combination thereof.

The compound represented by Chemical Formula 1 may have a core structure including three fused rings including a hetero atom. In the case of such a core structure, it may have high heat resistance and electron mobility may be improved.

In addition, the compound for an organic optoelectronic device represented by the formula (1) is a variety of other substituents to the substituents substituted in the core portion and the core portion

The introduction can lead to compounds having various energy band gaps.

By using a compound having an appropriate energy level in the organic optoelectronic device according to the substituent of the compound, the hole transfer ability or electron transfer ability is enhanced to have an excellent effect in terms of efficiency and driving voltage, and excellent in electrochemical and thermal stability. It is possible to improve the life characteristics when driving the device. More specifically, in one embodiment of the present invention, a substituted or unsubstituted C6 to C30 aryl group and / or a substituted or unsubstituted C2 to C30 heteroaryl group is a substituted or unsubstituted phenyl group, substituted or unsubstituted naph Tyl group, substituted or unsubstituted anthracenyl group, substituted or unsubstituted phenanthryl group, substituted or unsubstituted naphthacenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted biphenylyl group, substituted or unsubstituted P-terphenyl group, substituted or unsubstituted m-terphenyl group, substituted or unsubstituted chrysenyl group, substituted or unsubstituted

Triphenylenyl group, substituted or unsubstituted perylenyl group, substituted or unsubstituted indenyl group, substituted or unsubstituted furanyl group, substituted or unsubstituted thiophenyl group, substituted or unsubstituted pyrrolyl group, substituted or unsubstituted Substituted pyrazolyl group, substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted oxazolyl group, substituted or unsubstituted thiazolyl group, substituted or unsubstituted oxadiazoleyl group , Substituted or unsubstituted thiadiazolyl group, substituted or unsubstituted pyridyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted

Pyrazinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted banjofuranyl group, substituted or unsubstituted benzothiophenyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted indolyl group, substituted Or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted 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 phenoxazine It may be a diary or a combination thereof, but is not limited thereto.

In addition, by selectively adjusting the L ⁱ and L ² of the entire compound

The conjugation length can be determined, from which the triplet energy bend ¾ can be adjusted. Through this, it is possible to realize the characteristics of the material required in the organic optoelectronic device. In addition, triplet energy bandgap can be adjusted by changing the binding position of olso, para and meta.

Specific examples of the L ¹ and L ² are a substituted or unsubstituted phenylene group, substituted Or an unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted anthracenylene group, a substituted or unsubstituted phenanthrylene group, a substituted or unsubstituted pyrene Nylene group, substituted or unsubstituted fluorenylene group, substituted or unsubstituted P-terphenyl group, substituted or unsubstituted m-terphenyl group, substituted or unsubstituted peryleneyl group.

More specifically, L 'and L ² may be, independently of each other, a phenylene group. When the L ¹ to L ³ is a phenylene group, both core portions may be bonded to an oth, meta, or para based on the phenylene group.

More specifically, L ¹ and L ² may be independently a substituted or unsubstituted pyrimidinylene group. When L ¹ and L ² are substituted or unsubstituted pyrimidinylene groups, they may have high heat resistance, and electron mobility may be improved.

More specifically, L ¹ is a substituted or unsubstituted C2 to C30 heteroarylene group, ηΐ may be an integer of any one of 1 to 5. However, it is not limited thereto.

Ar ² may be a substituted or unsubstituted C6 to C30 aryl group, and Ax ¹ may be a substituted or unsubstituted C2 to C30 heteroaryl group. That is, the electronic properties of the entire compound can be controlled by adjusting the substituents of Aτ ¹ and Ar ² . More specifically, it is possible to improve the driving voltage in the device by reducing the energy difference between adjacent layers by controlling HOMO and LUMO energy, dipole moment, and molecular weight of all compounds.

More specifically, Ax ¹ and Ar ² may be each independently a substituted or unsubstituted C6 to C30 fused aryl group or a substituted or unsubstituted C2 to C30 fused heteroaryl group. In such a case, the heat resistance of the molecule may be improved due to the fused ring, and at the same time, the electron mobility may be improved. More specifically, Ar ¹ may be a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, or a substituted or unsubstituted phenanthrenyl group. However, it is not limited thereto.

At least one of the said Ar ¹ and Ar ² has an electronic characteristic substitution Or an unsubstituted C2 to C30 heteroaryl group.

More specifically, for example, the substituted or unsubstituted C2 to C30 heteroaryl group having the above electronic properties may be substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted tetrazolyl. Groups, substituted or unsubstituted oxadiazolyl groups, substituted or unsubstituted oxatriazolyl groups, substituted or unsubstituted thiatazolyl groups, substituted or unsubstituted

Benzimidazolyl group, substituted or unsubstituted benzotriazolyl group, substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted pyrazinyl Groups, substituted or unsubstituted pyridazinyl groups, substituted or unsubstituted purinyl groups, substituted or unsubstituted quinolinyl groups, substituted or unsubstituted isoquinolinyl groups, substituted or unsubstituted phthalazinyl groups, substituted Or unsubstituted naphpyridinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted acridinyl group, substituted or unsubstituted phenanthrolinyl group, or substituted or unsubstituted It may be a phenazinyl group phosphorus. However, it is not limited thereto.

However, more specifically, for example, the substituted or unsubstituted C2 to C30 heteroaryl group having the above electronic properties may be substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted. Triazinyl group, a substituted or unsubstituted quinolinyl group, or a substituted or unsubstituted isoquinolinyl group. In this case, electron mobility may be improved while having an appropriate energy band gap, thereby improving efficiency and lifespan of the device.

More specifically, for example, the substituted or unsubstituted C2 to C30 heteroaryl group having the above electronic properties may be represented by any one of the following Formulas E-1 to E-5. However, this is not limited.

[Formula E-1] [Formula E— 2] [Formula E-3] [Formula E-4] [Formula E-5]

As a specific example, the compound for an organic optoelectronic device may be It can be either. However, it is not limited thereto.



lnv-92 lnv-96

SI

ll800 / Cl0ia¾ / 13i

In another embodiment of the present invention, an anode, a cathode and at least one organic thin film layer interposed between the anode and the cathode, wherein at least one layer of the organic thin film layer comprises the compound for the organic optoelectronic device An organic optoelectronic device is provided.

The compound for an organic optoelectronic device is used in an organic thin film layer

Life Characteristics, Efficiency Characteristics, Electrochemical Stability and Thermal Properties of Organic Optoelectronic Devices It can improve the stability and lower the driving voltage.

Specifically, the organic thin film insect may be an electron injection layer or an electron transport layer.

The organic optoelectronic device may be an organic light emitting device, an organic photoelectric device, an organic solar cell, an organic transistor, an organic photosensitive drum, or an organic memory device.

More specifically, the organic optoelectronic device may be an organic light emitting device. 1 to 5 are cross-sectional views of an organic light emitting device including a compound for an organic optoelectronic device according to an embodiment of the present invention.

. 1 and 2, according to one embodiment of the present invention

The organic light emitting diodes 100 and 200 have a structure including an anode 120, a cathode 110 and at least one organic thin film layer 105 interposed between the anode and the cathode.

The anode 120 includes a cathode material, and a material having a large work function is preferable as the anode material so that hole injection can be smoothly performed into an organic thin film. Specific examples of the positive electrode material may include metals such as nickel, platinum, banana, chromium, copper, zinc, and gold or alloys thereof, zinc oxide, phosphate oxide, tin oxide (Π 듬), indium zinc oxide ( Metal oxides such as IZO), and combinations of metals and oxides such as ZnO and A1 or Sn0 ₂ and Sb; poly (3-methylthiophene), poly (3,4- (ethylene-1) , 2-dioxy) thiophene Xpolyehtylenedioxythiophene (PEDT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto. More specifically, a transparent electrode containing nO (indiumtinoxide) may be used as the anode.

The negative electrode 110 includes a negative electrode material, and the negative electrode material is generally a material having a small work function to facilitate electron injection into the organic thin film layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, rhythm, yttrium, litope, gadolinium, aluminum, silver, tin, lead, cesium, barium, or alloys thereof, and LiF / Al. Multi-layered materials such as, Li0 ₂ / Al, LiF / Ca, LiF / Al, and BaF ₂ / Ca, but are not limited thereto. More specifically, the cathode such as aluminum Metal electrodes can be used.

First, referring to FIG. 1, FIG. 1 illustrates an organic light emitting device 100 in which only a light emitting layer 130 exists as an organic thin film layer 105. The organic thin film layer 105 may exist only as a light emitting layer 130.

Referring to FIG. 2, FIG. 2 is a two-layered organic light emitting layer 105 including a light emitting layer 230 including an electron transport layer and a hole transport layer 140.

As an organic light emitting device 200 is shown, as shown in FIG.

The organic thin film layer 105 may be a two-layer type including the light emitting layer 230 and the hole transport layer 140. In this case, the light emitting layer 130 functions as an electron transporting layer, and holes

The transport layer 140 functions to improve the bonding property and the hole transporting property with the transparent electrode such as πΌ.

Although not shown, the organic thin film layer 105 of FIG. 1 and FIG. 2 may further include an electron injection layer, an auxiliary electron transport layer, an electron transport layer, a hole transport layer, an auxiliary hole transport layer, a hole injection layer, and a combination thereof. .

1 and 2, the organic thin film layer 105), the light emitting layer 130,

230), the hole transport layer 140, which is not shown but may further include an electron injection layer, auxiliary electron transport layer, electron transport layer, hole injection layer, auxiliary hole transport layer, hole transport layer, any one selected from the group consisting of One contains the said organic optoelectronic device material.

The organic light emitting device described above includes a dry film method such as vacuum evaporation, sputtering, plasma plating and silver plating after forming an anode on a substrate; Or spin gating, dipping,

After forming the organic thin film layer by a wet film method such as flow coating (flow coating), it can be produced by forming a cathode thereon.

In another embodiment of the present invention, a display device including the organic optoelectronic device is provided.

Example

Hereinafter, specific embodiments of the present invention are presented. However, the embodiments described below are intended to specifically illustrate or explain the present invention. The present invention should not be limited thereby.

Of starting materials (eg, formulas A to D) in the compounds of the present invention

The scheme is as follows.

[Scheme]

Synthesis Example 11 Synthesis of Chemical Formula

50 g (342.0206 mmol) of tetralone, 53.41 g (342.0206 mmol) of 1-Naphthaldehyde, and 20.52 g (513.0309 mmol) of sodium hydroxide were added to the back-bottom flask and stirred at room temperature for 12 hours. After the reaction, the resulting solid was filtered and washed / dried with ethanol to obtain the formula (1) 71 g (Yield 73%).

71 g (249.69 mmol) of Chemical Formula (1), 58.8 g (249.69 mmol) of 4-Bromobenzamidine hydrochloride, and 29.96 g (709.07 mmol) of sodium hydroxide were added to 1 L of Ethanol, followed by stirring under reflux for 12 hours. After the reaction was completed, the resulting solid was filtered and washed with ethanol to obtain 50 g (43% yield) of Chemical Formula (2).

50 hours (107.907 mmol) of formula (2) obtained in the synthesis and 73.5 g (323.72 mmol) of 2,3-dichloro-5,6-dicyano-/?-Benzoquinone were suspended in 500 ml of fu monochlorobenzene for 12 hours. While stirring at reflux. After completion of the reaction, the reaction mixture was cooled to room temperature, concentrated through a silica gel filter, and recrystallized from toluene to obtain 43 g (yield 86%) of the target compound (A).

calcd. C ₆₂ H ₄₀ N ₆ : C, 72.89; H, 3.71; N, 6.07; found: C, 72.78; H, 3.57; N, 5.91

Synthesis Example 21 Synthesis of Chemical Formula fB)

Synthesis of Formula (A) synthesized in Synthesis Example 1 except that 2-Naphthaldehyde was used instead of 1-Naphthaldehyde was synthesized in the same manner to obtain 41 g of the target compound (B).

calcd. C ₆₂ H ₄₀ N ₆ : C, 72.89; H, 3.71; N, 6.07; found: C, 72.51; H, 3.94; N, 6.21

Synthesis Example 31 Synthesis of Chemical Formula (C)

Except for using 4-Bromobenzaldehyde and 4-Bromobenzamidine instead of 1 -Naphthaldehyde and Benzamidine instead of 4-Bromobenzamidine in the synthesis of the formula (A) synthesized in Synthesis Example 1 to obtain the target compound of formula (C) 23g.

calcd. C ₆₂ H ₄₀ N ₆ : C, 70.09; H, 3.68; N, 6.81; found: C, 69.89; H, 3.72; N, 6.86 ί Synthesis Example 4 ᅵ Synthesis of

Synthesis of Chemical Formula (C) synthesized in Synthesis Example 3, except that 4-Bromobenzamidine was used instead of Benzamidine, the synthesis was carried out in the same manner to obtain the target compound of Formula (D) 25g.

calcd. C ₆₂ H ₄₀ N ₆ : C, 58.81; H, 2.88; N, 5.71; found: C, 58.62; H, 2.76; N, 5.93 ί Synthesis Example 51 Synthesis of Formula (E)

20 g (48.62 mmol) of the compound (C) synthesized in Synthesis Example 3 were suspended in 400 ml of Tetrahydrofbran, and kept at -78 ^° C. At this temperature, 3.73 g (58.35 mmol) of n-BuLi (2.5M in Hex) was slowly added dropwise to the reaction mixture, followed by stirring at -78 ^° C for 1 hour and at room temperature for 1 hour. After maintaining it at -78 ^° C, 10.66 g (145.86 mmol) of Ν, Ν-dimethylformamide was added and stirred at room temperature for 12 hours. After completion of reaction, 200 ml of distilled water was added, the mixture was stirred for 1 hour, the extract was extracted, the organic layer was concentrated, and Silicagel Columm Chromatography was performed to obtain 11 g (Yield: 63%) of the target compound (E).

calcd. C ₆₂ H ₄₀ N ₆ : C, 83.31; H, 4. 47; N, 7.77; found: C, 83.18; H, 4.53; N, 7.39 (Preparation of Compound for Organic Optoelectronic Devices)

Example l Synthesis of Compound Represented by Inv-17

[Banungsik 1]

14.49 g (31.4078 mmol) of formula (A), 4.63 g (37.6894 mmol) of 3-pyridine boronic acid (Aldrich),

1.09 g (0.9422 mmol) of tetrakis (triphenylphosphine) palladum (O) and 8.68 g (62.8156 mmol) of potassium carbonate were suspended in 80 ml of THF 160 ml After stirring for 12 hours at reflux. After the reaction was completed, the product was extracted and concentrated, and the silica gel column

After separation with chromatograph and recrystallized with teltuene to obtain the target compound Inv-17 11 g (76% yield).

calcd. C ₆₂ H ₄₀ N ₆ : C, 86.25; H, 4.61; N, 9.14; found: C, 85.93; H, 4. 82; N, 9.55 Example 2: Synthesis of Compound Represented by Inv-18

Scheme 2

7.35 g (15.9315 mmol) of formula (A), 3.31 g (19.1178 mmol) of 8-quinoline boronic acid,

0.55 g (0.4779 mmol) of tetrakis (triphenylphosphine) palladum (O), 4.40 g (31.8630 mmol) of potassium carbonate, suspended in 70 ml of THF 150 ml After stirring, reflux was stirred for 12 hours. After the reaction was completed, the product was extracted and concentrated, and the silica ¾ column

After separation with chromatograph and recrystallized with toluene to obtain 4.5 g (55% yield) of the target compound Inv-18.

calcd. C ₆₂ H ₄₀ N ₆ : C, 87.21; H, 4.55; N, 8.25; found: C, 87.1 1; H, 4.63; N, 8.17 Example 3: Synthesis of Compound Represented by Inv-33

[Banungsik 3]

14.49 g (31.4078 mmol) of formula (B), 4.63 g (37.6894 mmol) of 3-pyridine boronic acid,

1.09 g (0.9422 mmol) of tetrakis (triphenylphosphine) palladum (O), 8.68 g (62.8156 mmol) of potassium carbonate suspended in 160 ml of THF 160 ml distilled water After stirring, reflux was stirred for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, and the produced solid was separated and washed with distilled water and methyl alcohol. The solid was heated and dissolved in 130 ml of monochlorobenzene and charcoal was added thereto, followed by heating and stirring for 30 minutes. remind The reaction solution was separated by high temperature with silica gel, and the solid produced in the filtrate was separated and washed with methyl alcohol to obtain Inv-336.12 g (42% yield) of the target compound. calcd. C ₆₂ H ₄₀ N ₆ : C, 86.25; H, 4.61; N, 9.14; found: C, 85.98; H, 4. 49; N, 9.35 Example 4: Synthesis of Compound Represented by Inv-34

[Banungsik 4]

10 g (21.6755 mmol) of formula (B), 4.12 g (23.8431 mmol) of 8-quinoline boronic acid,

1.25 g (1.0838 mmol) of tetrakis (triphenylphosphine) paUadum (0) and 6.00 g (43.3510 mmol) of potassium carbonate are suspended in 100 ml of THF 200 ml. After stirring for 12 hours at reflux. After completion of reaction, the reaction mixture was cooled to room temperature, and the produced solid was separated and washed with distilled water and methyl alcohol. After dissolving the solid in 100 ml of monochlorobenzene, charcoal was added and the mixture was heated and stirred for 30 minutes. After the reaction solution was separated by high temperature with silica gel, 400 ml of methyl alcohol was added and stirred for 1 hour, and then the resulting solid was separated and washed with methyl alcohol to obtain Inv-347.1 g (64% yield) as a target compound. It was.

calcd. C ₆₂ H ₄₀ N ₆ : C, 87.21; H, 4.55; N, 8.25; found: C, 87.63; H, 4.79; N, 8.04 Example 5: Synthesis of Compound Represented by Inv39

[Banungsik 5]

8.7 g (18.8577 mmol) of formula (B), 3-quinoline boronic acid (Ruiyuan Group), 3.91 g (22.6292 mmol),

0.65 g (0.5657 mmol) of tetrakis (triphenylphosphine) palladum (0), 5.21 g (37.7154 mmol) of potassium carbonate, 80 ml of THF 170 ml After suspension, the mixture was stirred under reflux for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, and the resulting solid was separated and washed with distilled water and methyl alcohol. The solid

After heat dissolving in 240 ml of 0-dichlorobenzene, charcoal was added and the mixture was heated and stirred for 30 minutes. The reaction solution was separated by high temperature with silica gel, cooled to room temperature, and then the resulting solid was separated and washed with methyl alcohol to obtain 7.1 g (74% yield) of Inv-39 as a target compound.

calcd. C ₆₂ H ₄₀ N ₆ : C, 87.21; H, 4.55; N, 8.25; found: C, 87.52; H, 4. 36; N, 8.12 Example 6: Synthesis of Compound Represented by Inv-102

20 g (48.6275 mmol) of formula (c), 10.09 g (58.3530 mmol) of 8-quinoline boronic acid,

1.7 g (1.4588 mmol) of tetrakis (triphenylphosphine) palladum (O) and 13.44 g (97.2550 mmol) of potassium carbonate are suspended in 80 ml of THF 250 ml After stirring, reflux was stirred for 12 hours. After the reaction was completed, the mixture was cooled to room temperature, and the resulting solid was separated and washed with distilled water and methyl alcohol. After dissolving the solid in 300 ml of monochlorobenzene, charcoal was added, followed by heating and stirring for 30 minutes. The reaction mixture was separated by high temperature with silica gel, cooled to room temperature, separated from solids and washed with methyl alcohol to obtain 17.89 g (80% yield) of Inv-102 as a target compound. It was.

calcd. C ₆₂ H ₄₀ N ₆ : C, 86.25; H, 4.61; N, 9.14; found: C, 86.17; H, 4. 34; N, 9.02 Example 7: Synthesis of Compound Represented by Inv-106

Banungsik 7]

10 g (20.4003 mmol) of formula (D), 8.47 g (48.9606 mmol) of 8-quinoline boronic acid,

2.36 g (2.0400 mmol) of tetrakis (triphenylphosphine) palladum (0), 11.3 g (81.6012 mmol) of potassium carbonate, suspended 100 ml of THF 100 ml After stirring for 12 hours at reflux. After the reaction was completed, the mixture was cooled to room temperature, and the produced solid was separated and washed with distilled water and methyl alcohol. The solid

After heat dissolving in 300 ml of 0-dichlorobenzene, charcoal was added, followed by heating and stirring for 30 minutes. The reaction solution was separated by high temperature with silica gel, cooled to room temperature, and the resulting solid was separated and washed with methyl alcohol to obtain Inv-1069.65 g (81% yield) as a target compound.

calcd. C ₆₂ H ₄₀ N ₆ : C, 85.98; H, 4. 47; N, 9.55; found: C, 85.81; H, 4. 35; N, 9.62 Example 8: Synthesis of Compound Represented by Inv-131

Scheme 8

8.31 g (23.0570 mmol) of formula (E), 4.25 g (23.0570 mmol) of N-phenyl-o-phenylenediamine were suspended in 120 ml of toluene and 30 ml of acetic acid, followed by stirring under reflux for 48 hours. After completion of reaction, the resultant was concentrated and separated by silica gel column chromatography to obtain Inv-1315.1 g (42% Yield) as a target compound.

calcd. C ₆₂ H ₄₀ N ₆ : C, 84.71; H, 4.61; N, 10.68; found: C, 84.69; H, 4.67; N, 10.47

(Manufacture of organic light emitting device)

Example 9

As a positive electrode, πΌ was used at a thickness of 1000 A, and as a negative electrode, aluminum (A1) was used at a thickness of 1000 A.

Specifically, the method of manufacturing the organic light emitting device, the anode is cut in a glass substrate having a sheet resistance value of 15 n / cm ² to a size of 50 mm X 50 mm X 0.7 mm in acetone, isopropyl alcohol and pure water Ultrasonic cleaning was performed for 5 minutes each, followed by UV ozone cleaning for 30 minutes.

ΝΙ, ΝΙ '-(biphenyl-4,4'-diyl) bis (N1- (naphthalen-2-yl) -Ν4, Ν4-diphenylbenzene-1,4-diamond as a hole injection layer on the glass substrate Min) 65 nm was deposited, followed by depositing 40mn of Ν, Ν'-di (1-naphthyl) -Ν, Ν'-diphenylbenzidine as the hole transport layer.

Ν, Ν, Ν ′, Ν′-tetrakis (3,4-dimethylphenyl) crysen-6,12-diamine 4% and 9- (3- (naphthalen-1-yl) phenyl) -10 as light emitting layer -(Naphthalen-2-yl) anthracene 96% was deposited to a thickness of 25 nm.

Subsequently, 30 nm of the compound prepared in Example 1 was deposited as an electron transport layer.

Liq is vacuum deposited to a thickness of 0.5 nm as an electron injection layer on the electron transport layer, and A1 is vacuum deposited to a thickness of 100 nm to form a Liq / Al electrode.

Formed.

Example 10

An organic light emitting diode was manufactured according to the same method as Example 9 except for using the compound prepared in Example 2 instead of using the compound prepared in Example 1 as an electron transport layer. Example 11

An organic light emitting diode was manufactured according to the same method as Example 9 except for using the compound prepared in Example 3 as an electron transport layer, instead of using the compound prepared in Example 1.

Example 12

An organic light emitting diode was manufactured according to the same method as Example 9 except for using the compound fire prepared in Example 4 instead of using the compound prepared in Example 1 as the electron transport layer.

Example 13

An organic light emitting diode was manufactured according to the same method as Example 9 except for using the compound prepared in Example 5 as an electron transport layer, instead of using the compound prepared in Example 1.

Example 14

An organic light emitting diode was manufactured according to the same method as Example 9 except for using the compound prepared in Example 6 instead of using the compound prepared in Example 1 as an electron transport layer.

Example 15

An organic light emitting diode was manufactured according to the same method as Example 9 except for using the compound prepared in Example 7 instead of using the compound prepared in Example 1 as an electron transport layer.

Example 16

An organic light emitting diode was manufactured according to the same method as Example 9 except for using the compound prepared in Example 8 instead of using the compound prepared in Example 1 as an electron transport layer. Comparative Example 1

An organic light emitting diode was manufactured according to the same method as Example 9 except for using the compound represented by Chemical Formula R-1 as an electron transport layer, instead of using the compound prepared in Example 1.

[Formula R-1]

(Performance Measurement of Organic Light Emitting Diode)

Each of the prepared in Examples 9 to 16 and Comparative Example 1

For the organic light emitting diode, the current density change, luminance change, and luminous efficiency with pressure were measured. Specific accumulation method is as follows, and the results are shown in Table 1 below.

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

For the manufactured organic light emitting device, the voltage from 0V to 10V

While increasing, the current value flowing through the unit device was measured using a current-voltmeter (Keithley2400), and the measured current value was divided by the area to obtain a result.

(2) Measurement of luminance change according to voltage change

For the manufactured organic light emitting device, the voltage from 0V to 10V

While raising, the luminance at that time was measured using a luminance meter (Minolta Cs-IOOOA) to obtain a result.

(3) Measurement of luminous efficiency

The current efficiency (cd / A) and power efficiency (lm 八 V) of the same brightness (1000 cd / m2) are obtained using the brightness, current density, and voltage measured from (1) and (2).

Calculated.

TABLE 1

When the driving voltage is lower than in Comparative Example 1, luminous efficiency and power

It was found that the efficiency was excellent.

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 does not change the technical spirit or essential features of the present invention. It can be understood that the

will be. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

[Explanation of code]

100,200: organic light emitting device 110: the cathode

120: anode 105: organic thin film layer

130: light emitting layer 140: hole transport layer

230: light emitting layer

Claims

[Patent Claims]

[Claim 1]

Compound for an organic optoelectronic device represented by the general formula (1):

In Chemical Formula 1

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

L ¹ and L ² are each independently a substituted or unsubstituted C2 to C6 alkenylene group, a substituted or unsubstituted C2 to C6 alkynylene group, a substituted or unsubstituted C6 to .C30 arylene group, a substituted or unsubstituted C2 to C30 heteroarylene group or a combination thereof,

nl and n2 are each independently an integer of 0 to 5, and at least one of Ar ¹ or Ar ² is a substituted or unsubstituted C2 to C30 heteroaryl group; At least one of L ¹ or L ² is a substituted or unsubstituted C2 to C30 heteroarylene group,

R ¹ to R ³ independently of each other, hydrogen, hydrogen, halogen, cyano, hydroxyl, amino, substituted or unsubstituted C1 to C20 amine, nitro, carboxyl, ferrocenyl, substituted or unsubstituted A substituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C6 to C20 aryl Oxy group, substituted or unsubstituted C3 ⁷ J C40 silyloxy group, substituted or unsubstituted C1 to C20 acyl group, substituted or unsubstituted C2 to C20 alkoxycarbonyl group, substituted or unsubstituted C2 to C20

Acyloxy group, substituted or unsubstituted C2 to C20 acylamino group, substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, substituted or unsubstituted C1 to C20 Sulfamoylamino groups, substituted or unsubstituted ^' C1 to C20 sulfonyl groups, substituted or unsubstituted C1 to C20 alkylthiol groups, substituted seconds are unsubstituted C6 to C20 arylthiol groups, substituted or unsubstituted C1 to C20 hetero Cyclothiol group, substitution. Or an unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or a combination thereof.

[Claim 2]

The method of claim 1,

Wherein Ar ² is a substituted or unsubstituted C6 to C30 aryl group, and Ar ′ is a substituted or unsubstituted C2 to C30 heteroaryl group.

[Claim 3]

The method of claim 2,

L ¹ is a substituted or unsubstituted C2 to C30 heteroarylene group, nl is an organic optoelectronic device compound of any one of 1 to 5.

[Claim 4]

The method of claim 1,

Ar ¹ is a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, or a substituted or unsubstituted phenanthrenyl group

Compound for organic optoelectronic device.

[Claim 5]

The method of claim 1,

Ar ¹ and Ar ² are independently of each other, a substituted or unsubstituted C6 to C30 fused aryl group or a substituted or unsubstituted C2 to C30 fused heteroaryl group compound for an organic optoelectronic device.

[Claim 6] The method of claim 2,

L ¹ is a substituted or unsubstituted pyridinylene group

Compound for organic optoelectronic device.

[Claim 7]

The method of claim 1,

At least one of Ar ¹ and Ar ² is a compound for an organic optoelectronic device, which has an electronic property, a substituted or unsubstituted C2 to C30 heteroaryl group.

[Claim 8]

The method of claim 7, wherein

Having the electrical characteristics, a substituted or unsubstituted C2 to C30 heterocyclic aryl group, a substituted ^'or unsubstituted imidazolyl group, a substituted or unsubstituted triazolyl group, a substituted or unsubstituted tetrazolyl group, a substituted or unsubstituted A substituted oxadiazolyl group, a substituted or unsubstituted oxtriazolyl group, a substituted or unsubstituted thiatriazolyl group, a substituted or unsubstituted benzimidazolyl group, a substituted or unsubstituted benzotriazolyl group, a substituted Or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted pyrazinyl group, substituted or unsubstituted pyridazinyl group, substituted or unsubstituted Furinyl groups, substituted or unsubstituted quinolinyl groups, substituted or unsubstituted isoquinolinyl groups, substituted or unsubstituted phthalazinyl groups, substituted or unsubstituted naphpyridinyl groups, substituted or unsubstituted A substituted quinoxalinyl group, a substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenanthlinyl group, or a substituted or unsubstituted phenazinyl group

Compound for organic optoelectronic device.

[Claim 9]

The method of claim 7, wherein

The substituted or unsubstituted C2 to C30 heteroaryl group having the above electronic properties is substituted or unsubstituted pyridinyl group, substituted or unsubstituted pyrimidinyl group, substituted or unsubstituted triazinyl group, substituted or unsubstituted A quinolinyl group or a substituted or unsubstituted isoquinolinyl group Compound for organic optoelectronic device.

[Claim 10]

The method of claim 7, wherein

A compound for an organic optoelectronic device, wherein the substituted or unsubstituted C2 to C30 heteroaryl group having the electronic properties is represented by one of the following Formulas E-1 to E-5:

[Formula E-1] [Formula E-2] [Formula E-3] [Formula E-4] [Formula E-5]

[Claim 11]

The method of claim 1,

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

[Claim 12]

In an organic light emitting device comprising an anode, a cathode and at least one organic thin film layer interposed between the anode and the cathode,

At least one layer of the organic thin film layer is an organic light emitting device comprising the compound for an organic optoelectronic device according to claim 1.

[Claim 13]

The method of claim 12,

The organic thin film layer is any one selected from the group consisting of a light emitting layer, a hole transport layer, a hole injection layer, an electron transport layer, an electron injection layer, a hole blocking layer and a combination thereof.

[Claim 14]

The method of claim Π, wherein

The compound for an organic optoelectronic device is included in the electron injection layer or the electron transport layer. [Claim 15]

Display panel including the organic light emitting device of claim 12