WO2013100464A1

WO2013100464A1 - Compound for an organic optoelectronic element, organic light-emitting element comprising same, and display device comprising the organic light-emitting element

Info

Publication number: WO2013100464A1
Application number: PCT/KR2012/011022
Authority: WO
Inventors: 조영경; 홍진석; 강의수; 류동완; 이한일; 정성현; 채미영; 허달호
Original assignee: 제일모직 주식회사
Priority date: 2011-12-29
Filing date: 2012-12-17
Publication date: 2013-07-04
Also published as: KR20130077470A; KR101497134B1

Abstract

The present invention relates to a compound for an organic optoelectronic element, to an organic light-emitting element comprising same and to a display device comprising the organic light-emitting element; and provided is a compound for an organic optoelectronic element represented by a combination of chemical formulae 1 and 2, whereby it is possible to produce an organic light-emitting element which has outstanding lifespan characteristics due to outstanding electrochemical and thermal stability, and has high light-emission efficiency even at low drive voltages.

Description

Compound for an organic optoelectronic device, an organic light emitting device comprising the same and a display device comprising the organic light emitting device

The present invention relates to a compound for an organic optoelectronic device capable of providing an organic optoelectronic device having excellent life, efficiency, electrochemical stability, and thermal stability, an organic light emitting device including the same, and a display device including the organic light emitting device.

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, excitons are formed in the organic material layer by photons introduced into the device from an external light source, and the excitons are separated into electrons and holes, and these electrons and holes are transferred to different electrodes to be used as current sources (voltage sources). It is an electronic device of the form.

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

Examples of an organic optoelectronic device include an organic photoelectric device, an organic light emitting device, an organic solar cell, an organic photo conductor drum, and an organic transistor, 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 of converting electrical energy into light energy using an organic material.

Such an organic light emitting device converts electrical energy into light by applying a current to an organic light emitting material, and has a structure in which a functional organic material layer is inserted between an anode and a cathode. The organic material layer is often made of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic light emitting device, 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 the electrons meet and recombine by recombination. High energy excitons are formed. At this time, the excitons formed are moved 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, and these phosphorescent light emitting electrons transition 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 through intersystem crossing, and then triplet excitons emit light as they transition 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 realize 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 emission attenuation 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, materials constituting the organic material layer in the device, 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 a dopant in the light emitting material, etc. Supported by this stable and efficient material should be preceded, and 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 necessity of such a material development is the same in the other organic optoelectronic devices described above.

In addition, the low molecular weight organic light emitting diode is manufactured in the form of a thin film by vacuum evaporation method, so the efficiency and lifespan performance is good, and the high molecular weight organic light emitting diode using the inkjet or spin coating method has low initial investment cost. 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 a dark place or outside light is good cyanity, and no backlight is required, it can reduce the thickness and weight to 1/3 of the LCD.

In addition, the response speed is 1000 times faster than the LCD in microseconds, it is possible to implement a perfect video without afterimages. Therefore, it is expected to be spotlighted as the most suitable display in line with the recent multimedia era. Based on these advantages, we have made rapid technological developments with efficiency of 80 times and lifespan over 100 times since the first development in the late 1980s. Increasingly, large-scaled developments are being made with the introduction of organic light emitting diode panels.

In order to increase the size, the luminous efficiency must be increased and the life of the device must be accompanied. In this case, the light emitting efficiency of the device should be smoothly coupled to the holes and electrons in the light emitting layer. However, since the electron mobility of the organic material is generally slower than the hole mobility, in order to efficiently combine holes and electrons in the light emitting layer, an efficient electron transport layer is used to increase the electron injection and mobility from the cathode, It should be able to block the movement of holes.

In addition, in order to improve the life, it is necessary to prevent the material from crystallizing due to Joule heat generated when the device is driven. Therefore, there is a need for development of organic compounds having excellent electron injection and mobility and high electrochemical stability.

Provided are a compound for an organic optoelectronic device, which can play a role of hole injection and transport or electron injection and transport, and can act as a light emitting host with an appropriate dopant.

An organic light emitting diode having excellent lifespan, efficiency, driving voltage, electrochemical stability, and thermal stability and a display device including the same are provided.

In one embodiment of the present invention, a compound for an organic optoelectronic device represented by a combination of the following Chemical Formulas 1 and 2 is provided.

[Formula 1]

[Formula 2]

In Formulas 1 and 2, X is -O-, -S-, -S (O)-or -S (O) _2- , Ar ¹ and Ar ² are independently 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 a single bond, a substituted or unsubstituted C2 to C10 alkenylene group, a substituted or unsubstituted C2 to C10 alkynylene group, A substituted or unsubstituted C6 to C30 arylene group or a substituted or unsubstituted C2 to C30 heteroarylene group, m1 and m2 are independently an integer of 0 or 1, and any one of m1 and m2 is 1, n1 and n2 Is independently an integer of any one of 0 to 3, R ¹ to R ⁷ is independently hydrogen, deuterium, substituted or unsubstituted C1 to C10 alkyl group, substituted or unsubstituted C6 to C30 aryl group or substituted or unsubstituted C2 to C30 heteroaryl group, two * of Formula 2 are adjacent to the formula In combination with two - to form a fused ring.

Formula 1 may be represented by the following formula (3).

[Formula 3]

In Formula 3, Ar ² is a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group, L ² is a single bond, a substituted or unsubstituted C2 to C10 alkenylene group, A substituted or unsubstituted C2 to C10 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C2 to C30 heteroarylene group, m2 is 1, n2 is any one of 0 to 3 Is an integer, and R ¹ to R ³ , R ⁶ or R ⁷ are independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 Heteroaryl group, two * of the formula (2) is combined with two adjacent * of the formula (3) to form a fused ring.

The compound for an organic optoelectronic device may be represented by the following formula (4).

[Formula 4]

In Formula 4, X is -O-, -S-, -S (O)-or -S (O) _2- , Ar ¹ and Ar ² are independently 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 a single bond, a substituted or unsubstituted C2 to C10 alkenylene group, a substituted or unsubstituted C2 to C10 alkynylene group, a substituted or Unsubstituted C6 to C30 arylene group or substituted or unsubstituted C2 to C30 heteroarylene group, m1 and m2 are independently an integer of 0 or 1, either m1 and m2 is 1, n1 and n2 are independent Is an integer of any one of 0 to 3, R ¹ to R ⁷ are independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 To C30 heteroaryl group.

The compound for an organic optoelectronic device may be represented by the following formula (5).

[Formula 5]

In Formula 5, Ar ² is a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group, L ² is a single bond, a substituted or unsubstituted C2 to C10 alkenylene group, A substituted or unsubstituted C2 to C10 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C2 to C30 heteroarylene group, m2 is 1, n2 is any one of 0 to 3 Integer, R ¹ to R ⁷ are independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group.

Ar ¹ and Ar ² are independently substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted tetrazolyl group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted Substituted oxadiazolyl group, substituted or unsubstituted oxtriazolyl group, substituted or unsubstituted thiatriazolyl group, 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 group, substituted or unsubstituted pyridazinyl group, substituted or unsubstituted fury Nyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted phthalazinyl group, substituted or unsubstituted naphpyridinyl group, substituted or unsubstituted quinoxalinyl group , A substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenanthrolinyl group, a substituted or unsubstituted phenazinyl group, or a combination thereof.

Ar ¹ and Ar ² are independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted fluorenyl group , Substituted or unsubstituted triphenylenyl group, substituted or unsubstituted spiro-fluorenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted perrylenyl group, or May be a combination.

Ar ¹ and Ar ² are independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthryl group, a 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 Substituted triphenylenyl group, substituted or unsubstituted perenyl group, substituted or unsubstituted indenyl group, substituted or unsubstituted furanyl group, substituted or unsubstituted thiophenyl group, substituted or unsubstituted pyrrolyl group, substituted or Unsubstituted 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 oxadi Solyl 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 benzofuranyl group, substituted or unsubstituted benzothiophenyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted indolyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoqui Nolinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted benzoxazinyl group, substituted or unsubstituted benzthiazinyl group, It may be a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazineyl group, a substituted or unsubstituted phenothiazineyl group, a substituted or unsubstituted phenoxazineyl group, or a combination thereof.

The compound for an organic optoelectronic device may be a triplet excitation energy (T1) 2.0 eV or more.

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

In another embodiment of the present invention, in the 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 the above-described organic optoelectronic It provides an organic light emitting device comprising a compound for the device.

The organic thin film layer may be 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.

The compound for an organic optoelectronic device may be included in a hole transport layer or a hole injection layer.

The compound for an organic optoelectronic device may be included in a light emitting layer.

The compound for an organic optoelectronic device may be used as a phosphorescent or fluorescent host material in the light emitting layer.

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

Compounds having high hole or electron transport properties, film stability thermal stability and high triplet excitation energy can be provided.

Such a compound can be used as a hole injection / transport material, a host material, or an electron injection / transport material for the light emitting layer. The organic optoelectronic device using the same has excellent electrochemical and thermal stability, and has excellent life characteristics, and may have high luminous efficiency even at a low driving voltage.

1 to 5 are cross-sectional views illustrating 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.

100 organic light emitting device 110 cathode

120: anode 105: organic thin film layer

130: light emitting layer 140: hole transport layer

150: electron transport layer 160: electron injection layer

170: hole injection layer 230: light emitting layer + electron transport layer

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

In the present specification, "substituted", unless otherwise defined, at least one hydrogen of a substituent or a compound is a deuterium, a halogen group, a hydroxy group, an amino group, a substituted or unsubstituted C1 to C30 amine group, a nitro group, a substituted or unsubstituted C1 to C10 such as 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, fluoro group, trifluoromethyl group, etc. Mean substituted by a trifluoroalkyl group or a 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 of C1 to C10 trifluoroalkyl group or cyano group such as C30 cycloalkyl group, C6 to C30 aryl group, C1 to C20 alkoxy group, fluoro group and trifluoromethyl group may be fused to form a ring. .

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

In the present specification, "combination thereof" means that two or more substituents are bonded to a linking group or two or more substituents are condensed to each other unless otherwise defined.

As used herein, unless otherwise defined, an "alkyl group" means an aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double or triple bonds. The alkyl group may be branched, straight chain or cyclic.

"Alkenylene group" means a functional group consisting of at least two carbon atoms of at least one carbon-carbon double bond, and "alkynylene group" means at least two carbon atoms of at least one carbon-carbon triplet. It means a functional group consisting of a bond.

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 has 1 to 4 carbon atoms in the alkyl chain, i.e., the alkyl chain is methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl and t-butyl Selected from the group consisting of:

For example, the alkyl group is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohex It means a practical skill.

"Aromatic group" means a functional group in which all elements of the functional group in the ring form have p-orbitals, and these p-orbitals form conjugation. Specific examples include an aryl group and a heteroaryl group.

An "aryl group" includes a monocyclic or fused ring polycyclic (ie, a ring that divides 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 carbazole derivative refers to a structure in which a nitrogen atom of a substituted or unsubstituted carbazolyl group is substituted with a hetero atom or carbon instead of nitrogen. Specific examples thereof include dibenzofuran (dibenzofuranyl group), dibenzothiophene (dibenzothiophenyl group), fluorene (fluorenyl group) and the like.

In the present specification, the hole characteristic means a characteristic that has conductivity characteristics along the HOMO level to facilitate the injection of holes formed at the anode into the light emitting layer and movement in the light emitting layer.

In addition, an electronic characteristic means the characteristic which has electroconductive characteristic along LUMO level, and facilitates the injection of the electron formed in the cathode into the light emitting layer, and the movement in the light emitting layer.

Compound for an organic optoelectronic device according to an embodiment of the present invention is at least one substituted or unsubstituted aryl group in the bifluorene core of the spiro structure; Or a substituted or unsubstituted heteroaryl group.

In addition, some of the core of the spiro structure may be in the form of a fused ring.

The core structure may be used as a light emitting material, a hole injection material or a hole transport material of an organic optoelectronic device. It may be particularly suitable for hole injection materials or hole transport materials.

In addition, the compound for an organic optoelectronic device may be a compound having various energy band gaps by introducing a variety of other substituents to the substituents substituted in the core portion and the core portion.

By using a compound having an appropriate energy level in the organic optoelectronic device according to the substituent of the compound, the hole transport ability or electron transfer ability is enhanced to have an excellent effect in terms of efficiency and driving voltage, and excellent in organic chemical and thermal stability It is possible to improve the life characteristics when driving the device.

In one embodiment of the present invention, it is possible to provide a compound for an organic optoelectronic device represented by a combination of the following formula (1) and (2).

[Formula 1]

[Formula 2]

X may be -O-, -S-, -S (O)-or -S (O) _2- . Since the -O-, -S-, -S (O)-or -S (O) ₂ -has a polar group and can interact with the electrode, the charge can be easily injected.

When Ar ¹ or Ar ² is bonded to a bifluorene group having a spiro structure as the core, the mobility of charges may be increased, thereby lowering the driving voltage of the device.

In addition, since the compound has steric hindrance, the interaction between molecules is small, so that crystallization can be suppressed. For this reason, the yield which manufactures an element can be improved. In addition, the life characteristics of the manufactured device can be improved.

Moreover, since the said compound has a comparatively large molecular weight, decomposition | disassembly at the time of vapor deposition of a compound can be suppressed.

More specifically, Chemical Formula 1 may be represented by the following Chemical Formula 3.

[Formula 3]

More specifically, the compound for an organic optoelectronic device may be represented by the following formula (4). In the case of having the position of the fused ring as shown in the following formula (4), by introducing a spirofluorene group to the 3, 4 positions of dibenzofuran and dibenzothiophene, structural isomers do not occur, thereby increasing the synthesis yield. In addition, dibenzofuran and dibenzothiophene have high hole mobility and function as a hole transport group, and spirofluorene can improve thermal stability and electrochemical stability.

[Formula 4]

More specifically, the compound for an organic optoelectronic device may be represented by the following Formula 5.

[Formula 5]

By selectively adjusting the L ¹ and L ² to determine the conjugation length of the entire compound, it can be applied to the light emitting layer of the organic photoelectric device as a phosphorescent host by increasing the triplet energy band gap therefrom.

Specific examples of the L ¹ and L ² are a substituted or unsubstituted phenylene group, a substituted or unsubstituted biphenylene group, a substituted or unsubstituted terphenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted Anthracenylene group, substituted or unsubstituted phenanthryl group, substituted or unsubstituted pyrenylene group, substituted or unsubstituted fluorenylene group, substituted or unsubstituted triphenylene group and the like.

Ar ¹ and Ar ² are independently substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted tetrazolyl group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted Substituted oxadiazolyl group, substituted or unsubstituted oxtriazolyl group, substituted or unsubstituted thiatriazolyl group, 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 group, substituted or unsubstituted pyridazinyl group, substituted or unsubstituted fury Nyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted phthalazinyl group, substituted or unsubstituted naphpyridinyl group, substituted or unsubstituted quinoxalinyl group , A substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenanthrolinyl group, a substituted or unsubstituted phenazinyl group, or a combination thereof. In this case, bipolar structural compounds may be synthesized in combination with a substituent having high electron mobility to increase hole and electron transporting ability, thereby improving light emission efficiency and performance of the device.

Ar ¹ and Ar ² are independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted fluorenyl group , Substituted or unsubstituted triphenylenyl group, substituted or unsubstituted spiro-fluorenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted perrylenyl group, or May be a combination. In this case, the molecular weight can be adjusted to facilitate the sublimation purification.

Ar ¹ and Ar ² are independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthryl group, a 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 Substituted triphenylenyl group, substituted or unsubstituted perenyl group, substituted or unsubstituted indenyl group, substituted or unsubstituted furanyl group, substituted or unsubstituted thiophenyl group, substituted or unsubstituted pyrrolyl group, substituted or Unsubstituted 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 oxadi Solyl 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 benzofuranyl group, substituted or unsubstituted benzothiophenyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted indolyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoqui Nolinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted benzoxazinyl group, substituted or unsubstituted benzthiazinyl group, It may be a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazineyl group, a substituted or unsubstituted phenothiazineyl group, a substituted or unsubstituted phenoxazineyl group, or a combination thereof. In this case, a bipolar structural compound may be synthesized by a combination of substituents of a heteroaryl group having good electron transfer ability, and thus, light emission efficiency and performance improvement of the device may be expected by increasing hole and electron transfer ability.

The compound for an organic optoelectronic device due to the substituent is light emitting, hole or electronic properties; Membrane stability; Thermal stability and high triplet excitation energy (T1).

More specifically, the compound for an organic optoelectronic device may be represented by any one of the following Formulas A-1 to A-24, but is not limited thereto.

[Formula A-1] [Formula A-2] [Formula A-3] [Formula A-4]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula A-5] [Formula A-6]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula A-7] [Formula A-8]

[Correction under Article 91 of the Rule 21.02.2013]
d

[Formula A-9] [Formula A-10]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula A-11] [Formula A-12]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula A-13] [Formula A-14] [Formula A-15] [Formula A-16]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula A-17] [Formula A-18]

[Correction under Article 91 of the Rule 21.02.2013]

Formula A-19 Formula A-20

[Correction under Article 91 of the Rule 21.02.2013]

[Formula A-21] [Formula A-22]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula A-23] [Formula A-24]

[Correction under Article 91 of the Rule 21.02.2013]

More specifically, the compound for an organic optoelectronic device may be represented by any one of the following Formulas B-1 to B-257, but is not limited thereto.

[Formula B-1] [Formula B-2] [Formula B-3] [Formula B-4]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-5] [Formula B-6] [Formula B-7] [Formula B-8]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-9] [Formula B-10] [Formula B-11] [Formula B-12]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-13] [Formula B-14] [Formula B-15] [Formula B-16]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-17] [Formula B-18] [Formula B-19] [Formula B-20]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-21] [Formula B-22] [Formula B-23] [Formula B-24]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-25] [Formula B-26] [Formula B-27] [Formula B-28]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-29] [Formula B-30] [Formula B-31] [Formula B-32]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-33] [Formula B-34] [Formula B-35] [Formula B-36]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-37] [Formula B-38] [Formula B-39] [Formula B-40]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-41] [Formula B-42] [Formula B-43] [Formula B-44]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-45] [Formula B-46] [Formula B-47] [Formula B-48]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-49] [Formula B-50] [Formula B-51]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-52] [Formula B-53] [Formula B-54]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-55] [Formula B-56] [Formula B-57]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-58] [Formula B-59] [Formula B-60]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-61] [Formula B-62] [Formula B-63]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-64] [Formula B-65] [Formula B-66]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-67] [Formula B-68] [Formula B-69]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-70] [Formula B-71] [Formula B-72]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-73] [Formula B-74] [Formula B-75]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-76] [Formula B-77] [Formula B-78]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-79] [Formula B-80] [Formula B-81]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-82] [Formula B-83] [Formula B-84]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-85]

[Correction under Article 91 of the Rule 21.02.2013]

Formula B-86 Formula B-87

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-88] [Formula B-89]

[Correction under Article 91 of the Rule 21.02.2013]

Formula B-90 Formula B-91

[Correction under Article 91 of the Rule 21.02.2013]

Formula B-92 Formula B-93

[Correction under Article 91 of the Rule 21.02.2013]

Formula B-94 Formula B-95

[Correction under Article 91 of the Rule 21.02.2013]

Formula B-96 Formula B-97

[Correction under Article 91 of the Rule 21.02.2013]

Formula B-98 Formula B-99

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-100] [Formula B-101] [Formula B-102]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-103] [Formula B-104] [Formula B-105]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-106] [Formula B-107] [Formula B-108]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B109] [Formula B110] [Formula B111]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-112] [Formula B-113] [Formula B-114]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-115] [Formula B-116] [Formula B-117]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-118] [Formula B-119]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-120] [Formula B-121] [Formula B-122]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-123] [Formula B-124] [Formula B-125]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-126] [Formula B-127] [Formula B-128]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-129] [Formula B-130] [Formula B-131]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-132] [Formula B-133] [Formula B-134] [Formula B-135]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-136] [Formula B-137] [Formula B-138] [Formula B-139]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-140] [Formula B-141] [Formula B-142] [Formula B-143]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-144] [Formula B-145] [Formula B-146] [Formula B-147]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-148] [Formula B-149] [Formula B-150] [Formula B-151]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-152] [Formula B-153] [Formula B-154] [Formula B-155]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-156] [Formula B-157] [Formula B-158] [Formula B-159]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-160] [Formula B-161] [Formula B-162] [Formula B-163]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-164] [Formula B-165] [Formula B-166] [Formula B-167]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-168] [Formula B-169] [Formula B-170] [Formula B-171]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-172] [Formula B-173] [Formula B-174] [Formula B-175]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-176] [Formula B-177] [Formula B-178]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-179] [Formula B-180] [Formula B-181]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-182] [Formula B-183]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-184] [Formula B-185] [Formula B-186]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-187] [Formula B-188] [Formula B-189]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-190] [Formula B-191] [Formula B-192]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-193] [Formula B-194] [Formula B-195]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-196] [Formula B-197] [Formula B-198]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-199] [Formula B-200] [Formula B-201]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-202] [Formula B-203] [Formula B-204]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-205] [Formula B-206] [Formula B-207]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-208] [Formula B-209] [Formula B-210]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-211]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-212] [Formula B-213]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-214] [Formula B-215]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-216] [Formula B-217]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-218] [Formula B-219]

[Correction under Article 91 of the Rule 21.02.2013]

Formula B-220 Formula B-221

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-222] [Formula B-223]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-224] [Formula B-225]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-226] [Formula B-227] [Formula B-228]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-229] [Formula B-230] [Formula B-231]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-232] [Formula B-233] [Formula B-234]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-235] [Formula B-236] [Formula B-237]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-238] [Formula B-239] [Formula B-240]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-241] [Formula B-242] [Formula B-243]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-244] [Formula B-245]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-246] [Formula B-247] [Formula B-248]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-249] [Formula B-250] [Formula B-251]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-252] [Formula B-253] [Formula B-254]

[Correction under Article 91 of the Rule 21.02.2013]

[Formula B-255] [Formula B-256] [Formula B-257]

[Correction under Article 91 of the Rule 21.02.2013]

When the compound according to the embodiment of the present invention requires both electronic and hole characteristics, introducing a functional group having the electronic characteristics is effective for improving the lifespan and driving voltage of the organic light emitting diode.

Compound for an organic optoelectronic device according to an embodiment of the present invention described above has a maximum emission wavelength of about 320 to 500 nm, triplet excitation energy (T1) is 2.0 eV or more, more specifically 2.0 to 4.0 eV range The charge of the host having a high triplet excitation energy is well transferred to the dopant, thereby increasing the light emitting efficiency of the dopant and lowering the driving voltage by freely adjusting the HOMO and LUMO energy levels of the material. Because of the advantages it can be very useful as a host material or a charge transport material.

In addition, since the compound for an organic optoelectronic device has photoactive and electrical activity, nonlinear optical material, electrode material, color change material, optical switch, sensor, module, wave guide, organic transistor, laser, light absorber, dielectric and separator It can also be very usefully applied to materials such as (membrane).

The compound for an organic optoelectronic device including the compound as described above has a glass transition temperature of 90 ° C. or higher, and a thermal decomposition temperature of 400 ° C. or higher, thereby providing excellent thermal stability. This makes it possible to implement a high efficiency organic photoelectric device.

The compound for an organic optoelectronic device including the compound as described above may serve as light emission, electron injection and / or transport, and may also serve as a light emitting host with an appropriate dopant. That is, the compound for an organic optoelectronic device may be used as a host material of phosphorescence or fluorescence, a blue dopant material, or an electron transport material.

Compound for an organic optoelectronic device according to an embodiment of the present invention is used in the organic thin film layer to improve the life characteristics, efficiency characteristics, electrochemical stability and thermal stability of the organic optoelectronic device, it is possible to lower the driving voltage.

Accordingly, one embodiment of the present invention provides an organic optoelectronic device comprising the compound for an organic optoelectronic device. In this case, the organic optoelectronic device refers to an organic photoelectric device, an organic light emitting device, an organic solar cell, an organic transistor, an organic photosensitive drum, an organic memory device, and the like. In particular, in the case of an organic solar cell, a compound for an organic optoelectronic device according to an embodiment of the present invention is included in an electrode or an electrode buffer layer to increase quantum efficiency, and in the case of an organic transistor, a gate, a source-drain electrode, or the like may be used as an electrode material. Can be used.

Hereinafter, an organic light emitting diode will be described in detail.

Another embodiment of the present invention is 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 any one of the organic thin film layer is an embodiment of the present invention It provides an organic light emitting device comprising a compound for an organic optoelectronic device according to.

The organic thin film layer which may include the compound for an organic optoelectronic device may include a layer 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. At least one of the layers includes the compound for an organic optoelectronic device according to the present invention. In particular, the hole transport layer or the hole injection layer may include a compound for an organic optoelectronic device according to an embodiment of the present invention. In addition, when the compound for an organic optoelectronic device is included in a light emitting layer, the compound for an organic optoelectronic device may be included as a phosphorescent or fluorescent host, and in particular, may be included as a fluorescent blue dopant material.

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 to 5, the organic

light emitting diodes

100, 200, 300, 400, and 500 according to the embodiment of the present invention are interposed between the anode 120, the cathode 110, and the anode and the cathode. It has a structure including at least one organic thin film layer 105.

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 injected into the organic thin film layer. Specific examples of the positive electrode material include metals such as nickel, platinum, vanadium, chromium, copper, zinc, and gold or alloys thereof, and include zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO). And metal oxides such as ZnO and Al, or combinations of metals and oxides such as SnO ₂ and Sb, and poly (3-methylthiophene), poly [3,4- (ethylene-1, 2-dioxy) thiophene] (conductive polymers such as polyehtylenedioxythiophene (PEDT), polypyrrole and polyaniline, etc.), but is not limited thereto. Preferably, a transparent electrode including indium tin oxide (ITO) may be used as the anode.

The negative electrode 110 includes a negative electrode material, and the negative electrode material is preferably 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, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, lead, cesium, barium, or alloys thereof, and LiF / Al. , Multilayer structure materials such as LiO ₂ / Al, LiF / Ca, LiF / Al, and BaF ₂ / Ca, and the like, but are not limited thereto. Preferably, a metal electrode such as aluminum may be used as the cathode.

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 illustrates a two-layered organic light emitting diode 200 including an emission layer 230 and an hole transport layer 140 including an electron transport layer as the organic thin film layer 105, as shown in FIG. 2. Likewise, 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 the hole transporting layer 140 functions to improve bonding and hole transporting properties with a transparent electrode such as ITO.

Referring to FIG. 3, FIG. 3 is a three-layered organic light emitting device 300 having an electron transport layer 150, an emission layer 130, and a hole transport layer 140 as an organic thin film layer 105, and the organic thin film layer 105. The light emitting layer 130 is in an independent form, and has a form in which a film (electron transport layer 150 and hole transport layer 140) having excellent electron transport properties or hole transport properties is stacked in separate layers.

Referring to FIG. 4, FIG. 4 illustrates a four-layered organic light emitting diode 400 in which an electron injection layer 160, an emission layer 130, a hole transport layer 140, and a hole injection layer 170 exist as an organic thin film layer 105. As a result, the hole injection layer 170 may improve adhesion to ITO used as an anode.

Referring to FIG. 5, FIG. 5 shows different functions such as the electron injection layer 160, the electron transport layer 150, the light emitting layer 130, the hole transport layer 140, and the hole injection layer 170 as the organic thin film layer 105. The five-layer organic light emitting device 500 having five layers is present, and the organic light emitting device 500 is effective in lowering the voltage by separately forming the electron injection layer 160.

1 to 5, the electron transport layer 150, the electron injection layer 160, the

light emitting layers

130 and 230, the hole transport layer 140, and the hole injection layer 170 forming the organic thin film layer 105 and their Any one selected from the group consisting of a combination includes the compound for an organic optoelectronic device. In this case, the compound for an organic optoelectronic device may be used in the electron transport layer 150 including the electron transport layer 150 or the electron injection layer 160, and the hole blocking layer (not shown) is included in the electron transport layer. It is desirable to provide an organic light emitting device having a simplified structure because it does not need to be formed separately.

In addition, when the compound for an organic optoelectronic device is included in the

light emitting layers

130 and 230, the compound for an organic optoelectronic device may be included as a phosphorescent or fluorescent host, or may be included as a fluorescent blue dopant.

The above-described organic light emitting device includes a dry film method such as an evaporation, sputtering, plasma plating and ion plating after forming an anode on a substrate; Alternatively, the organic thin film layer may be formed by a wet film method such as spin coating, dipping, flow coating, or the like, followed by forming a cathode thereon.

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

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.

(유기광전자소자용 화합물의 제조)Preparation of Compound for Organic Optoelectronic Devices

중간체 생성물 (A), (B), (C) 및 (D)의 합성Synthesis of Intermediate Products (A), (B), (C) and (D)

Synthesis was carried out through a 4 step route as in Scheme 1 below.

Scheme 1

[Correction under Article 91 of the Rule 21.02.2013]

First step; Synthesis of Intermediate Product (A)

15.01 g (70.79 mmol) of 4-dibenzofuran boronic acid, 22.03 g (77.87 mmol) of 2-bromoiodobenzene and 11.74 g (84.95 mmol) of potassium carbonate, tetrakis- (triphenylphosphine) palladium (0) 1.64 g (1.42 mmmol) was suspended in 300 ml of toluene and 150 ml of ethanol, followed by stirring under reflux for 12 hours. After the completion of the reaction, the reaction solution was extracted with dichloromethane, filtered with silica gel, and distilled under reduced pressure, followed by silica gel column with hexane: dichloromethane = 9: 1 (v / v) to give 15 g of an intermediate product (A) (yield: 60%). ) Was obtained.

Second step; Synthesis of Intermediate Product (B)

It is suspended in 8.2 g (25.37 mmol) of the intermediate product (A) synthesized in Example 1 and 150 mL of tetrahydrofuran and slowly added 30.45 mL (19.04 mmol) of n-BuLi at -78 ° C. After 2 hours of stirring at -78 ° C, 9.43 g (27.91 mol) of 2,7-dibromofluorenone was slowly added thereto and stirred for 24 hours. After completion of the reaction, the mixture was quenched with aqueous ammonium chloride solution, extracted with dichloromethane, and the organic layer was filtered with silica gel. The organic solution was removed and silica gel column with hexane: ethyl acetate = 7: 3 (v / v) to give 11.8 g (yield: 80%) of the intermediate product (B).

Step 3: Synthesis of Intermediate Product (C)

Suspend 11.8 g (20.27 mmol) of intermediate product (B) in 200 mL of acetic acid, and slowly add 3.95 mL (60.8 mmol) of CH3SO3H at room temperature. Stir for 24 hours. After completion of the reaction, the resultant was quenched with 200 mL of sodium bicarbonate aqueous solution, the resulting solid was filtered, extracted with dichloromethane and distilled water, and the organic layer was filtered with silica gel. The organic solution was removed and silica gel column with hexane: dichloromethane = 6: 4 (v / v) gave 9.5 g (yield: 83%) of intermediate product (C).

Step 4: Synthesis of Intermediate Product (D)

10 g (17.72 mmol) of intermediate product (C), 5.85 g (23.04 mmol) of bispinacolatodiborane, 5.22 g (53.17 mmol) of potassium acetate and 0.29 g (0.35 mmol) of [bis (diphenylphosphino) ferrocene] dichloropalladium ) Was suspended in 100 mL of toluene and stirred under reflux for 12 hours. After completion of the reaction, the mixture was extracted with dichloromethane and distilled water, and the organic layer was filtered with silica gel. The organic solution was removed and silica gel column with hexane: ethylacetic acid = 8: 2 (v / v) afforded 5.6 g (yield: 48%) of intermediate product (D).

실시예 1: 화합물 A-1의 합성Example 1: Synthesis of Compound A-1

Scheme 2

[Correction under Article 91 of the Rule 21.02.2013]

9.5 g (16.84 mmol) of intermediate compound (C), 4.31 g (35.36 mmol) of 4-phenylboronic acid, 2.79 g (20.2 mmol) of potassium carbonate, 0.39 g (0.34) of tetrakis- (triphenylphosphine) palladium (0) mmmol) was suspended in 200 ml of toluene and 100 ml of distilled water and stirred under reflux for 12 hours. Extract with dichloromethane and distilled water and filter the organic layer with silica gel. The organic solution was removed and silica gel column with hexane: dichloromethane = 7: 3 (v / v) to recrystallize the product solid with dichloromethane and normal hexane to give 6.5 g (yield: 69%) of the compound of formula A-1. .

실시예 2: 화합물 A-6의 합성Example 2: Synthesis of Compound A-6

Scheme 3

[Correction under Article 91 of the Rule 21.02.2013]

7 g (12.41 mmol) of intermediate compound (C) and 5.16 g (26.05 mmol) of 4-biphenyl boronic acid and 2.06 g (14.89 mmol) of potassium carbonate, 0.29 g of tetrakis- (triphenylphosphine) palladium (0) 0.25 mmmol) was suspended in 50 ml of toluene and 10 ml of distilled water, followed by stirring under reflux for 12 hours. Extract with dichloromethane and distilled water and filter the organic layer with silica gel. The organic solution was removed and silica gel column with hexane: dichloromethane = 7: 3 (v / v) to recrystallize the product solid with dichloromethane and normal hexane to give 5.5 g (yield: 62%) of the compound of formula A-6. .

실시예 3: 화합물 A-8의 합성Example 3: Synthesis of Compound A-8

Scheme 4

[Correction under Article 91 of the Rule 21.02.2013]

5.6 g (8.51 mmol) of intermediate compound (D) and 5.52 g (17.86 mmol) of 1-bromo-3,5-diphenylbenzene and 1.41 g (10.21 mmol) of potassium carbonate, tetrakis- (triphenylphosphine) palladium (0) 0.2 g (0.17 mmmol) was suspended in 50 ml of toluene and 12 ml of distilled water, followed by stirring under reflux for 12 hours. Extract with dichloromethane and distilled water and filter the organic layer with silica gel. The organic solution was removed and silica gel column with hexane: dichloromethane = 7: 3 (v / v) to recrystallize the product solid with dichloromethane and normal hexane to give 3.7 g (yield: 50%) of the compound of formula A-8. .

실시예 4: 화합물 A-11의 합성Example 4: Synthesis of Compound A-11

Scheme 5

[Correction under Article 91 of the Rule 21.02.2013]

7 g (12.41 mmol) of intermediate compound (C) and 6.2 g (26.05 mmol) of 9,9'-dimethyl-2-fluorene boronic acid and 2.06 g (14.89 mmol) of potassium carbonate, tetrakis- (triphenylphosphine) 0.29 g (0.25 mmmol) of palladium (0) was suspended in 50 ml of toluene and 12 ml of distilled water, followed by stirring under reflux for 12 hours. Extract with dichloromethane and distilled water and filter the organic layer with silica gel. The organic solution was removed and silica gel column with hexane: dichloromethane = 7: 3 (v / v) to recrystallize the product solid with dichloromethane and normal hexane to give 5.4 g (yield: 55%) of the compound of formula B-8. .

실시예 5: 화합물 B-123의 합성Example 5: Synthesis of Compound B-123

Scheme 6

[Correction under Article 91 of the Rule 21.02.2013]

6 g (9.11 mmol) of intermediate compound (D) and 5.1 g (19.14 mmol) of 2-chloro-4,6-diphenylpyrimidine and 1.51 g (10.94 mmol) of potassium carbonate, tetrakis- (triphenylphosphine) palladium (0) 0.21 g (0.18 mmmol) was suspended in 50 ml of toluene and 10 ml of distilled water, followed by stirring under reflux for 12 hours. Extract with dichloromethane and distilled water and filter the organic layer with silica gel. The organic solution was removed and the product solid was recrystallized from dichloromethane and normal hexane by silica gel column with hexane: dichloromethane = 7: 3 (v / v) to give 4.7 g of a compound of formula B-123 (yield: 59%). .

실시예 6: 화합물 B-127의 합성Example 6: Synthesis of Compound B-127

Scheme 7

[Correction under Article 91 of the Rule 21.02.2013]

6 g (9.11 mmol) of intermediate compound (D) and 5.12 g (19.14 mmol) of 2-chloro-4,6-diphenyltriazine and 1.51 g (10.94 mmol) of potassium carbonate, tetrakis- (triphenylphosphine) palladium (0) 0.21 g (0.18 mmmol) was suspended in 50 ml of toluene and 10 ml of distilled water, followed by stirring under reflux for 12 hours. Extract with dichloromethane and distilled water and filter the organic layer with silica gel. The organic solution was removed and silica gel column with hexane: dichloromethane = 7: 3 (v / v) to recrystallize the product solid with dichloromethane and normal hexane to give 5 g of a compound of formula B-127 (yield: 63%). .

(유기발광소자의 제조)(Manufacture of organic light emitting device)

실시예 7: 유기발광소자의 제조Example 7: Fabrication of Organic Light Emitting Diode

The glass substrate coated with ITO (Indium tin oxide) having a thickness of 1500 Å was washed with distilled water ultrasonic waves. After washing the distilled water, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol and the like was dried and then transferred to a plasma cleaner, and then the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum depositor. Using the prepared ITO transparent electrode as an anode, HTM (see material structure below) was vacuum deposited on the ITO substrate to form a hole injection layer having a thickness of 1200 Å.

[HTM]

[Correction under Article 91 of the Rule 21.02.2013]

The material synthesized in Example 1 was used as a host on the hole injection layer, and a phosphorescent green dopant was doped with PhGD (see the figure below) at 7% by weight to form a light emitting layer having a thickness of 300 Pa by vacuum deposition.

[PhGD]

[Correction under Article 91 of the Rule 21.02.2013]

Then, BAlq [Bis (2-methyl-8-quinolinolato-N1, O8)-(1,1'-Biphenyl-4-olato) aluminum] 50um and Alq3 [Tris (8-hydroxyquinolinato) aluminium] 250Å Laminated sequentially to form an electron transport layer. An organic light emitting device was manufactured by sequentially depositing LiF 5 ′ and Al 1000 ′ on the electron transport layer to form a cathode.

Balq [Alq3]

[Correction under Article 91 of the Rule 21.02.2013]

실시 예 8Example 8

An organic light emitting diode was manufactured according to the same method as Example 7 except for using the compound prepared in Example 2 (A-6) instead of using the compound prepared in Example 1.

실시 예 9Example 9

An organic light emitting diode was manufactured according to the same method as Example 7 except for using the compound prepared in Example 3 (A-8) instead of using the compound prepared in Example 1.

실시 예 10Example 10

An organic light emitting diode was manufactured according to the same method as Example 7 except for using the compound prepared in Example 4 (A-11) instead of using the compound prepared in Example 1.

실시 예 11Example 11

An organic light emitting diode was manufactured according to the same method as Example 7 except for using the compound prepared in Example 5 (B-123), instead of using the compound prepared in Example 1.

실시 예 12Example 12

An organic light emitting diode was manufactured according to the same method as Example 7 except for using the compound prepared in Example 6 (B-127) instead of using the compound prepared in Example 1.

비교예 1Comparative Example 1

An organic light emitting diode was manufactured according to the same method as Example 4 except for using Compound C1 as a host instead of Example 1 (A-6).

[C1]

(유기발광소자의 성능 측정)(Performance Measurement of Organic Light Emitting Diode)

For each of the organic light emitting diodes manufactured in Examples 7 to 12 and Comparative Example 1, the current density change, luminance change, and luminous efficiency according to voltage were measured. Specific measurement methods are as follows, and the results are shown in Table 1 below.

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

For the organic light emitting device, the current value flowing through the unit device was measured 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-1000A) while increasing the voltage from 0V to 10V to obtain a result.

(3) Measurement of luminous efficiency

The current efficiency (cd / A) and power efficiency (lm / W) of the same brightness (3,000 cd / m ² ) were calculated using the brightness, current density, and voltage measured from (1) and (2) above.

(4) Color coordinates were measured using a luminance meter (Minolta Cs-100A), and the results are shown.

Table 1 summarizes the device evaluation results.

Table 1

Classification	Host	Vd	Cd / A	lm / W	cd / m ²	CIEx	CIEy
Comparative Example 1	C1	6.90	49.53	22.54	3000	0.333	0.623
Example 7	A-1	5.45	54.3	31.3	3000	0.356	0.613
Example 8	A-6	5.48	54.1	31	3000	0.348	0.608
Example 9	A-8	5.65	55.6	30.9	3000	0.345	0.611
Example 10	A-11	5.38	55.8	32.6	3000	0.359	0.615
Example 11	B-123	5.90	52.9	28.2	3000	0.354	0.607
Example 12	B-127	5.95	52.5	27.7	3000	0.362	0.609

It can be seen that all of the above Examples 7 to 12 lower the driving voltage of the organic light emitting device and improve the brightness and efficiency compared with the device of Comparative Example 1.

Based on this, low voltage, high efficiency, high brightness, long life organic light emitting device having excellent electron injection and electron transfer ability could be manufactured.

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

Compound for an organic optoelectronic device represented by a combination of the following formula (1) and (2):

[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,

X is -O-, -S-, -S (O)-or -S (O) 2- ,

Ar 1 and Ar 2 are 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 independently a single bond, a substituted or unsubstituted C2 to C10 alkenylene group, a substituted or unsubstituted C2 to C10 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group or a substituted or unsubstituted C2 to C30 heteroarylene group,

m1 and m2 are independently an integer equal to 0 or 1, either of m1 and m2 is 1,

n1 and n2 are each independently an integer of 0 to 3,

R 1 to R 7 are independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group,

Two * of Formula 2 is combined with two adjacent * of Formula 1 to form a fused ring.
The method of claim 1,

Formula 1 is a compound for an organic optoelectronic device that is represented by the following formula (3):

[Formula 3]

In Chemical Formula 3,

Ar 2 is a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group,

L 2 is a single bond, a substituted or unsubstituted C2 to C10 alkenylene group, a substituted or unsubstituted C2 to C10 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C2 to C30 hetero Arylene group,

m2 is 1,

n2 is an integer of any one of 0 to 3,

R 1 to R 3 , R 6 or R 7 are independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group ego,

Two * of Formula 2 combines with two adjacent * of Formula 3 to form a fused ring.
The method of claim 1,

The compound for an organic optoelectronic device is a compound for an organic optoelectronic device is represented by the following formula (4):

[Formula 4]

In Chemical Formula 4,

X is -O-, -S-, -S (O)-or -S (O) 2- ,

Ar 1 and Ar 2 are 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 independently a single bond, a substituted or unsubstituted C2 to C10 alkenylene group, a substituted or unsubstituted C2 to C10 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group or a substituted or unsubstituted C2 to C30 heteroarylene group,

m1 and m2 are independently an integer equal to 0 or 1, either of m1 and m2 is 1,

n1 and n2 are each independently an integer of 0 to 3,

R 1 to R 7 are independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group.
The method of claim 1,

The compound for an organic optoelectronic device is a compound for an organic optoelectronic device that is represented by the formula (5):

[Formula 5]

In Chemical Formula 5,

Ar 2 is a substituted or unsubstituted C6 to C30 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group,

L 2 is a single bond, a substituted or unsubstituted C2 to C10 alkenylene group, a substituted or unsubstituted C2 to C10 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group, or a substituted or unsubstituted C2 to C30 hetero Arylene group,

m2 is 1,

n2 is an integer of any one of 0 to 3,

R 1 to R 7 are independently hydrogen, deuterium, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C2 to C30 heteroaryl group.
The method of claim 1,

Ar 1 and Ar 2 are independently substituted or unsubstituted imidazolyl group, substituted or unsubstituted triazolyl group, substituted or unsubstituted tetrazolyl group, substituted or unsubstituted carbazolyl group, substituted or unsubstituted Substituted oxadiazolyl group, substituted or unsubstituted oxtriazolyl group, substituted or unsubstituted thiatriazolyl group, 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 group, substituted or unsubstituted pyridazinyl group, substituted or unsubstituted fury Nyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoquinolinyl group, substituted or unsubstituted phthalazinyl group, substituted or unsubstituted naphpyridinyl group, substituted or unsubstituted quinoxalinyl group , A substituted or unsubstituted quinazolinyl group, a substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenanthrolinyl group, a substituted or unsubstituted phenazinyl group, or a combination thereof.
The method of claim 1,

Ar 1 and Ar 2 are independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted phenanthrenyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted fluorenyl group , Substituted or unsubstituted triphenylenyl group, substituted or unsubstituted spiro-fluorenyl group, substituted or unsubstituted terphenyl group, substituted or unsubstituted pyrenyl group, substituted or unsubstituted perrylenyl group, or Compound for an organic optoelectronic device that is a combination.
The method of claim 1,

Ar 1 and Ar 2 are independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted anthracenyl group, a substituted or unsubstituted phenanthryl group, a 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 Substituted triphenylenyl group, substituted or unsubstituted perenyl group, substituted or unsubstituted indenyl group, substituted or unsubstituted furanyl group, substituted or unsubstituted thiophenyl group, substituted or unsubstituted pyrrolyl group, substituted or Unsubstituted 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 oxadi Solyl 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 benzofuranyl group, substituted or unsubstituted benzothiophenyl group, substituted or unsubstituted benzimidazolyl group, substituted or unsubstituted indolyl group, substituted or unsubstituted quinolinyl group, substituted or unsubstituted isoqui Nolinyl group, substituted or unsubstituted quinazolinyl group, substituted or unsubstituted quinoxalinyl group, substituted or unsubstituted naphthyridinyl group, substituted or unsubstituted benzoxazinyl group, substituted or unsubstituted benzthiazinyl group, An organic substituted or unsubstituted acridinyl group, a substituted or unsubstituted phenazineyl group, a substituted or unsubstituted phenothiazineyl group, a substituted or unsubstituted phenoxazinyl group, or a combination thereof Compound for an electronic device.
The method of claim 1,

The compound for an organic optoelectronic device is a compound for an organic optoelectronic device that is triplet excitation energy (T1) 2.0 eV or more.
The method of claim 1,

The organic optoelectronic device, an organic optoelectronic device, an organic light emitting device, an organic solar cell, an organic transistor, an organic photoelectric drum, and a compound for an organic optoelectronic device that is selected from the group consisting of an organic memory device.
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 of the organic thin film layer is an organic light emitting device comprising the compound for an organic optoelectronic device according to claim 1.
The method of claim 10,

The organic thin film layer is 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.
The method of claim 11,

The compound for an organic optoelectronic device is an organic light emitting device which is contained in a hole transport layer or a hole injection layer.
The method of claim 11,

The compound for an organic optoelectronic device is included in the light emitting layer.
The method of claim 11,

The compound for an organic optoelectronic device is used as a phosphorescent or fluorescent host material in the light emitting layer.
A display device comprising the organic light emitting device of claim 10.