KR20140123460A - Compound for organic photoelectric device and organic photoelectric device including the same - Google Patents

Abstract

The present invention relates to a compound for an organic photoelectric device and to an organic photoelectric device including the same. An organic photoelectric device with improved life properties due to improved electrochemical and thermal stability and high luminous efficiency at a low driving voltage can be manufactured using a compound for an organic photoelectric device represented by chemical formula 1. The definition of chemical formula 1 is as described in the specification.

Description

Technical Field [0001] The present invention relates to a compound for organic photoelectric conversion device and an organic photoelectric device including the same. BACKGROUND OF THE INVENTION [0002]

To an organic photoelectric device capable of providing an organic photoelectric device excellent in lifetime, efficiency, electrochemical stability, and thermal stability, and an organic photoelectric device containing the same.

An organic photoelectric device refers to a device that requires charge exchange between an electrode and an organic material using holes or electrons.

Organic photovoltaic devices can be roughly classified into two types according to their operating principles as follows. First, an exciton is formed in an organic material layer by a photon introduced into an element from an external light source. The exciton is separated into an electron and a hole, and the electrons and holes are transferred to different electrodes to be used as a current source Type electronic device.

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

Examples of the organic photoelectric device include an organic light emitting device, an organic solar cell, an organic photo conductor drum, and an organic transistor, all of which are used for injecting or transporting holes, , Or a luminescent material.

Particularly, organic light emitting diodes (OLEDs) have been attracting attention in recent years as the demand for flat panel displays increases. In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy.

Such an organic light emitting device is a device that converts electric energy into light by applying an electric current to an organic light emitting material, and is usually composed of a structure in which a functional organic layer is interposed between an anode and a cathode. Here, in order to increase the efficiency and stability of the organic photoelectric device, the organic material layer may have a multi-layered structure composed of different materials. For example, the organic material layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected into the anode and electrons are injected into the organic layer through the cathode, and injected holes and electrons are recombined Energy excitons are formed. At this time, the exciton formed again moves to the ground state, and light having a specific wavelength is generated.

In recent years, it has been known that not only a fluorescent light emitting material but also a phosphorescent light emitting material can be used as a light emitting material of an organic photoelectric device. Such phosphorescence emission is a phenomenon in which electrons are transferred from a ground state to an excited state, The mechanism consists of a non-luminescent transition of a singlet exciton to a triplet exciton through intersystem crossing, followed by a luminescence of the triplet exciton transitioning to the ground state.

As described above, a material used as an organic material layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions.

Further, the light emitting material can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural color depending on the luminescent color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system can be used as a light emitting material in order to increase the light emitting efficiency and stability through the light emitting layer.

In order for the organic luminescent device to fully exhibit the above-described excellent characteristics, a host material and / or a dopant such as a hole injecting material, a hole transporting material, a luminescent material, an electron transporting material, an electron injecting material, The organic material layer for organic light emitting devices has not been sufficiently developed yet. Therefore, development of new materials has been continuously required. The necessity of developing such a material is the same in other organic photoelectric devices described above.

In addition, the low-molecular organic light-emitting device has good efficiency and long life performance because it is manufactured in the form of a thin film by a vacuum deposition method. The polymer organic light-emitting device uses an inkjet or spin coating method, There is an advantage that the large area is advantageous.

The low molecular weight organic light emitting devices and the polymer organic light emitting devices are attracting attention as next generation displays because they have advantages such as self light emission, high speed response, wide viewing angle, ultra-thin type, high image quality, durability, crystal display, it is a self-luminous type. It has good visibility even in the dark place or outside light, and it can reduce the thickness and weight to 1/3 of that of LCD without backlight.

In addition, the response speed is 1000 times faster than that of LCD, so it is possible to realize perfect video without residual image. Therefore, it is anticipated that it will be seen as an optimal display in accordance with the multimedia age in recent years. Based on these advantages, after the first development in the late 1980s, the technology has been rapidly developed 80 times and lifespan 100 times. And organic light-emitting device panels have been announced, and the size of the organic light-emitting device panel is rapidly increasing.

In order to increase the size, it is necessary to increase the luminous efficiency and the lifetime of the device. At this time, the luminous efficiency of the device should be such that the holes and electrons in the light emitting layer are smoothly coupled. However, since the electron mobility of an organic material is generally slower than the hole mobility, in order to efficiently bond holes and electrons in the light-emitting layer, an efficient electron transport layer is used to increase electron injection and mobility from the cathode, It should be able to block the movement of holes.

Further, in order to improve the lifetime, the material should be prevented from crystallizing due to joule heat generated when the device is driven. Therefore, it is necessary to develop organic compounds having excellent electron injection and mobility and high electrochemical stability.

A hole injecting and transporting role, an electron injecting and transporting role, and can function as a luminescent host together with an appropriate dopant.

To provide an organic photoelectric device excellent in lifetime, efficiency, driving voltage, electrochemical stability, and thermal stability.

In one aspect of the present invention, there is provided an organic photoelectric device compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, Ar is a substituted or unsubstituted triphenylenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted dibenzofuranyl group; Or a substituted or unsubstituted dibenzothiophenyl group; X is N, B or P; L ¹ and L ² are the same or different from each other and independently represent a single bond, a substituted or unsubstituted C2 to C10 alkenylene group, A substituted or unsubstituted C6 to C30 arylene group or a substituted or unsubstituted C2 to C30 heteroarylene group; n and m are the same as or different from each other, R ¹ to R ⁹ are the same or different and independently represent hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine group, a nitro group A substituted or unsubstituted 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, group , A substituted or unsubstituted C6 to C20 aryloxy group, a substituted or unsubstituted C3 to C40 silyloxy group, a substituted or unsubstituted C1 to C20 acyl group, a substituted or unsubstituted C2 to C20 alkoxycarbonyl group, A substituted or unsubstituted C2 to C20 acyloxy group, a substituted or unsubstituted C2 to C20 acyloxy group, a substituted or unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, a substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, A substituted or unsubstituted C1 to C20 alkylthiol group, a substituted or unsubstituted C6 to C20 arylthiol group, a substituted or unsubstituted C1 to C20 alkylthiol group, A substituted C1 to C20 heterocyclythiol group, a substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or a combination thereof.

The organic optoelectronic device compound may be represented by the following formula (2).

(2)

In Formula 2, Ar is a substituted or unsubstituted triphenylenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted dibenzofuranyl group; Or a substituted or unsubstituted dibenzothiophenyl group; X is N, B or P; L ¹ and L ² are the same or different from each other and independently represent a single bond, a substituted or unsubstituted C2 to C10 alkenylene group, A substituted or unsubstituted C6 to C30 arylene group or a substituted or unsubstituted C2 to C30 heteroarylene group; n and m are the same as or different from each other, R ¹ to R ⁹ are the same or different and independently represent hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine group, a nitro group A substituted or unsubstituted 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, group , A substituted or unsubstituted C6 to C20 aryloxy group, a substituted or unsubstituted C3 to C40 silyloxy group, a substituted or unsubstituted C1 to C20 acyl group, a substituted or unsubstituted C2 to C20 alkoxycarbonyl group, A substituted or unsubstituted C2 to C20 acyloxy group, a substituted or unsubstituted C2 to C20 acyloxy group, a substituted or unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, a substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, A substituted or unsubstituted C1 to C20 alkylthiol group, a substituted or unsubstituted C6 to C20 arylthiol group, a substituted or unsubstituted C1 to C20 alkylthiol group, A substituted C1 to C20 heterocyclythiol group, a substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or a combination thereof.

 The compound for organic photoelectric conversion may be represented by the following formula (3).

(3)

Wherein X is N, B or P, L ¹ and L ² are the same or different and independently represent a single bond, a substituted or unsubstituted C2 to C10 alkenylene group, a substituted or unsubstituted C2 to C10 alkenylene group, C10 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group or a substituted or unsubstituted C2 to C30 heteroarylene group, n and m are the same or different and independently represent an integer of 0 to 3 , R ¹ to R ⁹ are the same or different and independently represent hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine group, a nitro group, a carboxyl group, , A substituted or unsubstituted 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, C6 to C A substituted or unsubstituted C2 to C20 acyloxy group, a substituted or unsubstituted C1 to C20 acyl group, a substituted or unsubstituted C2 to C20 alkoxycarbonyl group, a substituted or unsubstituted C2 to C20 acyloxy group , A substituted or unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, a substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfa A substituted or unsubstituted C1 to C20 alkylthiol group, a substituted or unsubstituted C6 to C20 arylthiol group, a substituted or unsubstituted C1 to C20 heterocyclothiol A substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or a combination thereof.

The compound for organic photoelectric conversion may be represented by the following general formula (4).

[Chemical Formula 4]

Wherein X is N, B or P, L ¹ and L ² are the same or different and independently represent a single bond, a substituted or unsubstituted C2 to C10 alkenylene group, a substituted or unsubstituted C2 to C10 alkenylene group, C10 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group or a substituted or unsubstituted C2 to C30 heteroarylene group, n and m are the same or different and independently represent an integer of 0 to 3 , R ¹ to R ⁹ are the same or different and independently represent hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine group, a nitro group, a carboxyl group, , A substituted or unsubstituted 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, C6 to C A substituted or unsubstituted C2 to C20 acyloxy group, a substituted or unsubstituted C1 to C20 acyl group, a substituted or unsubstituted C2 to C20 alkoxycarbonyl group, a substituted or unsubstituted C2 to C20 acyloxy group , A substituted or unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, a substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfa A substituted or unsubstituted C1 to C20 alkylthiol group, a substituted or unsubstituted C6 to C20 arylthiol group, a substituted or unsubstituted C1 to C20 heterocyclothiol A substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or a combination thereof.

The compound for organic photoelectric conversion may be represented by the following general formula (5).

[Chemical Formula 5]

In Formula 5, X is N, B or P, L ¹ and L ² are the same or different and independently represent a single bond, a substituted or unsubstituted C2 to C10 alkenylene group, a substituted or unsubstituted C2 to C10 alkenylene group, C10 alkynylene group, a substituted or unsubstituted C6 to C30 arylene group or a substituted or unsubstituted C2 to C30 heteroarylene group, n and m are the same or different and independently represent an integer of 0 to 3 , R ¹ to R ⁹ are the same or different and independently represent hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine group, a nitro group, a carboxyl group, , A substituted or unsubstituted 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, C6 to C A substituted or unsubstituted C2 to C20 acyloxy group, a substituted or unsubstituted C1 to C20 acyl group, a substituted or unsubstituted C2 to C20 alkoxycarbonyl group, a substituted or unsubstituted C2 to C20 acyloxy group , A substituted or unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, a substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfa A substituted or unsubstituted C1 to C20 alkylthiol group, a substituted or unsubstituted C6 to C20 arylthiol group, a substituted or unsubstituted C1 to C20 heterocyclothiol A substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or a combination thereof.

The compound for organic photoelectric conversion may be represented by the following formula (6).

[Chemical Formula 6]

In Formula 6, X is N, B or P, L ¹ 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 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group, n is from 0 to a third any integer of, R ¹ to R ⁹ are the same or different, are independently hydrogen, deuterium, halogen A substituted or unsubstituted C1 to C20 amine group, a nitro group, a carboxyl group, a ferrocenyl group, a substituted or unsubstituted 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 aryloxy group, a substituted or unsubstituted C3 to C40 silyloxy group, Unsubstituted C1 to C20 A substituted or unsubstituted C2 to C20 alkoxycarbonyl group, a substituted or unsubstituted C2 to C20 acyloxy group, a substituted or unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group , A substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfamoylamino group, a substituted or unsubstituted C1 to C20 sulfonyl group, a substituted or unsubstituted C1 to C20 alkylthiol group , A substituted or unsubstituted C6 to C20 arylthiol group, a substituted or unsubstituted C1 to C20 heterocyclothiol group, a substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, It is a combination of these.

X may be N.

The organic optoelectronic device compound may be represented by one of the following formulas A-1 to A-95.

The compound for organic photoelectric conversion may be represented by one of the following formulas (B-1) to (B-6).

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

[Formula B-4] [Formula B-5] [Formula B-6]

The compound for an organic photoelectric device may be one that can be used as a hole transporting material or a hole injecting material of an organic light emitting device.

The compound for an organic photoelectric device may have a triplet excitation energy (T1) of 2.0 eV or more.

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

According to another aspect of the present invention, there is provided an organic light emitting device comprising a cathode, a cathode, and at least one organic thin film layer interposed between the anode and the cathode, wherein at least one of the organic thin film layers comprises And a compound represented by the following general formula (1).

The organic thin film layer may be selected from the group consisting of a light emitting layer, a hole transporting layer, a hole injecting layer, an electron transporting layer, an electron injecting layer, a hole blocking layer, and combinations thereof.

The compound for an organic photoelectric device may be contained in a hole transporting layer, a hole injecting layer, an electron transporting layer, or an electron injecting layer.

The compound for an organic photoelectric device may be included in the light emitting layer.

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

The compound for an organic photoelectric device may be one used as a fluorescent blue dopant material in the light emitting layer.

According to another aspect of the present invention, there is provided a display device including the organic light emitting element described above.

A compound having high hole or electron transporting property, film stability, thermal stability and high triplet excitation energy can be provided.

Such a compound can be used as a hole injecting / transporting material, a host material, or an electron injecting / transporting material of a light emitting layer. The organic photoelectric device using the organic electroluminescent device has excellent electrochemical and thermal stability, and has excellent lifetime characteristics, and can have a high luminous efficiency even at a low driving voltage.

1 to 5 are cross-sectional views illustrating various embodiments of an organic photoelectric device that can be manufactured using the compound for organic photoelectric conversion devices according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

As used herein, unless otherwise defined, at least one of the substituents or at least one hydrogen in the compound is substituted with one or more substituents selected from the group consisting of deuterium, a halogen group, a hydroxy group, an amino group, a substituted or unsubstituted C1 to C20 amine group, a nitro group, C1 to C10 alkyl groups such as a C3 to C40 silyl group, a C1 to C30 alkyl group, a C1 to C10 alkylsilyl group, a C3 to C30 cycloalkyl group, a C6 to C30 aryl group, a C1 to C20 alkoxy group, a fluoro group, A trifluoroalkyl group, or a cyano group.

 Means one to three heteroatoms selected from the group consisting of N, O, S and P in one functional group, and the remainder is carbon, unless otherwise defined.

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

As used herein, the term "alkyl group" means an aliphatic hydrocarbon group, unless otherwise defined. The alkyl group may be a "saturated alkyl group" meaning that it does not contain any alkene or alkyne groups. An alkyl group may be an "unsaturated alkyl group" meaning that it contains at least one alkenyl group or alkynyl group. "Alkenene group" means a functional group in which at least two carbon atoms are composed of at least one carbon-carbon double bond, and "alkyne group" means that at least two carbon atoms have at least one carbon- ≪ / RTI > The alkyl group, whether saturated or unsaturated, can be branched, straight chain or cyclic.

The alkyl group may be an alkyl group of C1 to C20. The alkyl group may be a C1 to C10 medium-sized alkyl group. The alkyl group may be a C1 to C6 lower alkyl group.

For example, the C1 to C4 alkyl groups may have 1 to 4 carbon atoms in the alkyl chain, i.e., the alkyl chain may be optionally substituted with one or more substituents selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, Indicating that they are selected from the group.

Typical examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, an ethenyl group, a propenyl group, a butenyl group, a cyclopropyl group, A pentyl group, a cyclohexyl group, and the like, which may be optionally substituted with one or more groups individually and independently selected.

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

An "aryl group" includes a monocyclic or fused ring polycyclic (i. E., A ring that divides adjacent pairs of carbon atoms) functional groups.

"Heteroaryl group" means that the aryl group contains 1 to 3 heteroatoms selected from the group consisting of N, O, S and P, and the remainder is carbon. When the heteroaryl group is a fused ring, it may contain 1 to 3 heteroatoms in each ring.

"Spiro structure" means a ring structure having one carbon as a point of contact. The spiro structure may also be used as a substituent comprising a spiro structure or a compound containing a spiro structure.

The compound for an organic photoelectric device according to an embodiment of the present invention may have a core structure containing a carbazolyl group and a fluorenyl group as substituents on N, B or P atoms.

The core structure may be used as a hole injecting material or a hole transporting material of an organic light emitting device because a carbazolyl group having excellent hole properties is bonded to N, B, or P atoms.

At least one of the substituents bonded to the core may be a substituent having excellent electron characteristics. Therefore, the compound can enhance the electronic characteristics of the core structure having excellent hole characteristics, thereby satisfying the requirements of the light emitting layer. More specifically, it can be used as a host material for a light emitting layer.

The hole property refers to a property of facilitating the injection of holes formed in the anode into the light emitting layer and the movement of the hole in the light emitting layer because of the conduction characteristics along the HOMO level.

Further, the electron characteristic means a property of facilitating the injection of electrons formed in the cathode into the light emitting layer and the movement in the light emitting layer due to conduction characteristics along the LUMO level.

In addition, the compound for organic optoelectronic devices can be a compound having various energy bandgaps by introducing various substituents to the substituents substituted in the core and core.

By using a compound having an appropriate energy level according to the substituent of the compound in an organic photoelectric device, the hole transporting ability or the electron transporting ability is enhanced to have an excellent effect in terms of efficiency and drive voltage, excellent electrochemical and thermal stability, The lifetime characteristics can be improved when the device is driven.

According to one embodiment of the present invention, there is provided an organic photoelectric device compound represented by Formula 1 below.

[Chemical Formula 1]

In Formula 1, Ar is a substituted or unsubstituted triphenylenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted dibenzofuranyl group; Or a substituted or unsubstituted dibenzothiophenyl group; X is N, B or P; L ¹ and L ² are the same or different from each other and independently represent a single bond, a substituted or unsubstituted C2 to C10 alkenylene group, A substituted or unsubstituted C6 to C30 arylene group or a substituted or unsubstituted C2 to C30 heteroarylene group; n and m are the same as or different from each other, R ¹ to R ⁹ are the same or different and independently represent hydrogen, deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine group, a nitro group A substituted or unsubstituted 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, group , A substituted or unsubstituted C6 to C20 aryloxy group, a substituted or unsubstituted C3 to C40 silyloxy group, a substituted or unsubstituted C1 to C20 acyl group, a substituted or unsubstituted C2 to C20 alkoxycarbonyl group, A substituted or unsubstituted C2 to C20 acyloxy group, a substituted or unsubstituted C2 to C20 acyloxy group, a substituted or unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group, a substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, A substituted or unsubstituted C1 to C20 alkylthiol group, a substituted or unsubstituted C6 to C20 arylthiol group, a substituted or unsubstituted C1 to C20 alkylthiol group, A substituted C1 to C20 heterocyclythiol group, a substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, or a combination thereof.

By appropriately combining the Ar and R ¹ to R ⁹ substituents, compounds for organic photoelectric devices having hole or electron characteristics, film stability, thermal stability, and high triplet excitation energy (T1) can be produced. In addition, by appropriately combining the substituents, it becomes possible to produce a compound having a structure that is excellent in thermal stability or resistance to oxidation.

The structure of the compound represented by Formula 1 is asymmetric bipolar, and the structure of the asymmetric bipolar characteristic can improve the luminous efficiency and performance of the device by improving the hole and electron transfer capability.

In addition, in the above structure, the structure of the compound can be bulk produced by controlling the substituent, thereby lowering the crystallinity. If the crystallinity of the compound is lowered, the lifetime of the device may be prolonged.

In the above formula (1), Ar can not be a carbazolyl group. In other words, two or more carbazolyl groups can not be present as a substituent of X, which is the core atom of Formula 1 above. This is because the crystallinity of the compound may increase due to the increase of the symmetry.

The length of the compound can be controlled by controlling the above-mentioned L ¹ , L ² , n and m, and thereby the pi conjugation length of the whole compound can be controlled. As a result, the triplet energy bandgap can be controlled so that it can be very usefully applied to the light emitting layer of the organic photoelectric device as a phosphorescent host. Also, when a heteroaryl group is introduced as the substituent, bipolar characteristics are realized in the molecular structure, which can exhibit high efficiency as a phosphorescent host.

In the above formula (1), since the asymmetry of the whole molecule is increased due to the presence of the fluorenyl group as a substituent of the core, the recrystallization of the compound is not easily caused and the effect of exhibiting long life and high efficiency when used in the hole injection and hole transport layer of the organic electroluminescent device have.

Ar is a substituted or unsubstituted triphenylenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted dibenzofuranyl group; Or a substituted or unsubstituted dibenzothiophenyl group.

Since the triphenylenyl group has a bulk structure and causes a resonance effect, the triphenylenyl group has an effect of suppressing side reactions that may occur in a solid state, thereby increasing the performance of the organic light emitting device.

It can also have the effect of making the compound bulk, lowering the crystallinity and increasing the lifetime.

Unlike other substituents, the triphenylenyl group has a wide band gap and a large triplet excitation energy. Therefore, it binds to carbazole and does not decrease the bandgap or triplet excitation energy of the compound.

The dibenzofuranyl group or the dibenzothiophenyl group exhibits hole transporting property, and when it is asymmetrically bonded as in the above formula (1), it contains an electron-withdrawing heteroaromatic ring to exhibit an asymmetric bipolar characteristic as a whole molecule.

The "substitution" in the definition of the "substituted or unsubstituted" means that at least one of the hydrogen atoms of the substituents is a group selected from the group consisting of deuterium, a halogen group, a cyano group, a hydroxyl group, an amino group, a substituted or unsubstituted C1 to C20 amine group, , A substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C1 to C20 alkoxy group, a substituted or unsubstituted C3 to C40 silyl group, and combinations thereof.

In the case of the "substituted" structure as compared with the basic compound structure described above, the electro-optical property for optimizing the performance as a material for an organic photoelectric device while maintaining the basic characteristics of the compound, .

The compound for organic photoelectric conversion may be represented by the following formula (2).

(2)

The description of Formula 2 is almost the same as that of Formula 1 described above, but there is a difference in that there is a limitation of the bonding position. If the binding position is satisfied, it may be advantageous in terms of practical synthesis. Other explanations are omitted in FIG.

The compound for organic photoelectric conversion may be represented by the following formula (3).

(3)

In the structure of Formula 3, the substituent of Ar in the structure of Formula 1 is limited to a dibenzofuranyl group. Such a structure has an advantage that the thermal stability of the material is improved and the half life time of the device is remarkably increased.

The compound for organic photoelectric conversion may be represented by the following formula (4).

[Chemical Formula 4]

In the structure of Formula 4, the substituent of Ar in the structure of Formula 1 is limited to a dibenzothiophenyl group. Such a structure has an advantage that the thermal stability of the material is improved and the half life time of the device is remarkably increased.

The compound for organic photoelectric conversion may be represented by the following formula (5).

[Chemical Formula 5]

The structure of Formula 5 is such that the substituent of Ar in the structure of Formula 1 is limited to a triphenylenyl group. This structure not only increases the thermal stability of the material but also has an advantage that it can be used as a hole transporting and injecting layer of a phosphorescent light emitting material because the T1 energy of triphenylene is wide.

The compound for organic photoelectric conversion may be represented by the following formula (6).

[Chemical Formula 6]

In Formula 6, X is N, B or P, L ¹ 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 aryl group or a substituted or unsubstituted C2 to C30 heteroaryl group, n is from 0 to a third any integer of, R ¹ to R ⁹ are the same or different, are independently hydrogen, deuterium, halogen A substituted or unsubstituted C1 to C20 amine group, a nitro group, a carboxyl group, a ferrocenyl group, a substituted or unsubstituted 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 aryloxy group, a substituted or unsubstituted C3 to C40 silyloxy group, Unsubstituted C1 to C20 A substituted or unsubstituted C2 to C20 alkoxycarbonyl group, a substituted or unsubstituted C2 to C20 acyloxy group, a substituted or unsubstituted C2 to C20 acylamino group, a substituted or unsubstituted C2 to C20 alkoxycarbonylamino group , A substituted or unsubstituted C7 to C20 aryloxycarbonylamino group, a substituted or unsubstituted C1 to C20 sulfamoylamino group, a substituted or unsubstituted C1 to C20 sulfonyl group, a substituted or unsubstituted C1 to C20 alkylthiol group , A substituted or unsubstituted C6 to C20 arylthiol group, a substituted or unsubstituted C1 to C20 heterocyclothiol group, a substituted or unsubstituted C1 to C20 ureide group, a substituted or unsubstituted C3 to C40 silyl group, It is a combination of these.

In formula (6), L ¹ may be phenylene, and n may be 1.

When an organic photoelectric device (for example, an organic light emitting device) is manufactured using the structure as shown in Formula 6, lifetime characteristics of the device can be excellent.

In the case of the compound for the organic photoelectric device, the thermal stability is significantly increased by the phenyl group substituted at 9 and 9 'position of the fluorene and the biphenyl group substituted by X, and the material is easily decomposed by heat even when the deposition rate is increased There are properties that do not.

In the general formulas (1) to (6), X may be N. When X is N, it becomes a core type of tertiary amine, and the hole properties of the whole compound can be further improved.

The organic optoelectronic device compound may be represented by any one of the following formulas A-1 to A-95. The following structure has an advantage of exhibiting excellent long hole lifetime and high efficiency when used in the hole injection and hole transport layer of an organic electroluminescent device because of excellent hole transportability of the carbazolyl group and excellent asymmetry of the molecule due to its excellent thin film characteristics and thermal stability have.

The compound for organic photoelectric conversion may be represented by one of the following formulas (B-1) to (B-6).

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

[Formula B-4] [Formula B-5] [Formula B-6]

When an organic photoelectric device (for example, an organic light emitting device) is manufactured using the above structure, lifetime characteristics of the manufactured device can be excellent.

When the compound for an organic photoelectric device according to one embodiment of the present invention is used in an electron blocking layer (or hole transporting layer) of an organic light emitting device, the electron blocking property, which is one of the important characteristics required at this time, The electron blocking property tends to be lowered by the functional group. For this reason, in order to be used as an electron blocking layer, it is preferable that the compound does not contain a functional group having an electron characteristic. Examples of the functional group having an electron characteristic include benzoimidazole, pyridine, pyrazine, pyrimidine, triazine, quinoline, isoquinoline and the like. However, this is an explanation that is limited when it is used as an electron blocking layer or a hole transporting layer (or a hole injecting layer).

In the case where the compound according to one embodiment of the present invention requires both the electronic property and the hole property, it is effective to improve the lifetime of the organic light emitting device and reduce the driving voltage by introducing the functional group having the electron characteristic.

The organic optoelectronic device compound according to an embodiment of the present invention has a maximum emission wavelength in a range of about 320 to 500 nm, a triplet excitation energy (T1) in a range of 2.0 eV or more, more specifically 2.0 to 4.0 eV The charge of a host having a high triplet excitation energy can be transferred to the dopant to increase the luminous efficiency of the dopant and freely adjust the HOMO and LUMO energy levels of the material to lower the driving voltage It can be very useful as a host material or a charge transport material.

In addition, since the compound for organic optoelectronic devices has a photoactive and electrical activity, it can be used as a nonlinear optical material, an electrode material, a coloring material, an optical switch, a sensor, a module, a waveguide, an organic transistor, it can be very usefully applied to materials such as a membrane.

The compound for organic optoelectronic devices including the above compound has a glass transition temperature of 90 ° C or higher and a thermal decomposition temperature of 400 ° C or higher, which is excellent in thermal stability. As a result, it is possible to realize a highly efficient organic photoelectric device.

The compound for organic optoelectronic devices including the above compound can play a role of luminescence, electron injection and / or transport, and can function as a luminescent host together with an appropriate dopant. That is, the compound for organic optoelectronic devices can be used as a phosphorescent or fluorescent host material, a blue luminescent dopant material, or an electron transporting material.

The compound for an organic photoelectric device according to an embodiment of the present invention can be used in an organic thin film layer to improve lifetime characteristics, efficiency characteristics, electrochemical stability and thermal stability of an organic photoelectric device, and lower a driving voltage.

Accordingly, one embodiment of the present invention provides an organic photoelectric device including the compound for an organic photoelectric device. Here, the organic photovoltaic elements include organic light emitting devices, organic solar cells, organic transistors, organic photoconductive drums, and organic memory devices. In particular, in the case of an organic solar cell, the compound for an organic photoelectric device according to an embodiment of the present invention is included in an electrode or an electrode buffer layer to increase quantum efficiency. In the case of an organic transistor, an electrode material in a gate, a source- Can be used.

Hereinafter, the organic photoelectric device will be described in detail.

Another embodiment of the present invention is an organic light emitting device comprising a cathode, a cathode, and at least one or more organic thin film layers interposed between the anode and the cathode, wherein at least one of the organic thin film layers is an organic thin film And a compound for an organic photoelectric device according to the present invention.

The organic thin film layer that can include the organic photoelectric conversion layer 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, At least one of the layers includes a compound for an organic photoelectric device according to the present invention. In particular, the hole transport layer or the hole injection layer may include the organic photoelectric device compound according to one embodiment of the present invention. When the compound for an organic photoelectric device is contained in the light emitting layer, the compound for organic photoelectric conversion 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 sectional views of an organic light emitting device including a compound for an organic photoelectric device according to an embodiment of the present invention.

1 to 5, organic photoelectric devices 100, 200, 300, 400, and 500 according to an embodiment of the present invention include an anode 120, a cathode 110, And a structure including at least one organic thin film layer (105).

The anode 120 includes a cathode material. As the anode material, a material having a large work function is preferably used to facilitate injection of holes 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 zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide ), And combinations of metals and oxides such as ZnO and Al or SnO ₂ and Sb, and poly (3-methylthiophene), poly [3,4- (ethylene- 2-dioxythiophene] (PEDT), conductive polymers such as polypyrrole and polyaniline, but are not limited thereto. Preferably, a transparent electrode including ITO (indium tin oxide) may be used as the anode.

The cathode 110 includes a cathode material, and the anode 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 and the like, , LiO ₂ / Al, LiF / Ca, LiF / Al, and BaF ₂ / Ca. However, the present invention is not limited thereto. Preferably, a metal electrode such as aluminum or the like may be used for the negative electrode.

1 illustrates an organic photoelectric device 100 in which only a light emitting layer 130 is present as an organic thin film layer 105. The organic thin film layer 105 may exist only in the light emitting layer 130. FIG.

2 shows a two-layer type organic photoelectric device 200 in which a light emitting layer 230 including an electron transporting layer and a hole transporting layer 140 are present as an organic thin film layer 105, Similarly, the organic thin film layer 105 may be of a two-layer type including a light emitting layer 230 and a hole transporting 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 the bonding property with a transparent electrode such as ITO and the hole transporting property.

3 is a three-layer organic photoelectric device 300 in which an electron transport layer 150, a light emitting layer 130 and a hole transport layer 140 are present as an organic thin film layer 105. The organic thin film layer 105, The emissive layer 130 is in the form of an independent layer and has a form in which a film having excellent electron transportability and hole transportability (the electron transport layer 150 and the hole transport layer 140) is stacked as a separate layer.

4, a four-layer type organic photoelectric device 400 having an electron injection layer 160, a light emitting layer 130, a hole transport layer 140, and a hole injection layer 170 is formed as an organic thin film layer 105. And the hole injection layer 170 can improve the bonding property with ITO used as the anode.

5, the organic thin film layer 105 has different functions such as an electron injection layer 160, an electron transport layer 150, a light emitting layer 130, a hole transport layer 140, and a hole injection layer 170 Layer type organic photoelectric device 500. The organic photoelectric device 500 is effective for lowering the voltage by forming the electron injection layer 160 separately.

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, the hole injection layer 170, and the organic thin film layer 105, And combinations thereof. The organic electroluminescent device according to any one of claims 1 to 3, In this case, the organic photoelectric conversion layer compound may be used for the electron transport layer 150 or the electron transport layer 150 including the electron injection layer 160. Among them, a hole blocking layer (not shown) is included in the electron transport layer It is not necessary to separately form the organic electroluminescent device, and it is possible to provide an organic electrooptic device of a more simplified structure.

When the compound for organic photoelectric conversion is contained in the light emitting layers 130 and 230, the compound for organic photoelectric conversion may be included as a phosphorescent or fluorescent host, or may be included as a fluorescent blue dopant.

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

According to another embodiment of the present invention, there is provided a display device including the organic photoelectric device.

Hereinafter, specific embodiments of the present invention will be described. However, the embodiments described below are only intended to illustrate or explain the present invention, and thus the present invention should not be limited thereto.

( For organic optoelectronic devices  Preparation of compounds <

Synthesis of intermediates

Synthesis of intermediate M-1

[Reaction Scheme 1]

A mixture of 50 g (155.18 mmol) of 3-bromo-9-phenyl-9H-carbazole and 3.41 g (4.65 mmol) of Pd (dppf) Cl ₂ , ) 51.32 g (201.8 mmol) of bis (pinacolato diboron) and 45.8 g (465.5 mmol) of potassium acetate are dissolved in 520 ml of 1,4-dioxane.

The reaction was refluxed under nitrogen atmosphere for 12 hours, and extracted three times with dichloromethane and distilled water. The extract was dried with magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure.

The product was purified by silica gel column chromatography with n-hexane / dichloromethane (7: 3 by volume) to obtain 43 g of intermediate M-1 as a white solid (yield 75% ).

LC-Mass (calculated: 369.19 g / mol, measured: M + l = 370 g / mol)

Synthesis of intermediate M-2

[Reaction Scheme 2]

(108.3 mmol) of Intermediate M-1, 30.6 g (108.3 mmol) of 1-bromo-4-iodobenzene and 1.25 g (1.08 mmol) of tetrakistriphenylphosphine palladium And the solution was dissolved in 270 ml of toluene and 135 ml of ethanol under a nitrogen atmosphere, 135 ml of an aqueous solution obtained by dissolving 31.9 g (58.9 mmol) of potassium carbonate was added, and the mixture was refluxed for 12 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate. The extract was dried with magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure.

The product was purified by silica gel column chromatography with n-hexane / dichloromethane (7: 3 by volume) to give 35 g (81% yield) of intermediate compound M-2 as a white solid .

LC-Mass (theory: 398.29 g / mol, measured: M + 1 = 399 g / mol)

Synthesis of intermediate M-3

[Reaction Scheme 3]

10 g (59.5 mmol) of dibenzofuran was added to a 2-necked round-bottomed flask heated and dried under vacuum, and 119 mL of anhydrous tetrahydrofuran was added to dissolve the solution. The solution was cooled to -40 ° C and stirred.

Thereto was slowly added 26 mL of 2.5 M n-butyllithium (in hexane, 65.5 mmol), followed by stirring at room temperature under a nitrogen atmosphere for 5 hours. After the reaction solution was cooled to -78 ° C, 22.4 g (119 mmol) of 1,2-dibromoethane dissolved in 10 mL of anhydrous tetrahydrofuran was slowly added thereto, followed by stirring at room temperature for 5 hours.

After completion of the reaction, the solution was concentrated under reduced pressure to remove the solvent. The solvent was then extracted with distilled water and dichloromethane. The extract was dried with magnesium sulphate, filtered and the filtrate was concentrated under reduced pressure. The reaction solution was recrystallized with n-hexane to obtain 11 g (yield 75%) of intermediate compound M-3 as a white solid.

GC-Mass (calculated 245.97 g / mol, measured: 246 g / mol)

Synthesis of intermediate M-4

[Reaction Scheme 4]

10 g (54.3 mmol) of dibenzothiophene was added to a 2-necked round-bottomed flask heated and dried under vacuum, 120 mL of anhydrous tetrahydrofuran was added to dissolve the solution, and the solution was cooled to -40 ° C and stirred.

24 ml of 2.5 M n-butyllithium (in hexane, 59.7 mmol) was slowly added thereto, followed by stirring at room temperature under a nitrogen atmosphere for 5 hours. After the reaction solution was cooled to -78 ° C, 20.4 g (108.6 mmol) of 1,2-dibromoethane dissolved in 10 mL of anhydrous tetrahydrofuran was slowly added thereto, followed by stirring at room temperature for 5 hours.

After completion of the reaction, the solution was concentrated under reduced pressure to remove the solvent, followed by extraction with distilled water and dichloromethane. The extract was dried with magnesium sulfite, filtered, and the filtrate was concentrated under reduced pressure. The reaction solution was recrystallized from n-hexane to obtain 11 g (yield 77%) of intermediate compound M-4 as a white solid.

GC-Mass (theory: 261.95 g / mol, measured: 262 g / mol)

Synthesis of intermediate M-5

[Reaction Scheme 5]

 (94.4 mmol) of 4-dibenzofuranboronic acid, 28 g (99.2 mmol) of 1-bromo-4-iodobenzene and 1.08 g (0.94 mmol) of tetrakistriphenylphosphine palladium were placed in a flask (240 ml) and ethanol (120 ml) under nitrogen atmosphere, 120 ml of an aqueous solution containing 28 g (188.8 mmol) of potassium carbonate was added, and the mixture was refluxed with stirring for 12 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate. The extract was dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (9: 1 by volume) to give 27 g (yield 89%) of intermediate compound M-5 as a white solid.

LC-Mass (theory: 322.00 g / mol, measured: M + 1 = 323 g / mol)

Synthesis of intermediate M-6

[Reaction Scheme 6]

(87.69 mmol) of 4-dibenzothiophene boronic acid, 27.3 g (96.46 mmol) of 1-bromo-4-iodobenzene and 1.01 g (0.88 mmol) of tetrakistriphenylphosphine palladium were placed in a flask, , 110 ml of an aqueous solution obtained by dissolving 25.8 g (175.4 mmol) of potassium carbonate in 120 ml of toluene and 110 ml of ethanol was added, and the mixture was refluxed for 12 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate. The extract was dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (9: 1 by volume) to give 25 g (83% yield) of intermediate compound M-6 as a white solid.

LC-Mass (theory: 337.98 g / mol, measured: M + 1 = 338 g / mol)

Synthesis of intermediate M-7

[Reaction Scheme 7]

30 g (178.4 mmol) of dibenzofuran was added to a round bottom flask and dissolved in 270 g of acetic acid. Then, 29 g (181.5 mmol) of bromine dissolved in 6 g of acetic acid at 50 ° C was slowly added for 4 hours. The reaction solution is further stirred at 50 캜 for 8 hours, cooled, and reacted with distilled water. The orange solid was dissolved in dichloromethane, washed with an aqueous sodium thiosulfate solution, the organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure.

The product was recrystallized from dichloromethane / n-hexane (1: 3 by volume) to obtain 10.1 g (yield: 23%) of intermediate compound M-7 as a white solid.

GC-Mass (calculated 245.97 g / mol, measured: 246 g / mol)

Synthesis of intermediate M-8

[Reaction Scheme 8]

30 g (162.8 mmol) of dibenzothiophene was added to a round bottom flask and dissolved in 2 L of chloroform. Then, 27.3 g (170.9 mmol) of bromine was added slowly at room temperature for 6 hours. The reaction solution is further stirred at 40 DEG C for 12 hours, cooled, and extracted with an aqueous sodium thiosulfite solution. The organic layer was dried over magnesium sulfate, filtered, and the filtrate was concentrated under reduced pressure.

The product was recrystallized from ethylacetate / n-hexane (1: 3 by volume) to obtain 15.4 g (yield 36%) of intermediate compound M-8 as a white solid.

GC-Mass (theory: 261.95 g / mol, measured: 262 g / mol)

Synthesis of intermediate M-9

[Reaction Scheme 9]

(127.9 mmol) of 4-chlorophenylboronic acid, 30.0 g (121.5 mmol) of Intermediate M-7 and 1.48 g (1.28 mmol) of tetrakistriphenylphosphine palladium were placed in a flask and 320 ml of toluene and 160 ml of ethanol After dissolving, 160 ml of an aqueous solution of 37.7 g (255.8 mmol) of potassium carbonate was added and the mixture was refluxed for 12 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate, and the extract was dried with magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (9: 1 by volume) to give 28.1 g (83% yield) of intermediate compound M-9 as a white solid.

LC-Mass (theoretical value: 278.05 g / mol, measured: M + 1 = 279 g / mol)

Synthesis of intermediate M-10

[Reaction Scheme 10]

(127.9 mmol) of 4-chlorophenylboronic acid, 32.0 g (121.5 mmol) of Intermediate M-8 and 1.48 g (1.28 mmol) of tetrakistriphenylphosphine palladium were placed in a flask and 320 ml of toluene and 160 ml of ethanol After dissolving, 160 ml of an aqueous solution of 37.7 g (255.8 mmol) of potassium carbonate was added and the mixture was refluxed for 12 hours.

After completion of the reaction, the reaction mixture was extracted with ethyl acetate, and the extract was dried with magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (9: 1 by volume) to give 30.4 g (85% yield) of intermediate compound M-9 as a white solid.

LC-Mass (theory: 294.03 g / mol, measurement: M + 1 = 295 g / mol)

Synthesis of intermediate M-11

[Reaction Scheme 11]

A mixture of 30 g (75.3 mmol) of Intermediate M-2, 18.92 g (90.39 mmol) of 2-amino-9,9'-dimethylfluorene, 26.06 g (271.16 mmol) of sodium t-butoxide, g (2.26 mmol) were dissolved in 600 ml of toluene, 1.3 g (2.26 mmol) of Pd (dba) ₂ was added, and the mixture was refluxed under nitrogen atmosphere for 12 hours.

After completion of the reaction, the reaction mixture was extracted with toluene and distilled water. The organic layer was dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (1: 1 by volume) and then recrystallized in a methylene chloride / n-hexane mixed solvent to obtain 30.9 g of intermediate compound M-11 as a white solid 78%).

LC-Mass (calculated: 526.24 g / mol, measured: M + 1 = 527.24 g / mol)

Synthesis of intermediate M-12

[Reaction Scheme 12]

30.06 g (75.3 mmol) of Intermediate M-2, 15.29 g (90.39 mmol) of 4-aminobiphenyl, 26.06 g (271.16 mmol) of sodium t-butoxide and 0.46 g (2.26 mmol) of tri- And 1.3 g (2.26 mmol) of Pd (dba) ₂ were added thereto, followed by stirring under reflux in a nitrogen atmosphere for 12 hours.

After completion of the reaction, the reaction mixture was extracted with toluene and distilled water. The organic layer was dried over magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with n-hexane / dichloromethane (1: 1 by volume) and then recrystallized in a methylene chloride / n-hexane mixed solvent to obtain 28.4 g of intermediate compound M-12 as a white solid 77.5%).

LC-Mass (calculated: 486.21 g / mol, measured: M + 1 = 487.21 g / mol)

Example  1: Compound A- 1 of  Produce

[Reaction Scheme 13]

(5.6 g, 18.23 mmol), 8.0 g (15.19 mmol) of Intermediate M-11, 5.26 g (54.68 mmol) of sodium t-butoxide and 0.09 g (0.46 mmol) of tri- Is dissolved in 200 ml of toluene, 0.26 g (0.46 mmol) of Pd (dba) ₂ is added, and the mixture is refluxed under nitrogen atmosphere for 12 hours.

After completion of the reaction, the reaction mixture was extracted with toluene and distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with normal hexane / dichloromethane (1: 1 by volume) and recrystallized in a methylene chloride / ethyl acetate mixed solvent to obtain 6.88 g (yield: 60.1%) of the desired compound A-1 as a white solid .

LC-Mass (theory: 752.32 g / mol, measured: M + 1 = 753.32 g / mol)

Example  2: Preparation of Compound A-2

[Reaction Scheme 14]

A mixture of 4.13 g (16.71 mmol) of 4-bromodibenzofurane, 8.0 g (15.19 mmol) of Intermediate M-11, 4.82 g (50.13 mmol) of sodium t-butoxide and 0.09 g (0.46 mmol) Is dissolved in 200 ml of toluene, 0.26 g (0.46 mmol) of Pd (dba) 2 is added, and the mixture is refluxed under nitrogen atmosphere for 12 hours.

After completion of the reaction, the reaction mixture was extracted with toluene and distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with normal hexane / dichloromethane (1: 1 by volume) to obtain 9.0 g (yield 85.5%) of the object compound A-2 as a white solid.

LC-Mass (calculated: 692.28 g / mol, measured: M + 1 = 693.28 g / mol)

Example  3: Preparation of Compound A-3

[Reaction Scheme 15]

A mixture of 4.4 g (16.71 mmol) of 4-bromodibenzothiophene, 8.0 g (15.19 mmol) of Intermediate M-11, 4.82 g (50.13 mmol) of sodium t- butoxide and 0.09 g ) Were dissolved in 200 ml of toluene, 0.26 g (0.46 mmol) of Pd (dba) ₂ was added, and the mixture was refluxed under nitrogen atmosphere for 12 hours.

After completion of the reaction, the reaction mixture was extracted with toluene and distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with normal hexane / dichloromethane (1: 1 by volume) to obtain 9.0 g (83.58% yield) of target compound A-3 as a white solid.

LC-Mass (theory: 708.91 g / mol, measurement: M + 1 = 709.91 g / mol)

Example  4: Preparation of Compound A-4

[Reaction Scheme 16]

A mixture of 4.13 g (16.71 mmol) of 2-bromodibenzofuran and 8.0 g (15.19 mmol) of Intermediate M-11, 4.82 g (50.13 mmol) of sodium t- butoxide and 0.09 g (0.46 mmol) of tri- Is dissolved in 200 ml of toluene, 0.26 g (0.46 mmol) of Pd (dba) ₂ is added, and the mixture is refluxed under nitrogen atmosphere for 12 hours.

After completion of the reaction, the reaction mixture was extracted with toluene and distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with normal hexane / dichloromethane (1: 1 by volume) to obtain 8.7 g (yield 82.6%) of the target compound A-4 as a white solid.

LC-Mass (calculated: 692.28 g / mol, measured: M + 1 = 693.28 g / mol)

Example  5: Preparation of Compound A-5

[Reaction Scheme 17]

A mixture of 4.4 g (16.71 mmol) of 2-bromodibenzothiophene, 8.0 g (15.19 mmol) of Intermediate M-11, 4.82 g (50.13 mmol) of sodium t-butoxide and 0.09 g ) Were dissolved in 200 ml of toluene, 0.26 g (0.46 mmol) of Pd (dba) ₂ was added, and the mixture was refluxed under nitrogen atmosphere for 12 hours.

After completion of the reaction, the reaction mixture was extracted with toluene and distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with normal hexane / dichloromethane (1: 1 by volume) to give 8.4 g (yield 78%) of the target compound A-5 as a white solid.

LC-Mass (theory: 708.91 g / mol, measurement: M + 1 = 709.91 g / mol)

Example  6: Preparation of Compound A-6

[Reaction Scheme 18]

To a mixture of 5.4 g (16.71 mmol) of Intermediate M-5, 8.0 g (15.19 mmol) of Intermediate M-11, 4.82 g (50.13 mmol) of sodium t- butoxide and 0.09 g (0.46 mmol) of Tri- ml, 0.26 g (0.46 mmol) of Pd (dba) ₂ was added thereto, and the mixture was stirred under reflux for 12 hours under a nitrogen atmosphere.

After completion of the reaction, the reaction mixture was extracted with toluene and distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with normal hexane / dichloromethane (4: 1 by volume) to give 9.2 g (yield 78.7%) of the target compound A-6 as a white solid.

LC-Mass (theory: 768.31 g / mol, measured: M + 1 = 769.31 g / mol)

Example  7: Preparation of Compound A-7

[Reaction Scheme 19]

A solution of 5.67 g (16.71 mmol) of intermediate M-6, 8.0 g (15.19 mmol) of intermediate M-11, 4.82 g (50.13 mmol) of sodium t- 300 ml, and 0.26 g (0.46 mmol) of Pd (dba) ₂ was added thereto, followed by stirring under reflux for 12 hours under a nitrogen atmosphere.

After completion of the reaction, the reaction mixture was extracted with toluene and distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with normal hexane / dichloromethane (4: 1 by volume) to obtain 9.5 g (yield 79.6%) of the target compound A-7 as a white solid.

LC-Mass (theory: 784.29 g / mol, measured: M + 1 = 785.29 g / mol)

Example  8: Preparation of Compound A-8

[Reaction Scheme 20]

(4.66 g, 16.71 mmol), Intermediate M-11 (8.0 g, 15.19 mmol), sodium tert-butoxide (4.82 g, 50.13 mmol) and tri- tert- ml, 0.26 g (0.46 mmol) of Pd (dba) ₂ was added thereto, and the mixture was stirred under reflux for 12 hours under a nitrogen atmosphere.

After completion of the reaction, the reaction mixture was extracted with toluene and distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with normal hexane / dichloromethane (4: 1 by volume) to obtain 9.0 g (yield 77%) of the target compound A-8 as a white solid.

LC-Mass (theory: 768.31 g / mol, measured: M + 1 = 769.31 g / mol)

Example  9: Preparation of Compound A-9

[Reaction Scheme 21]

(4.93 g, 16.71 mmol), Intermediate M-11 (8.0 g, 15.19 mmol), sodium tert-butoxide (4.82 g, 50.13 mmol) and tri- tert- ml, 0.26 g (0.46 mmol) of Pd (dba) ₂ was added thereto, and the mixture was stirred under reflux for 12 hours under a nitrogen atmosphere.

After completion of the reaction, the reaction mixture was extracted with toluene and distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was purified by silica gel column chromatography with normal hexane / dichloromethane (4: 1 by volume) to obtain 9.4 g (yield 78.8%) of the target compound A-9 as a white solid.

LC-Mass (theory: 784.29 g / mol, measured: M + 1 = 785.29 g / mol)

Example Name -1: Preparation of compound B-1

[Reaction Scheme 22]

A mixture of 6 g (15.1 mmol) of 2-bromo-9,9'-diphenylfluorene and 6.52 g (13.4 mmol) of intermediate M-12, 4.82 g (50.13 mmol) of sodium tert- 0.09 g (0.46 mmol) of pyridine are dissolved in 300 ml of toluene, 0.26 g (0.46 mmol) of Pd (dba) ₂ is added, and the mixture is refluxed under nitrogen atmosphere for 12 hours.

After completion of the reaction, the reaction mixture was extracted with toluene and distilled water. The organic layer was dried over anhydrous magnesium sulfate, filtered and the filtrate was concentrated under reduced pressure. The product was recrystallized twice in methylene chloride / acetone solvent to obtain 9.5 g (yield: 88.7%) of the target compound B-1 as a white solid.

LC-Mass (theoretical value: 802.33 g / mol, measurement: M + 1 = 803.33 g / mol)

(Production of organic light emitting device)

Example  10

Glass substrate coated with ITO (Indium tin oxide) thin film with thickness of 1500Å was washed with distilled water ultrasonic wave. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, dried, and transferred to a plasma cleaner. Then, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transferred to a vacuum deposition machine. The prepared ITO transparent electrode was used as an anode to form a 4,4'-bis [N- [4- {N, N-bis (3-methylphenyl) amino} -phenyl] -N-phenylamino] biphenyl ) Was vacuum-deposited to form a hole injection layer having a thickness of 600 Å. Subsequently, a 300 Å thick hole transport layer was formed by vacuum deposition using the compound prepared in Example 1. (2-naphthyl) anthracene (ADN) was used as a host on top of the hole transport layer, and 3, 5 wt% of 2,5,8,11-tetra (tert- Doped and vacuum evaporated to form a 250 Å thick light emitting layer.

Thereafter, Alq3 was vacuum deposited on the light emitting layer to form an electron transporting layer having a thickness of 250 ANGSTROM. LiF 10 Å and Al 1000 Å were sequentially vacuum-deposited on the electron transport layer to form a cathode, thereby preparing an organic light emitting device.

The organic light emitting device has a structure having five organic thin film layers. Specifically, the organic EL device has a structure of Al (1000 Å) / LiF (10 Å) / Alq 3 (250 Å) / EML [ADN: TBPe = -1 (300 ANGSTROM) / DNTPD (600 ANGSTROM) / ITO (1500 ANGSTROM).

Example  11

An organic light emitting device was prepared in the same manner as in Example 10, except that Example 6 (A-6) was used instead of Example 1 (A-1).

Example  12

An organic luminescent device was prepared in the same manner as in Example 10, except that Example 7 (A-7) was used instead of Example 1 (A-1).

Example Name -2

An organic light emitting device was prepared in the same manner as in Example 10, except that Example Ad-1 (B-1) was used instead of Example 1 (A-1).

Comparative Example  One

In Example 10, an organic light emitting device was manufactured in the same manner except that NPB was used in place of Example 1 (A-1).

Comparative Example  2

An organic luminescent device was prepared in the same manner as in Example 10, except that H1 was used in place of Example 1 (A-1).

The compounds used in the above Examples and Comparative Examples are as follows.

[DNTPD] [AND] [TBPe]

[NPB] [HT1]

(Evaluation of thermal stability of materials)

DSC and TGA of each sample were measured and the glass transition temperature and decomposition temperature were measured. The results are shown in Table 1 below.

Name of material Tg ( ^o C ) Td ( ^o C ) Example  1 (A-1) 161 483 Example  6 (A-6) 142 487 Example  7 (A-7) 142 513 Example Name -1 (B-1) 150 507

Tg: glass transition temperature

Td: decomposition temperature

As can be seen from Table 1, the decomposition temperatures of Examples 1, 6, 7 and Ad-1 of the present invention were measured at about 500 ° C, which is the decomposition temperature of common carbazole biphenyl (CBP) Lt; 0 > C), the compounds of Examples 1, 6, 7 and Ad-1 have very high thermal stability.

It was also found that the compounds of Examples 1, 6, 7 and Ad-1 had a glass transition temperature remarkably higher than 90 占 폚, which is generally known glass transition temperature of a compound for an organic photoelectric device.

(Performance Measurement of Organic Light Emitting Device)

For each of the organic light emitting devices manufactured in Examples 10 to 12 and Ad-2 and Comparative Examples 1 and 2, the current density change, the luminance change, and the luminous efficiency were measured according to the voltage. Specific measurement methods are as follows, and the results are shown in Table 2 below.

(1) Measurement of change in current density with voltage change

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

(2) Measurement of luminance change according to voltage change

For the organic light emitting device manufactured, the luminance was measured using a luminance meter (Minolta Cs-1000A) while increasing the voltage from 0 V to 10 V, and the result was obtained.

(3) Measurement of luminous efficiency

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

device HTL Voltage (V) EL color Efficiency (cd / A) Half life (h)
@ 1000 cd / m ² Example 10 A-1 6.2 Blue 6.0 1,500 Example 11 A-6 6.2 Blue 5.7 1,700 Example 12 A-7 6.1 Blue 5.9 2,000 Example Ad-2 Ad-1 6.0 Blue 5.6 2,000 Comparative Example 1 NPB 7.1 Blue 4.9 1,250 Comparative Example 2 HT1 6.2 Blue 5.5 1,500

According to the results shown in Table 2, in the case of Examples 10 to 12 and Ad-2, the efficiency and half life time of the organic light emitting device are significantly superior to those of Comparative Examples 1 and 2.

The half life of Examples 10 to 12 and Ad-2 was significantly improved as compared with Comparative Examples 1 and 2. Particularly, the half life of Example 12 and Ad-2 was 2,000 hours (h) Which is about 1.6 times higher than the half life of 1250 hours. Considering that lifetime of a device is one of the biggest problems of commercialization in terms of commercialization of an actual device, the results of the above embodiments are considered sufficient to commercialize the device.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the following claims. As will be understood by those skilled in the art. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive.

100: organic photoelectric device 110: cathode
120: anode 105: organic thin film layer
130: luminescent layer 140: hole transport layer
150: electron transport layer 160: electron injection layer
170: Hole injection layer 230: Emission layer + Electron transport layer

Claims (18)

A compound for an organic photoelectric device represented by the following Formula 1:
[Chemical Formula 1]

In Formula 1,
Ar is a substituted or unsubstituted triphenylenyl group; A substituted or unsubstituted dibenzofuranyl group; Or a substituted or unsubstituted dibenzothiophenyl group,
X is N or P,
L ¹ is a substituted or unsubstituted C6 to C30 arylene group,
L ² is a single bond or a substituted or unsubstituted C6 to C30 arylene group,
n is an integer of 1 to 3,
m is an integer of 0 to 3,
R ¹ to R ⁹ are the same or different from each other and independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group , Or a combination thereof. The method according to claim 1,
Wherein the compound for an organic photoelectric device is represented by the following formula (2): < EMI ID =
(2)

In Formula 2,
Ar is a substituted or unsubstituted triphenylenyl group; A substituted or unsubstituted dibenzofuranyl group; Or a substituted or unsubstituted dibenzothiophenyl group,
X is N or P,
L ¹ is a substituted or unsubstituted C6 to C30 arylene group,
L ² is a single bond or a substituted or unsubstituted C6 to C30 arylene group,
n is an integer of 1 to 3,
m is an integer of 0 to 3,
R ¹ to R ⁹ are the same or different from each other and independently represent hydrogen, deuterium, a C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, or combinations thereof. The method according to claim 1,
Wherein the compound for an organic photoelectric device is represented by the following Formula 3:
(3)

In Formula 3,
X is N or P,
L ¹ is a substituted or unsubstituted C6 to C30 arylene group,
L ² is a single bond or a substituted or unsubstituted C6 to C30 arylene group,
n is an integer of 1 to 3,
m is an integer of 0 to 3,
R ¹ to R ⁹ are the same or different from each other and independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group , Or a combination thereof. The method according to claim 1,
Wherein the compound for an organic photoelectric device is represented by the following formula (4): < EMI ID =
[Chemical Formula 4]

In Formula 4,
X is N or P,
L ¹ is a substituted or unsubstituted C6 to C30 arylene group,
L ² is a single bond or a substituted or unsubstituted C6 to C30 arylene group,
n is an integer of 1 to 3,
m is an integer of 0 to 3,
R ¹ to R ⁹ are the same or different from each other and independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group , Or a combination thereof. The method according to claim 1,
Wherein the compound for an organic photoelectric device is represented by the following formula (5): < EMI ID =
[Chemical Formula 5]

In Formula 5,
X is N or P,
L ¹ is a substituted or unsubstituted C6 to C30 arylene group,
L ² is a single bond or a substituted or unsubstituted C6 to C30 arylene group,
n is an integer of 1 to 3,
m is an integer of 0 to 3,
R ¹ to R ⁹ are the same or different from each other and independently represent hydrogen, deuterium, a substituted or unsubstituted C1 to C20 alkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C2 to C30 heteroaryl group , Or a combination thereof. 3. The method of claim 2,
Wherein X is N. < RTI ID = 0.0 > 11. < / RTI > The method according to claim 1,
The compound for organic photoelectric conversion may be represented by the following formulas A-1, A-10, A-19, A-28, A-37, A-46, A-55, A-56, A- -67, A-76, A-77 A-86 or A-87.

The method according to claim 1,
The organic optoelectronic device compound is represented by the following chemical formulas A-2, A-4, A-6, A-8, A-11, A-13, A-15, A-17, A- -24, A-26, A-29, A-31, A-33, A-35, A-38, A-40, A-42, A- , A-53, A-57, A-59, A-62, A-64, A-69, A-71, A-72, A-74, A-79, A-81, -84, A-89, A-91, A-92 or A-94.

The method according to claim 1,
The compound for organic photoelectric conversion may be represented by the following formulas A-3, A-5, A-7, A-9, A-12, A-14, A-16, A-18, A- -25, A-27, A-30, A-32, A-34, A-36, A-39, A-41, A-43, A-45, A-48, , A-54, A-58, A-60, A-63, A-65, A-68, A-70, A-73, A-75, A-78, -85, A-88, A-90, A-93 or A-95.

The method according to claim 1,
Wherein the compound for an organic photoelectric device can be used as a hole transporting material or a hole injecting material of an organic light emitting device. The method according to claim 1,
Wherein the compound for an organic photoelectric device has a triplet excitation energy (T1) of 2.0 eV or more. The method according to claim 1,
Wherein the organic photoelectric device is selected from the group consisting of an organic light emitting device, an organic solar cell, an organic transistor, an organic photoreceptor drum, and an organic memory device. 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,
Wherein at least one of the organic thin film layers comprises the organic photoelectric device compound according to any one of claims 1 to 12. 14. The method of claim 13,
Wherein the organic thin film layer is selected from the group consisting of a light emitting layer, a hole transporting layer, a hole injecting layer, an electron transporting layer, an electron injecting layer, a hole blocking layer, and combinations thereof. 14. The method of claim 13,
Wherein the compound for an organic photoelectric device is contained in a hole transporting layer or a hole injecting layer. 14. The method of claim 13,
Wherein the compound for an organic photoelectric conversion element is contained in the light emitting layer. 14. The method of claim 13,
Wherein the compound for organic photoelectric conversion element 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 13.

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