KR101515555B1 - Compound Containing Ring Linked Via Carbazole and Fluorene And Organic Electronic Element Using The Same, Terminal Thereof - Google Patents

Abstract

The present invention provides a compound in which carbazole and fluorene are bonded to each other to form a ring, and an organic electric device using the compound and a terminal thereof.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound having a carbazole bond and a fluorene bond,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound in which carbazole and fluorene are bonded to each other to form a ring, and an organic electronic device using the compound.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic electric device using an organic light emitting phenomenon generally has a structure including an anode, an anode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic electronic device, the organic material layer may have a multi-layer structure composed of different materials, and may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

A material used as an organic material layer in an organic electric device may 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. The light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight, and may be classified into a phosphorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons . 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 may be used as the light emitting material in order to increase the light emitting efficiency through the light emitting layer. When the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with a small amount of the light emitting layer, the excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on the type of the dopant used.

In order to sufficiently exhibit the excellent characteristics of the organic electroluminescent device described above, a material constituting the organic material layer in the device, such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material is supported by a stable and efficient material However, stable and efficient development of an organic material layer for an organic electric device has not yet been sufficiently developed, and therefore development of a new material is continuously required.

The present inventors have discovered a compound in which a carbazole having a novel structure is bonded to fluorene to form a ring, and that when this compound is applied to an organic electric device, the luminous efficiency, stability and lifetime of the device can be greatly improved I found out the truth.

Accordingly, it is an object of the present invention to provide a compound in which a novel carbazole and fluorene are bonded to form a ring, and an organic electric device using the compound and a terminal thereof.

In one aspect, the invention provides compounds of the formula:

The present invention relates to a hole injecting material, a hole transporting material, a light emitting material, and / or an electron transporting material suitable for the fluorescence of all colors such as red, green, blue, and white and phosphorescent devices according to a compound in which carbazole and fluorene are bonded to form a ring. And is useful as a host material for phosphorescent dopants of various colors.

The present invention also provides an organic electronic device using the compound having the above formula and a terminal including the organic electronic device.

The compound of the present invention can play various roles in an organic electric device and a terminal, and when applied to an organic electric device and a terminal, the driving voltage of the device can be lowered, and the light efficiency, lifetime, and stability of the device can be improved.

1 to 6 show examples of organic electroluminescent devices to which the compounds of the present invention can be applied.

Hereinafter, some embodiments of the present invention will be described in detail with reference to exemplary drawings. It should be noted that, in adding reference numerals to the constituent elements of the drawings, the same constituent elements are denoted by the same reference numerals even though they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are intended to distinguish the constituent elements from other constituent elements, and the terms do not limit the nature, order or order of the constituent elements. When a component is described as being "connected", "coupled", or "connected" to another component, the component may be directly connected to or connected to the other component, It should be understood that an element may be "connected,""coupled," or "connected."

The present invention provides the compounds of Formulas 1 to 6 below.

In the above Formulas 1 to 6,

(1) R ₁ To R ₆ are each independently of the other a hydrogen atom, a halogen atom, a cyano group, an alkyl group, a substituted or unsubstituted C _{1 -50,} Substituted or unsubstituted C _{1 -50} alkoxy group, a substituted or unsubstituted C _{1 -50} alkyl thiol group, a substituted or unsubstituted aryl thiol group, a substituted C _{6 -50} or unsubstituted C _{2 -50} A substituted or unsubstituted C _{6 -50} arylene group, a substituted or unsubstituted C _{4 -60} aryl group, -N (R ₇ ) ₂ or -N (R ₇ ) (R ₈ ) A substituted or unsubstituted amino group, a substituted or unsubstituted amino group represented by -N (R ₇ ) ₂ or -N (R ₇ ) (R ₈ ), a substituted or unsubstituted C _{4 -60} aryl group, Substituted or unsubstituted C _{1 -50} alkyl group containing at least one heteroatom of O, P and Si, C _{3 -50} substitution comprising at least one hetero atom among S, N, O, P and Si Or an unsubstituted alkenyl group, a C _{6 -50} substituted or unsubstituted arylene group containing at least one hetero atom selected from S, N, O, P and Si, at least one of S, N, O, P and Si The above- May be one selected from the group consisting of substituted or unsubstituted aryl group of C _4, including the _-60, wherein R ₇ to R ₈ are a substituted or unsubstituted alkyl group, a substituted or unsubstituted of C ₁ C _{2 -50} Exchange _-50 Substituted or unsubstituted C _{6 -50} arylene group, substituted or unsubstituted C _{4 -60} aryl group, S, N, O, P and Si, hwandoen C _{1 -50} of the alkyl group, S, N, O, P and Si, at least one heteroatom _{2 -50} C a substituted or unsubstituted alkenyl group, S, N, O of, containing P and Si in substitution of C _{2 -50} containing at least one heteroatom or unsubstituted arylene group, S, N, O, optionally substituted containing P and Si, at least one or more hetero atoms in the or unsubstituted aryl of C _{4 -60} Group, and R < _{1 >} And R ₂ , and When a, b, and c are each 2 or more, R ₃ And R ₃ , R ₄ and R ₄ , R ₆ And R < ₆ > may combine with each other to form a ring.

(2) A to F are each independently a substituted or unsubstituted C _{2 -50} each other _- alkenyl, C ₂ comprising a substituted or unsubstituted C _{6 -50} aryl group, a substituted or unsubstituted C for _4-60 aryl group, or more S, N, O, at least one of P and Si heteroatoms ₅₀ substituted or unsubstituted alkenyl group, S, N, O, P and Si at least _-50 C ₆ substituted or unsubstituted arylene group, S, in containing one or more heteroatoms of N, O, P and Si A substituted or unsubstituted C _{6 -60} aryl group containing at least one heteroatom, a substituted or unsubstituted amino group represented by -N (R ₇ ) ₂ or -N (R ₇ ) (R ₈ ) A substituted C _{4 -60} aryl group, wherein R ₇ to R ₈ are as defined above.

(3) X must be one of N, O, and S, and when X is O or S, p and q are zero.

(4) a to c are integers of 0 to 4, 1 to q are integers of 0 to 4, and r is an integer of 1 to 3. In this case, the condition of l + m + n + o + p + q ≥ 1 must be satisfied.

(5) The present invention also relates to a process for producing a compound represented by any one of the above formulas (1) to (6), wherein the compound represented by the general formulas (1) to (6) is used as a hole injection material, a hole transport material and a host material suitable for all color phosphorescent dopants such as red, green, An electroluminescent device is provided.

(6) The compounds of the above formulas (1) to (6) may be used in a soluble process.

As used herein, the term "substituted or unsubstituted C _{4 -60} An aryl group or a substituted or unsubstituted aryl group having _{4 to 60} carbon atoms containing at least one hetero atom selected from the group consisting of S, N, O, P and Si "means a phenyl group, a 1-naphthyl group, Anthryl group, 1-phenanthryl group, 2-phenanthryl group, 3-phenanthryl group, 4-phenanthryl group, 9-phenanthryl group, Naphthacene group, a 1-pyrene group, a 2-pyrene group, a 4-pyrene group, a 2-biphenyl group, a 3-biphenyl group, a 4- M-terphenyl-3-yl group, m-terphenyl-2-yl group, (2-phenylpropyl) phenyl group, 3-methyl-2-naphthyl group, 4-methyl-1-naphthyl group, 4-methylpyridyl group, Methyl-1-anthryl group, 4'-methylbiphenylyl group, 4'-t-butyl-p-terphenyl-4-yl group, 9,9-dimethylfluorenyl group, 9,9-diethylfluorenyl group , 9,9-methylethylfluorenyl group, 9,9-diphenylfluor A 2-pyrrolyl group, a 3-pyrrolyl group, a pyrazinyl group, a 2-pyridyl group, a 2-pyridyl group, a 2-pyridyl group, 3-indolyl, 4-indolyl, 5-indolyl, 6-indolyl, 7-indolyl, 1-isoindolyl, 3-pyridinyl, Isoindolinyl, isoindolinyl, isoindolinyl, 4-isoindolyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl, 2- furyl, 3- furyl, Benzofuranyl group, 3-benzofuranyl group, 4-benzofuranyl group, 5-benzofuranyl group, 6-benzofuranyl group, 7-benzofuranyl group, 1-isobenzofuranyl group, Isobenzofuranyl group, 3-quinolyl group, 4-quinolyl group, 5-quinolyl group, 6-quinolyl group, Quinolyl group, 8-quinolyl group, 1-isoquinolyl group, 3-isoquinolyl group, 4-iso Isoquinolinyl group, 2-quinoxalinyl group, 5-quinoxalinyl group, 6-quinoxalinyl group, 1- A carbazolyl group, a 3-carbazolyl group, a 4-carbazolyl group, a 1-phenanthridinyl group, a 2-phenanthridinyl group, a 3-phenanthridinyl group, Phenanthridinyl group, 10-phenanthridinyl group, 1-acridinyl group, 2-acridinyl group, 3-phenanthridinyl group, An acridine group, a 4-acridine group, a 9-acridine group, a 1,7-phenanthroline-2-yl group, a 1,7-phenanthroline- Yl group, a 1,7-phenanthroline-6-yl group, a 1,7-phenanthroline-8-yl group, a 1,7-phenanthroline- A 1,8-phenanthroline-3-yl group, a 1,8-phenanthroline-4-yl group, Dienes, 1,8-phenanthroline-5-yl groups, 1,8-phenanthroline-6-yl groups, 1,8-phenanthroline A 1,8-phenanthroline-9-yl group, a 1,8-phenanthroline-10-yl group, a 1,9-phenanthroline- A 1,9-phenanthroline-4-yl group, a 1,9-phenanthroline-5-yl group, a 1,9-phenanthroline- A 1,10-phenanthroline-2-yl group, a 1,10-phenanthroline-3-yl group, a 1,1-phenanthroline- , A 10-phenanthroline-1-yl group, a 2,9-phenanthroline-3-yl group, a 2,9-phenanthroline- A 2,9-phenanthroline-6-yl group, a 2,9-phenanthroline-7-yl group, a 2,9-phenanthroline- Yl group, a 2,9-phenanthroline-10-yl group, a 2,8-phenanthroline-1-yl group, a 2,8-phenanthroline- Yl group, a 2,8-phenanthroline-7-yl group, a 2,8-phenanthroline-9-yl group, -Yl group, a 2,8-phenanthroline-10-yl group, a 2,7-phenanthroline-1-yl group, a 2,7-phenanthroline- -Yl group, 2,7-phenanthroline-5-yl group, 2,7-phenanthroline-6-yl group, 2,7-phenanthroline- , 2-phenanthroline-10-yl group, 1-phenanazine group, 2-phenanthrene group, 1-phenothiazine group, 2-phenothiazine group, 3-phenothiazine group, 4- A 2-oxazolyl group, a 4-oxazolyl group, a 5-oxazolyl group, a 2-oxadiazolyl group, 2-methylpyrrol-1-yl group, 2-methylpyrrol-3-yl group, 2-methylpyrrol-1-yl group, Methylpyrrol-4-yl group, 3-methylpyrrol-5-yl group, 2-methylpyrrol-5-yl group, methyl-1-indolyl group, 2-methyl-3-indolyl group, 2-methyl-1-indolyl group, Indolyl group, 2-t-butyl 1-indolyl group, 4-t-butyl 1-indolyl group, 2- A 4-t-butyl 3-indolyl group, and the like.

Examples of the "substituted or unsubstituted C _{1 -50} alkyl group" in the present invention include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, n-pentyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, hydroxymethyl, hydroxyethyl, 2-hydroxyethyl, A dihydroxyethyl group, a 1,3-dihydroxyisopropyl group, a 2,3-dihydroxy-t-butyl group, a 1,2,3-trihydroxypropyl group, a chloromethyl group, Dichloro isobutyl group, 1,2-dichloroethyl group, 1,3-dichloroisopropyl group, 2,3-dichloro-t-butyl group, 1,2,3-trichloro Propyl group, a 1-bromoethyl group, a 2-bromoethyl group, a 2-bromoisobutyric group, a 1,2-dibromoethyl group, -t-butyl A 1,2,3-tribromopropyl group, an iodomethyl group, a 1-iodoethyl group, a 2-iodoethyl group, a 2-iodo isobutyl group, Diiodo isopropyl group, 2,3-diiodo-t-butyl group, 1,2,3-triiodopropyl group, aminomethyl group, 1-aminoethyl group, 2-aminoethyl group, A 1,2-diaminoethyl group, a 1,3-diaminoisopropyl group, a 2,3-diamino-t-butyl group, a 1,2,3-triaminopropyl group, a cyanomethyl group, Dicyano isopropyl group, 2,3-dicyano-t-butyl group, 2,3-dicyano-iso-propyl group, A 1,2,3-triisopropyl group, a 1,2,3-triacyanopropyl group, a nitrormethyl group, a 1-nitroethyl group, a 2-nitroethyl group, a 2-nitroisobutyl group, A nitroisopropyl group, a 2,3-di A cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a 4-methylcyclohexyl group, a 1-adamantyl group, a 2-adamantyl group, a 2-naphthyl group, -Adamantyl group, 1-norbornyl group, 2-norbornyl group and the like.

The term "substituted or unsubstituted C _{1 -50} alkoxy group" used in the present embodiment may be represented by -OR, and examples of R include a methyl group, an ethyl group, a propyl group, an isopropyl group, Butyl group, n-hexyl group, n-heptyl group, n-octyl group, hydroxymethyl group, 1-hydroxyethyl group, 2-hydroxy An isopropyl group, an ethyl group, a 2-hydroxyisobutyl group, a 1,2-dihydroxyethyl group, a 1,3-dihydroxyisopropyl group, a 2,3-dihydroxy- A chloropropyl group, a chloromethyl group, a 1-chloroethyl group, a 2-chloroethyl group, a 2-chloroisobutyl group, a 1,2-dichloroethyl group, t-butyl group, t-butyl group, 1,2,3-trichloropropyl group, bromomethyl group, 1-bromoethyl group, 2-bromoethyl group, 2-bromoisobutyric group, - Dive in Propyl group, isopropyl group, 2,3-dibromo-t-butyl group, 1,2,3-tribromopropyl group, iodomethyl group, 1-iodoethyl group, 2-iodoethyl group, , A 1,2-diiodoethyl group, a 1,3-diiodoisopropyl group, a 2,3-diiodo-t-butyl group, a 1,2,3-triiodopropyl group, 2-aminoethyl group, 2-aminoisobutyl group, 1,2-diaminoethyl group, 1,3-diaminoisopropyl group, 2,3-diamino- A 2-cyano iso-butyl group, a 1,2-dicyanamoyl group, a 1,3-dicyanoisopropyl group, a 2- , A 2,3-dicyano-t-butyl group, a 1,2,3-triacyanopropyl group, a nitromethyl group, a 1-nitroethyl group, a 2-nitroethyl group, a 2-nitroisobutyl group, 1,2-dinitroethyl group, 1,3-di And the like, nitro-isopropyl group, 2,3-dimethyl-1,2,3-tri-nitro--t- view group and a propyl group, nitro.

Further, the terms of "substituted or unsubstituted C _6-60 aryloxy of a C _6-60 containing group or a heteroatom substituted or unsubstituted aryloxy group" used in this embodiment is-represented by OY ' And examples of Y 'include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a 1-anthryl group, a 2-anthryl group, a 9-anthryl group, a 1-phenanthryl group, Phenanthryl group, a 9-phenanthryl group, a 1-naphthacenylene group, a 2-naphthacene group, a 9-naphthacenylene group, a 1-pyreneyl group, , A p-terphenyl-3-yl group, a p-terphenyl-2-yl group, a m-terphenyl group, M-tolyl group, p-tolyl group, pt-butylphenyl group, p- (2-phenylpropyl) Methyl-1-naphthyl group, 4-methyl-1-anthryl group, 4'-methylbiphenyl group, 4 " 4-yl group, 2-pyrrolyl group, 3 Indolyl group, 4-indolyl group, 5-indolyl group, 6-indolyl group, 7-indolyl group, 2-pyridyl group, Isoindolinyl, 3-isoindolinyl, 4-isoindolinyl, 5-isoindolyl, 6-isoindolyl, 7-isoindolyl, A 2-benzofuranyl group, a 3-benzofuranyl group, a 4-benzofuranyl group, a 5-benzofuranyl group, a 6-benzofuranyl group, a 7-benzofuranyl group, a 1-isobenzofuranyl group, Isobenzofuranyl group, 2-quinolyl group, 3-quinolyl group, 4-quinolyl group, 4-isobenzofuranyl group, Isoquinolyl group, 4-isoquinolyl group, 5-isoquinolyl group, 4-isoquinolyl group, 4-isoquinolyl group, 4-isoquinolyl group, Isoquinolyl group, 8-isoquinolinyl group, 2-quinoxalinyl group, 5-quinoxalyl group, A thiazolyl group, a 2-thienylthio group, a 2-thienylthio group, a thiomorpholinyl group, a thiomorpholinyl group, a thiazolyl group, Phenanthridinyl group, 9-phenanthridinyl group, 10-phenanthridinyl group, 1-acridine group, 2-phenanthridine group, Acridine group, 3-acridine group, 4-acridine group, 9-acridine group, 1,7-phenanthroline-2-yl group, 1,7-phenanthroline- Yl group, a 1,7-phenanthroline-6-yl group, a 1,7-phenanthroline-8-yl group, Dienes, 1,7-phenanthroline-9-yl groups, 1,7-phenanthroline-10-yl groups, 1,8-phenanthroline- A 1,8-phenanthroline-7-yl group, a 1,8-phenanthroline-5-yl group, A 1,9-phenanthroline-2-yl group, a 1,9-phenanthroline-3-yl group, a 1,9-phenanthroline- Pernant Yl group, a 1,9-phenanthroline-6-yl group, a 1,9-phenanthroline-7-yl group, a 1,9-phenanthroline- Dienes, 1,10-phenanthroline-3-yl groups, 1,10-phenanthroline-4-yl groups, Dienes, 2,10-phenanthroline-1-yl groups, 2,9-phenanthroline-3-yl groups, 2,9- Yl group, 2,9-phenanthroline-8-yl group, 2,9-phenanthroline-6-yl group, 2,9- A 2,8-phenanthroline-1-yl group, a 2,8-phenanthroline-4-yl group, a 2,8-phenanthroline- Phenanthroline-6-yl group, 2,8-phenanthroline-7-yl group, 2,8-phenanthroline-9-yl group, 2,8-phenanthrol Yl group, a 2,7-phenanthroline-4-yl group, a 2,7-phenanthroline-1-yl group, 6-yl group, 2,7-phenanthroline-8-yl group, 2,7-phenanthroline-9-yl group, 2,7-phenanthrol A 2-phenothiazinyl group, a 2-phenothiazinyl group, a 3-phenothiazinyl group, a 4-phenothiazinyl group, a 1-phenoxyryl group, , A 2-phenoxyl group, a 3-phenoxyl group, a 4-phenoxyl group, a 2-oxazolyl group, a 4-oxazolyl group, a 5-oxazolyl group, , 2-methylpyrrol-4-yl group, 2-methylpyrrol-1-yl group, Methylpyrrol-4-yl group, 3-methylpyrrol-5-yl group, 2-t-butylpyrrole- Indolyl group, 2-methyl-3-indolyl group, 4-methyl-3-indole group, Indolyl group, 2-t-butyl 1-indolyl group, 4-t-butyl 1-indolyl group, 2-t-butyl 3-indolyl group and 4-t-butyl 3-indolyl group.

The term "substituted or unsubstituted C _{1 -50} alkylthiol group" used in the present embodiment may be represented by -SR, and R is as defined above.

The term "substituted or unsubstituted C _{6 -50} arylthiol group" used in the present embodiment may be represented by -SY ', and Y' is as defined above.

The term "halogen atom" used in this embodiment includes fluorine, chlorine, bromine and iodine.

Specific examples of the compound represented by the formula (1), which is a compound in which a carbazole and a fluorene are combined to form a ring according to an embodiment of the present invention, include compounds represented by the following formula (7), but the present invention is not limited thereto.

As specific examples of the compound belonging to the formula (2), which is a compound in which carbazole and fluorene are bonded to form a ring according to an embodiment of the present invention, there are compounds of the following formula (8), but the present invention is not limited thereto.

As specific examples of the compounds belonging to the general formula (3), which is a compound in which a carbazole and a fluorene are combined to form a ring according to an embodiment of the present invention, there are compounds of the following general formula (9), but the present invention is not limited thereto.

Specific examples of the compounds belonging to the formula (4), which is a compound in which carbazole and fluorene are combined to form a ring according to an embodiment of the present invention, include the compounds of the following formula (10), but the present invention is not limited thereto.

As specific examples of the compounds belonging to Chemical Formula 5, which is a compound in which carbazole and fluorene are combined to form a ring according to an embodiment of the present invention, there are the following compounds of Chemical Formula 11, but the present invention is not limited thereto.

Specific examples of the compounds belonging to the formula (6), which is a compound in which carbazole and fluorene are combined to form a ring according to an embodiment of the present invention, include the compounds of the following formula (12), but the present invention is not limited thereto.

There are various organic electric devices in which the carbazole and fluorene bond to form a ring are used as organic layers. Organic electric devices in which compounds having a carbazole-fluorene bond to form rings can be used, for example, an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC) Drums, organic transistors (TFTs), photodiodes, organic lasers, and laser diodes.

An organic electroluminescent device (OLED) will be described below as one example of an organic electroluminescent device to which compounds having a carbazole-fluorene bond to form a ring can be applied, as described with reference to Formulas 1 to 12, but the present invention is not limited thereto A compound in which a carbazole and a fluorene are bonded to each other to form a ring can be applied to various organic electroluminescent devices.

Another embodiment of the present invention is directed to an organic electronic device including a first electrode, a second electrode, and an organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers includes an organic electric field A light emitting device is provided.

1 to 6 show examples of organic electroluminescent devices to which the compounds of the present invention can be applied.

An organic electroluminescent device according to another embodiment of the present invention includes a hole injecting layer, a hole transporting layer, a light emitting layer, And an organic compound layer including an electron injecting layer are formed so as to include the compounds of the above Chemical Formulas 1 to 12. The organic layer may be formed using a conventional method and materials known in the art . ≪ / RTI >

The structure of an organic electroluminescent device according to another embodiment of the present invention is illustrated in FIGS. 1 to 6, but the present invention is not limited to these structures. Reference numeral 101 denotes a substrate, 102 denotes an anode, 103 denotes a hole injection layer (HIL), 104 denotes a hole transport layer (HTL), 105 denotes a light emitting layer (EML), 106 denotes an electron injection layer (EIL) ETL), and 108 denotes a cathode. However, the organic EL device may further include a hole blocking layer (HBL) for blocking the movement of holes, an electron blocking layer (EBL) for blocking the movement of electrons, and a protective layer. In the case of the protective layer, it may be formed to protect the organic layer at the uppermost layer or to protect the cathode.

At this time, the compound having a carbazole-fluorene bond to form a ring as described with reference to Formulas 1 to 12 may be included in at least one of organic compound layers including a hole injecting layer, a hole transporting layer, a light emitting layer, and an electron transporting layer. Specifically, the compound having a carbazole-fluorene bond as described with reference to the formulas (1) to (12) may form a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, May be used in place of or in addition to one or more of the layers. Of course, it can be used for more than two layers, not only one layer of the organic material layer.

Particularly, it is possible to prepare a hole injecting material and a hole transporting material suitable for the fluorescence of all colors such as red, green, blue, and white and the phosphorescent device according to the compound in which the carbazole and fluorene are combined to form a ring, , A light emitting material and / or an electron transporting material, and is useful as a host material for phosphorescent dopants of various colors.

For example, the organic electroluminescent device according to another embodiment of the present invention may be formed by depositing a metal or a metal having conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation Oxide or an alloy thereof to form an anode, forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer and an electron injecting layer on the anode, depositing a material usable as a cathode thereon .

In addition to such a method, the organic material may be formed by sequentially depositing a negative electrode material, an organic material layer, and a positive electrode material on a substrate. The organic material layer may have a multi-layer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, but is not limited thereto and may have a single layer structure. In addition, the organic material layer may be formed using a variety of polymer materials by a solvent process such as a spin coating process, a dip coating process, a doctor blading process, a screen printing process, an inkjet printing process or a thermal transfer process, Layer.

The organic electroluminescent device according to another embodiment of the present invention may form an organic material layer, for example, a light emitting layer, by a solution process in which the above-described carbazole and fluorene bond to form a ring.

The substrate may be a silicon wafer, a quartz or glass plate, a metal plate, a plastic film, a sheet, or the like, which is a support for an organic electroluminescent device.

An anode is placed on the substrate. Such an anode injects holes into the hole injection layer located thereon. As the anode material, a material having a large work function is preferably used so as to smoothly inject holes into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline.

A hole injection layer is located on the anode. The conditions required for the material of the hole injection layer are that the hole injection efficiency from the anode is high and the injected holes must be efficiently transported. For this purpose, the ionization potential is small, the transparency to visible light is high, and the stability against holes is excellent.

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene, quinacridone-based organic materials, perylene-based organic materials, Anthraquinone, polyaniline and a polythiophene-based conductive polymer, but are not limited thereto.

A hole transport layer is disposed on the hole injection layer. The hole transport layer transports holes from the hole injection layer to an organic light emitting layer disposed thereon, and has high hole mobility, stability to holes, and electrons. In addition to these general requirements, a material having a glass transition temperature (Tg) of 70 DEG C or more is preferable when heat resistance is required for a device for application to a vehicle body. Materials satisfying such conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene, silicon germanium oxide Compounds, silicone-based arylamine compounds, and the like.

An organic light emitting layer is disposed on the hole transporting layer. The organic light emitting layer is a layer in which holes and electrons injected from the anode and the cathode respectively recombine to emit light, and the organic light emitting layer is made of a material having high quantum efficiency. The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having a high quantum efficiency for fluorescence or phosphorescence.

Materials or compounds that satisfy these conditions include Alq3 in the case of green, Balq (8-hydroxyquinoline beryllium salt) in the case of blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) biphenyl series, Spiro materials, Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenol lithium and metal complexes of imidazole, thiazole and oxazole, and perylene and BczVBi (3,3 ', 2', 2 ', 2'- Bis (9-ethyl) -9H-carbazole (DSA (distrylamine)) may be used as a dopant. In the case of red, the green luminescent material was doped with DCJTB ([2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl- -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile). Polymer such as polyphenylene vinylene (PPV) -based polymer or polyfluorene (polyfluorene) can be formed on the organic light-emitting layer (light-emitting layer) when the light-emitting layer is formed using processes such as inkjet printing, roll coating, .

An electron transporting layer is disposed on the organic light emitting layer. Such an electron transporting layer requires a material capable of efficiently injecting electrons with a high electron injection efficiency from a cathode disposed thereon. For this purpose, it is required to be made of a material having high electron affinity, high electron transfer rate and excellent stability against electrons. Specific examples of the electron transporting material satisfying such conditions include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

An electron injection layer is deposited on the electron transport layer. The electron injection layer may be a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI or Tf-6P, boron compounds, and the like. At this time, the electron injection layer may be formed in a thickness range of 100 ANGSTROM to 300 ANGSTROM.

On the electron injection layer, a cathode is positioned. These cathodes serve to inject electrons. As the material used for the cathode, materials used for the anode can be used, and a metal having a low work function is more preferable for efficient electron injection. Particularly suitable metals such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or their alloys may be used. Also, an electrode having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum, etc., having a thickness of 100 μm or less may be used.

As described above, depending on the compound that forms the ring by bonding carbazole and fluorene described with reference to Formulas 1 to 12, it is possible to produce a hole injection material suitable for the fluorescence of all colors such as red, green, blue, and white and phosphorescent device, Emitting material, an electron transporting material, and an electron injecting material, and can be used as a host material for phosphorescent dopants of various colors.

The organic electroluminescent device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

Meanwhile, the present invention includes a display device including the above-described organic electronic device and a terminal including a control unit for driving the display device. This terminal means a current or future wired or wireless communication terminal. The terminal according to the present invention may be a mobile communication terminal such as a mobile phone and includes all terminals such as a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

Example

Hereinafter, the present invention will be described in more detail with reference to Production Examples and Experimental Examples. However, the following Production Examples and Experimental Examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Manufacturing example

Hereinafter, preparation examples or synthesis examples of compounds in which carbazole and fluorene bonded to formulas (7) to (12) form a ring are described. However, since there are a large number of compounds in which carbazole and fluorene bonded to formulas (7) to (12) form a ring to form a ring, one or two of the compounds in which carbazole and fluorene bonded to formulas Will be described by way of example. Those skilled in the art will recognize that the compounds of the present invention, which are not exemplified in the present invention, can form a ring by combining carbazole and fluorene, by those skilled in the art, .

의 합성 Synthesis Example 1 : Compound 6

Synthesis of

1. Synthesis of intermediate 6-1 [2-bromo-2'-nitrobiphenyl]

[Reaction Scheme 1]

1000 mL round bottom flask 2 gu 1-iodo-2-nitrobenzene (100 mmol, 24.9g), 2- bromo-phenyl boronic acid (100 mmol, 20.0g), Pd (PPh 3) 4 (3.0 mmol, 3.47 g), sodium hydroxide (300 mmol, 12.0 g) was added, 400 mL of tetrahydrofuran and 100 mL of water were added, and the mixture was refluxed at 75 ° C. for 12 hours. When the reaction is completed, the reaction solution is cooled to room temperature and extracted with dichloromethane. The organic solvent layer is dried using MgSO _4, and the solvent is removed by drying under reduced pressure. The obtained reaction product was separated and purified by silica gel tube chromatography to obtain 22.0 g (yield: 79%) of Intermediate 6-1 as a white solid.

¹ H-NMR (CDCl ₃ , 400MHz)? 8.05-8.00 (m, 2H), 7.90 (t, 1H), 7.68-7.66 (m, 3H), 7.45 (t, 1H), 7.30 (t, 1H).

2. Synthesis of intermediate 6-2 [4-bromo-9 H -carbazole]

[Reaction Scheme 2]

Add intermediate 6-1 (100.0 mmol, 27.8 g) and triethyl phosphite (700.0 mmol, 116.3 g) into a 250 mL two-neck round bottom flask and reflux at 160 ° C for 12 hours. The temperature of the reaction solution was lowered to room temperature and extracted with ethyl acetate. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to obtain crude product. The crude product was purified by silica gel column chromatography to obtain intermediate 6-2 as a yellow solid 15.5 g (yield: 63%) was obtained.

¹ H-NMR (CDCl ₃ , 400MHz)? 10.10 (s, 1H), 8.12 (d, 1H), 7.63-7.50 (m, 3H), 7.34-7.26 (m, 3H).

3. Synthesis of Intermediate Compound 6-3 [4-bromo-9- phenyl-9 H -carbazole]

[Reaction Scheme 3]

Intermediate 6-2 (100.0 mmol, 24.6 g), iodobenzene (120.0 mmol, 24.5 g), Cu-metal (110.0 mmol, 7.0 g) and K ₂ CO ₃ (150.0 mmol, 20.7 g) and 18-Crown-6 (10.0 mmol, 2.64 g) were charged and charged with nitrogen. 500 mL of dimethylformamide as a solvent is added thereto, and the mixture is refluxed at 190 DEG C for 12 hours. The temperature of the reaction solution was lowered to room temperature and extracted with water and diethyl ether. The obtained extract was dried with MgSO ₄ and dried under reduced pressure to obtain crude product. The crude product was purified by silica gel column chromatography to obtain intermediate 6-3 as a yellow solid 23.5 g (yield: 73%) was obtained.

4. Synthesis of Intermediate Compound 6-4 [9-phenyl-4- ( 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9 H -carbazole]

[Reaction Scheme 4]

(100.0 mmol, 32.2 g), bispina coli todiboron (150.0 mmol, 38.1 g), PdCl ₂ (dppf) (3.0 mmol, 2.45 g), potassium acetate mmol, 29.4 g) were charged and charged with nitrogen. 500 mL of dimethylformamide as a solvent was added thereto, followed by stirring at 80 DEG C for 6 hours. The temperature of the reaction solution was lowered to room temperature and extracted with dichloromethane. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain intermediate 6-4 as a yellow solid 19.9 g (Yield: 54%) was obtained.

5. Synthesis of Intermediate 6-5 [methyl 2- (9-phenyl- 9 H -carbazol-4-yl) benzoate]

[Reaction Scheme 5]

1000 mL 2-neck round bottom flask intermediate 6-4 (100.0 mmol, 36.9g), 2- bromomethyl benzoate (100.0 mmol, 21.5g), Pd (PPh 3) 4 (3.0 mmol, 3.47g), potassium Carbonate (300.0 mmol, 41.5 g), 400 mL of tetrahydrofuran as a solvent and 100 mL of water are added, followed by stirring at 80 ° C for 6 hours. The temperature of the reaction solution was lowered to room temperature and extracted with dichloromethane. The obtained extract was dried over MgSO _{4 and} then dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain Intermediate 6-5 as a yellow solid 24.9 g (Yield: 66%) was obtained.

6. Synthesis of Intermediate Compound 6-6 [5-phenylindeno [2, 1-c] carbazol-8 (5 H) -one]

[Reaction Scheme 6]

(50.0 mmol, 18.9 g), methanesulfonic acid (50.0 mmol, 4.8 g) and polyphosphoric acid (0.5 M, 100.0 mL) were placed in a 250 mL two-neck round bottom flask and refluxed at 200 ° C. for 48 hours . The temperature of the reaction solution was lowered to room temperature and extracted with diethyl ether. The obtained extract was dried with MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain intermediate 6-6 as a yellow solid 12.4 g (Yield: 72%) was obtained.

7. Intermediates 6-7 Synthesis of [5-phenyl-5,8-dihydroindeno [2, 1-c] carbazole]

[Reaction Scheme 7]

(50.0 mmol, 17.3 g) and LiAlH ₄ (150.0 mmol, 5.69 g) were added to a 500 mL two-neck round bottom flask, and 150 mL of tetrahydrofuran as a solvent was added thereto. The mixture was stirred at room temperature for 6 hours do. After the reaction was completed, an appropriate amount of hydrochloric acid was added, and the reaction solution was extracted with diethyl ether. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was separated and purified by silica gel column chromatography to obtain 10.6 g (yield: 64%) of intermediate 6-7 as a yellow solid.

8. Synthesis of Intermediate Compound 6-8 [8,8-dimethyl-5- phenyl-5,8-dihydroindeno [2, 1-c] carbazole]

[Reaction Scheme 8]

Intermediate 6-7 (50.0 mmol, 16.6 g), iodomethane (110.0 mmol, 15.6 g) and potassium hydroxide (150 mmol, 8.42 g) were added to a 500 mL two-necked round bottom flask, and 150 mL of methanol Followed by stirring at room temperature for 3 hours. When the reaction was completed, the solvent, methanol, was removed with a concentrator, and then water and diethyl ether were added thereto and then extracted. The obtained extract was dried with MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain intermediate 6-8 as a yellow solid 15.1 g (Yield: 84%) was obtained.

9. Synthesis of Intermediate Compound 6-9 [2-bromo-8,8- dimethyl-5-phenyl-5,8-dihydroindeno [2, 1- c] carbazole]

[Reaction Scheme 9]

Add intermediate (6-8) (50.0 mmol, 18.0 g) and NBS (52.5 mmol, 5.31 g) to a 500 mL 2-necked round bottom flask, add 150 mL of dichloromethane as a solvent and stir at room temperature for 5 hours. When the reaction was completed, dichloromethane as a solvent was diluted with an appropriate amount and extracted. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to obtain a crude product. The resulting crude product was recrystallized from diethyl ether and normal hexane and then purified by silica gel column chromatography to obtain intermediate 6-9 (Yield: 91%) as a yellow solid.

10. Synthesis of intermediate 6-10 [2- (4-iodophenyl) -8,8-dimethyl-5-phenyl-5,8-dihydroindeno [2, 1-c] carbazole]

[Reaction Scheme 10]

(50 mmol, 24.9 g), 4-iodophenylboronic acid (50 mmol, 12.4 g), Pd (PPh ₃ ) ₄ (1.5 mmol, 1.74 g), hydroxyl salt (150 mmol, 6.0 g), add 200 mL of tetrahydrofuran and 50 mL of water, reflux at 75 ° C for 12 hours after filling with nitrogen. When the reaction is completed, the reaction solution is cooled to room temperature and extracted with dichloromethane. The organic solvent layer is dried using MgSO _4, and the solvent is removed by drying under reduced pressure. The reaction product thus obtained was recrystallized from dichloromethane and n-hexane and then purified by silica gel column chromatography to obtain 23.9 g (yield: 85%) of Intermediate 6-10 as a yellow solid.

_{^{1 H-NMR (CDCl 3,}} 400MHz) δ 8.13 (d, 1H), 8.06 (d, 1H), 7.98-7.91 (m, 3H), 7.81 (s, 1H), 7.68-7.52 (m, 11H), 7.43 (td, 1 H), 1.69 (s, 6 H).

11. Intermediate 6-11 - Synthesis of [N (biphenyl-4-yl ) -9,9-dimethyl-9 H -fluoren-2-amine]

[Reaction Scheme 11]

In 500 mL 2-neck round bottom flask 4-amino-biphenyl (50.0 mmol, 8.45g), 2- bromo-9,9-dimethyl -9 H - fluorene (50.0 mmol, 13.7g), Pd 2 (dba) ₃ (1.5 mmol, 1.35 g) and t- BuONa (100.0 mmol, 9.6 g) were charged and charged with nitrogen. To this was added 150 mL of toluene as a solvent and P ( t- Bu) ₃ (1.5 mmol, 0.3 g) was added thereto, followed by stirring at 90 ° C for 3 hours. When the reaction was completed, the temperature of the reaction solution was extracted with dichloromethane to room temperature. The obtained extract was dried with MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain Intermediate 6-11 as a yellow solid 14.1 g (Yield: 78%) was obtained.

12. Synthesis of Compound 6

[Reaction Scheme 12]

Intermediate 6-11 (25.0 mmol, 9.04 g), intermediate 6-10 (25.0 mmol, 14.0 g), Pd ₂ (dba) ₃ (0.75 mmol, 0.68 g), t- BuONa 75.0 mmol, 14.4 g) were charged and charged with nitrogen. 100 mL of toluene as a solvent was added thereto, and P ( t- Bu) ₃ (0.75 mmol, 0.15 g) was added thereto, followed by stirring at 110 ° C for 3 hours. When the reaction was completed, the temperature of the reaction solution was lowered to room temperature and extracted with dichloromethane. The obtained extract was dried with MgSO ₄ and dried under reduced pressure to obtain a crude product. The thus-obtained crude product was recrystallized from dichloromethane and acetonitrile, and then purified by silica gel column chromatography to obtain Compound 6 as yellow In solid form 15.1 g (Yield: 76%).

¹ H-NMR (CDCl ₃ , 400 MHz)? 8.16 (dd, 1 H), 8.10 (dd, 1 H), 7.98 (D, 2H), 6.77 (d, 2H), 7.27 (d, 1H), 7.65-7.58 (m, 12H), 7.43-7.36 (d, 2 H), 6.61 (d, 1 H), 1.70 (s, 6 H).

의 합성 Synthesis Example 2 : Compound 7

Synthesis of

1. Synthesis of Intermediate Compound 7-1 [4- (8,8-dimethyl- 5-phenyl-5,8-dihydroindeno [2, 1- c] carbazol-2-yl) aniline]

[Reaction Scheme 13]

500 mL round bottom flask 2 gu intermediate 6-9 (50 mmol, 24.9g), 4- amino-phenyl boronic acid (55 mmol, 7.53g), Pd (PPh 3) 4 (1.5 mmol, 1.74g), sodium hydroxide (150 mmol, 6.0 g), add 200 mL of tetrahydrofuran and 50 mL of water, reflux at 75 ° C for 12 hours after filling with nitrogen. When the reaction is completed, the reaction solution is cooled to room temperature and extracted with dichloromethane. The organic solvent layer is dried using MgSO _4, and the solvent is removed by drying under reduced pressure. The obtained reaction product was separated and purified by silica gel tube chromatography to obtain 15.3 g (yield: 68%) of Intermediate 7-1 as a yellow solid.

2. Synthesis of Compound 7

[Reaction Scheme 14]

(25.0 mmol, 11.3 g), 4-bromo-N, N-diphenyl aniline (50.0 mmol, 16.2 g) and Pd ₂ (dba) ₃ (0.75 mmol, 0.68 g) and t- BuONa (75.0 mmol, 14.4 g) were charged and charged with nitrogen. 100 mL of toluene as a solvent was added thereto, and P ( t- Bu) ₃ (0.75 mmol, 0.15 g) was added thereto, followed by stirring at 110 ° C for 3 hours. When the reaction was completed, the temperature of the reaction solution was lowered to room temperature and extracted with dichloromethane. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to obtain a crude product. The obtained crude product was recrystallized from dichloromethane and normal hexane and then purified by silica gel column chromatography to obtain Compound 7 as a yellow solid in 16.6 g (Yield: 71%) was obtained.

_{^{1 H-NMR (CDCl 3,}} 400MHz) δ 8.13 (dd, 1H), 8.07 (dd, 1H), 8.01 (d, 1H), 7.83-7.65 (m, 11H), 7.43 (td, 1H), 7.14 ( t, 4H), 6.86 (d, 2H), 6.61 (d, 8H), 6.56-6.43 (m, 8H), 1.73 (s, 6H).

의 합성 Synthesis Example 3 : Compound 30

Synthesis of

1. Synthesis of intermediate 30-1 [(2-bromophenyl) ( 9 H -carbazol-4-yl) methanone]

[Reaction Scheme 15]

Add a mixture of intermediate 6-2 (67.2 mmol, 16.5 g) in a 500 mL 2-necked round bottom flask and fill with nitrogen. And is added dropwise slowly and the mixture of furan in 300 mL of tetra hadid dissolved in a solvent and then at -78 ^{o C n -BuLi (2.5M in n} -Hexane soln., 70.6 mmol, 28.2 mL). Then, the temperature was raised to room temperature, and the mixture was stirred for 30 minutes. After the temperature was lowered to -78 ^° C, 2-bromobenzoyl chloride (67.2 mmol, 14.7 g) was slowly added dropwise to the solvent tetrahydrofuran. The temperature is raised to room temperature, and stirring is continued for another 2 hours. After the reaction was completed, the reaction mixture was extracted with dichloromethane, and the obtained extract was dried over MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain intermediate 30-1 as a yellow solid (Yield: 77%) of the title compound.

_{^{1 H-NMR (CDCl 3,}} 400MHz) δ 10.12 (s, 1H), 8.74 (s, 1H), 8.12 (d, 1H), 7.98 (d, 1H), 7.73-7.50 (m, 7H), 7.29 ( t, 1 H).

2. Synthesis of intermediate 30-2 [indeno [1, 2- c] carbazol-12 (5 H) -one]

[Reaction Scheme 16]

P (oAc) ₂ (0.86 mmol, 0.19 g) and P (o-tol) ₃ (1.71 mmol, 0.52 g) were added to a 1000 mL 2-necked round bottom flask, Lt; / RTI > Add 500 mL of dimethylformamide as a solvent and stir at 90 ^° C for 8 hours. When the reaction is completed, the temperature of the reaction solution is lowered to room temperature, ethanol is added thereto, and the precipitate is filtered. The obtained mixture was separated and purified by silica gel column chromatography to obtain Intermediate 30-2 as a white solid (Yield: 50%) of the title compound.

_{^{1 H-NMR (CDCl 3,}} 400MHz) δ 10.08 (s, 1H), 8.44-7.29 (m, 9H).

3. Synthesis of intermediate 30-3 [5-phenylindeno [1, 2-c] carbazol-12 (5 H) -one]

[Reaction Scheme 17]

(68.6 mmol, 18.5 g), bromobenzene (68.6 mmol, 10.8 g), Pd ₂ (dba) ₃ (2.06 mmol, 1.88 g), t- BuONa (205.7 mmol, 19.8 g) is charged and charged with nitrogen. Add 250 mL of toluene as a solvent, add P ( t- Bu) ₃ (6.86 mmol, 1.39 g), and stir at 110 ^° C for 3 hours. When the reaction is completed, the temperature of the reaction solution is lowered to room temperature and extracted with dichloromethane. The obtained extract was dried with MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was purified by silica gel column chromatography to obtain Intermediate 30-3 as a white solid (Yield: 76%) of the title compound.

4. Synthesis of intermediate 30-4 [5-phenyl-5,12- dihydroindeno [1, 2-c] carbazole]

[Reaction Scheme 18]

(50.0 mmol, 17.3 g) and LiAlH ₄ (150.0 mmol, 5.69 g) were added to a 500 mL two-neck round bottom flask, and 150 mL of tetrahydrofuran as a solvent was added thereto. The mixture was stirred at room temperature for 6 hours do. After the reaction was completed, an appropriate amount of hydrochloric acid was added, and the reaction solution was extracted with diethyl ether. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to obtain crude product, which was purified by silica gel column chromatography to obtain 9.45 g (yield: 57%) of intermediate 30-4 as a yellow solid.

5. Synthesis of Intermediate 30-5 [12,12-dimethyl-5-phenyl-5,12-dihydroindeno [ 1,2 - c] carbazole]

[Reaction Scheme 19]

Intermediate 30-4 (50.0 mmol, 16.6 g), iodomethane (110.0 mmol, 15.6 g) and potassium hydroxide (150 mmol, 8.42 g) were added to a 500 mL two-necked round bottom flask, and 150 mL of methanol Followed by stirring at room temperature for 3 hours. When the reaction was completed, the solvent, methanol, was removed with a concentrator, and then water and diethyl ether were added thereto and then extracted. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to obtain crude product. The crude product was separated and purified by silica gel column chromatography to obtain 15.8 g (yield: 88%) of Intermediate 30-5 as a yellow solid.

6. Synthesis of intermediate 30-6 [2-bromo-12,12- dimethyl-5-phenyl-5,12-dihydroindeno [1, 2- c] carbazole]

[Reaction Scheme 20]

50.0 mmol, 18.0 g) and NBS (52.5 mmol, 5.31 g) were added to a 500 mL two-necked round bottom flask, and 150 mL of dichloromethane was added as a solvent thereto, followed by stirring at room temperature for 5 hours. When the reaction was completed, dichloromethane as a solvent was diluted with an appropriate amount and extracted. The obtained extract was dried with MgSO ₄ and dried under reduced pressure to obtain a crude product. The resulting crude product was recrystallized from diethyl ether and n-hexane and purified by silica gel column chromatography to obtain intermediate 30-6 (Yield: 87%) as a yellow solid.

7. Synthesis of intermediate 30-7 [2- (4-iodophenyl) -12,12-dimethyl-5-phenyl-5,12-dihydroindeno [1, 2-c] carbazole]

[Reaction Scheme 21]

(50 mmol, 24.9 g), 4-iodophenylboronic acid (50 mmol, 12.4 g), Pd (PPh ₃ ) ₄ (1.5 mmol, 1.74 g), hydroxyl salt (150 mmol, 6.0 g), add 200 mL of tetrahydrofuran and 50 mL of water, reflux at 75 ° C for 12 hours after filling with nitrogen. When the reaction is completed, the reaction solution is cooled to room temperature and extracted with dichloromethane. The organic solvent layer is dried using MgSO _4, and the solvent is removed by drying under reduced pressure. The reaction product thus obtained was recrystallized from dichloromethane and normal hexane and then purified by silica gel column chromatography to obtain 23.9 g (yield: 86%) of Intermediate 30-7 as a yellow solid.

¹ H-NMR (CDCl ₃ , 400MHz) δ 8.15 (d, 1H), 8.03 (d, 1H), 7.93-7.86 7.43 (m, 10H), 7.31 (td, 1H), 1.73 (s, 6H).

8. Synthesis of Compound 30

[Reaction Scheme 22]

Intermediate 6-11 (25.0 mmol, 9.04 g), intermediate 30-7 (25.0 mmol, 14.0 g), Pd ₂ (dba) ₃ (0.75 mmol, 0.68 g), t- BuONa 75.0 mmol, 14.4 g) were charged and charged with nitrogen. 100 mL of toluene as a solvent was added thereto, and P ( t- Bu) ₃ (0.75 mmol, 0.15 g) was added thereto, followed by stirring at 110 ° C for 3 hours. When the reaction was completed, the temperature of the reaction solution was lowered to room temperature and extracted with dichloromethane. The obtained extract was dried over MgSO _{4 and} then dried under reduced pressure to obtain a crude product. The obtained crude product was recrystallized from dichloromethane and acetonitrile and purified by silica gel column chromatography to obtain Compound 30 In solid form 13.9 g (Yield: 70%) was obtained.

¹ H-NMR (CDCl ₃ , 400 MHz) 隆 8.09 (dd, 1 H), 8.02 (dd, 1 H), 7.84 2H), 6.74 (d, 2H), 6.74 (dd, 1H), 7.61-7.56 (m, 12H), 7.40-7.32 (d, 2 H), 6.63 (d, 1 H), 1.71 (s, 6 H).

의 합성 Synthesis Example 4: Synthesis of Compound 33

Synthesis of

1. Synthesis of Intermediate 33-1 [N -phenylnaphthalen-1-amine N - - (4-bromophenyl)]

[Reaction Scheme 23]

500 mL round bottom flask 2 gu N - phenyl-naphthalene-1-amine (50.0 mmol, 11.0g), 1- bromo-4-iodo-benzene (50.0 mmol, 14.1g), Pd 2 (dba) 3 (1.5 mmol, 1.35 g) and t- BuONa (100.0 mmol, 9.6 g) were charged and charged with nitrogen. To this was added 150 mL of toluene as a solvent and P ( t- Bu) ₃ (1.5 mmol, 0.3 g) was added thereto, followed by stirring at 110 ° C for 2 hours. When the reaction was completed, the temperature of the reaction solution was extracted with dichloromethane to room temperature. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to obtain crude product. The crude product was separated and purified by silica gel column chromatography to obtain Intermediate 33-1 (12.0 g, Yield: 64%) as a yellow solid.

2. Synthesis of intermediate 33-2 [N -phenylnaphthalen-1-amine N - - (4-bromophenyl)]

[Reaction Scheme 24]

(50.0 mmol, 18.7 g), aniline (50.0 mmol, 4.65 g), Pd ₂ (dba) ₃ (1.5 mmol, 1.35 g), t- BuONa (100.0 mmol, 9.6 g) was charged and charged with nitrogen. To this was added 150 mL of toluene as a solvent and P ( t- Bu) ₃ (1.5 mmol, 0.3 g) was added thereto, followed by stirring at 110 ° C for 2 hours. When the reaction was completed, the temperature of the reaction solution was extracted with dichloromethane to room temperature. The obtained extract was dried with MgSO ₄ and dried under reduced pressure to obtain crude product. The crude product was separated and purified by silica gel column chromatography to obtain 13.3 g (yield: 69%) of intermediate 33-2 as a yellow solid.

3. Synthesis of Compound 33

[Reaction Scheme 25]

(25.0 mmol, 9.66 g), Intermediate 30-7 (25.0 mmol, 14.0 g), Pd ₂ (dba) ₃ (0.75 mmol, 0.68 g), t- BuONa 75.0 mmol, 14.4 g) were charged and charged with nitrogen. 100 mL of toluene as a solvent was added thereto, and P ( t- Bu) ₃ (0.75 mmol, 0.15 g) was added thereto, followed by stirring at 110 ° C for 3 hours. When the reaction was completed, the temperature of the reaction solution was lowered to room temperature and extracted with dichloromethane. The obtained extract was dried with MgSO ₄ and dried under reduced pressure to obtain a crude product. The resulting crude product was recrystallized from dichloromethane and acetonitrile and purified by silica gel column chromatography to obtain Compound 33 as yellow In solid form (Yield: 73%) of the title compound.

_{^{1 H-NMR (CDCl 3,}} 400MHz) δ 8.13 (dd, 1H), 8.10-8.01 (m, 4H), 7.91 (d, 1H), 7.83 (s, 1H), 7.70-7.43 (m, 14H), 1H), 6.74 (d, 2H), 7.28 (t, 2H), 7.08 (d, (d, 2H), 6.59 (d, 2H), 6.47 (d, 2H), 6.31 (d, 2H), 1.75 (s, 6H).

의 합성 Synthesis Example 5: Compound 47

Synthesis of

1. Synthesis of intermediate 47-1 [9-phenyl-3- ( 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9 H -carbazole]

[Reaction Scheme 26]

1000 mL 2 gu round bottom flask 3-iodo-9-phenyl -9 H - carbazole (100.0 mmol, 36.9g), bis Pina kolreyi Todi boron (150.0 mmol, 38.1g), PdCl 2 (dppf) (3.0 mmol, 2.45 g) and potassium acetate (300.0 mmol, 29.4 g) were charged and charged with nitrogen. 500 mL of dimethylformamide as a solvent was added thereto, followed by stirring at 80 DEG C for 3 hours. The temperature of the reaction solution was lowered to room temperature and extracted with dichloromethane. The obtained extract was dried with MgSO ₄ and dried under reduced pressure to obtain crude product. The crude product was separated and purified by silica gel column chromatography to obtain 22.9 g (yield: 62%) of Intermediate 47-1 as a yellow solid.

2. Synthesis of intermediate 47-2 [methyl 2- (9-phenyl -9 H -carbazol-3-yl) benzoate]

[Reaction Scheme 27]

(100.0 mmol, 36.9 g), 2-bromomethylbenzoate (100.0 mmol, 21.5 g), Pd (PPh ₃ ) ₄ (3.0 mmol, 3.47 g), potassium Carbonate (300.0 mmol, 41.5 g), 400 mL of tetrahydrofuran as a solvent and 100 mL of water are added, followed by stirring at 80 ° C for 6 hours. The temperature of the reaction solution was lowered to room temperature and extracted with dichloromethane. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was separated and purified by silica gel column chromatography to obtain 26.0 g (yield: 69%) of Intermediate 47-2 as a yellow solid.

3. Synthesis of intermediate 47-3 [3-phenylindeno [2, 1-b] carbazol-1 (3 H) -one]

[Reaction Scheme 28]

(50.0 mmol, 18.9 g), methanesulfonic acid (50.0 mmol, 4.8 g) and polyphosphoric acid (0.5 M, 100.0 mL) were placed in a 250 mL two-necked round bottom flask and refluxed at 200 ° C. for 48 hours . The temperature of the reaction solution was lowered to room temperature and extracted with diethyl ether. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to obtain crude product. The crude product was separated and purified by silica gel column chromatography to obtain 5.87 g (yield: 34%) of intermediate 47-3 as a yellow solid.

4. Synthesis of intermediate 47-4 [3-phenyl-1,3- dihydroindeno [2, 1-b] carbazole]

[Reaction Scheme 29]

(50.0 mmol, 17.3 g) and LiAlH ₄ (150.0 mmol, 5.69 g) were added to a 500 mL two-neck round bottom flask, and 150 mL of tetrahydrofuran as a solvent was added thereto. The mixture was stirred at room temperature for 6 hours do. After the reaction was completed, an appropriate amount of hydrochloric acid was added, and the reaction solution was extracted with diethyl ether. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was separated and purified by silica gel column chromatography to obtain 11.4 g (yield: 69%) of intermediate 47-4 as a yellow solid.

5. Synthesis of Intermediate Compound 47-5 [1,1-dimethyl-3- phenyl-1,3-dihydroindeno [2, 1- b] carbazole]

[Reaction Scheme 30]

Intermediate 47-4 (50.0 mmol, 16.6 g), iodomethane (110.0 mmol, 15.6 g) and potassium hydroxide (150 mmol, 8.42 g) were added to a 500 mL two-necked round bottom flask, and 150 mL of methanol Followed by stirring at room temperature for 3 hours. When the reaction was completed, the solvent, methanol, was removed with a concentrator, and then water and diethyl ether were added thereto and then extracted. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to obtain a crude product. The crude product was separated and purified by silica gel column chromatography to obtain 12.9 g (yield: 72%) of intermediate 47-5 as a yellow solid.

6. Synthesis of intermediate 47-6 [6-bromo-1,1- dimethyl-3-phenyl-1,3-dihydroindeno [2, 1- b] carbazole]

[Reaction Scheme 31]

Into a 500 mL 2-necked round bottom flask, add intermediate 47-5 (50.0 mmol, 18.0 g) and NBS (52.5 mmol, 5.31 g), add 150 mL of dichloromethane as a solvent thereto, and stir at room temperature for 5 hours. When the reaction was completed, dichloromethane as a solvent was diluted with an appropriate amount and extracted. The resulting extract was dried over MgSO _{4 and} then dried under reduced pressure to obtain a crude product. The obtained crude product was recrystallized from diethyl ether and n-hexane and purified by silica gel column chromatography to obtain intermediate 47-6 (Yield: 64%) as a yellow solid.

7. Synthesis of intermediate 47-7 [6- (4-iodophenyl) -1,1-dimethyl-3-phenyl-1,3-dihydroindeno [2, 1-b] carbazole]

[Reaction Scheme 32]

500 mL 2 gu Intermediate 47-6 (50 mmol, 21.9g) in a round bottom flask, 4-iodo phenyl boronic acid (50 mmol, 12.4g), Pd (PPh 3) 4 (1.5 mmol, 1.74g), hydroxide salt (150 mmol, 6.0 g) was added, and 200 mL of tedrahydrofuran and 50 mL of water were added. After the addition of nitrogen, the mixture was refluxed at 90 ° C. for 12 hours. When the reaction is completed, the reaction solution is cooled to room temperature and extracted with dichloromethane. The organic solvent layer is dried using MgSO _4, and the solvent is removed by drying under reduced pressure. The reaction product thus obtained was recrystallized from dichloromethane and n-hexane and then purified by silica gel column chromatography to obtain 22.7 g (yield: 81%) of Intermediate 47-7 as a yellow solid.

_{^{1 H-NMR (CDCl 3,}} 400MHz) δ 8.11 (d, 1H), 8.02 (dd, 1H), 7.93 (d, 1H), 7.88 (d, 2H), 7.73 (s, 1H), 7.66 (s, 1H), 7.54-7.42 (m, 9H), 7.36 (s, IH), 7.29 (td, IH), 1.74 (s, 6H).

8. Synthesis of intermediate 47-8 [ N- phenyldibenzo [ b , d ] thiophen-2-amine]

[Reaction Scheme 33]

Bromodibenzo [ b , d ] thiophene (50.0 mmol, 13.2 g), aniline (50.0 mmol, 4.66 g) and Pd ₂ (dba) ₃ (1.5 mmol, 1.35 g) in a 500 mL two- , t- BuONa (100.0 mmol, 9.6 g) were charged and charged with nitrogen. To this was added 150 mL of toluene as a solvent and P ( t- Bu) ₃ (1.5 mmol, 0.3 g) was added thereto, followed by stirring at 90 ° C for 3 hours. When the reaction was completed, the temperature of the reaction solution was extracted with dichloromethane to room temperature. The obtained extract was dried over MgSO ₄ and dried under reduced pressure to obtain crude product. The crude product was separated and purified by silica gel column chromatography to obtain 7.43 g (yield: 54%) of Intermediate 47-8 as a yellow solid.

9. Synthesis of Compound 47

[Reaction Scheme 34]

Intermediate 47-8 (25.0 mmol, 6.88 g), Intermediate 47-7 (25.0 mmol, 14.0 g), Pd ₂ (dba) ₃ (0.75 mmol, 0.68 g), t- BuONa 75.0 mmol, 14.4 g) were charged and charged with nitrogen. 100 mL of toluene as a solvent was added thereto, and P ( t- Bu) ₃ (0.75 mmol, 0.15 g) was added thereto, followed by stirring at 110 ° C for 3 hours. When the reaction was completed, the temperature of the reaction solution was lowered to room temperature and extracted with dichloromethane. The obtained extract was dried with MgSO ₄ and dried under reduced pressure to obtain a crude product. The obtained crude product was recrystallized from dichloromethane and acetonitrile, and then purified by silica gel column chromatography to obtain 47 (Yield: 75%) as a solid.

¹ H-NMR (CDCl ₃ , 400 MHz) 隆 8.32 (d, 1 H), 8.13 (dd, 1 H), 8.07 1H), 7.68 (d, 1H), 7.61 (s, 1H), 7.53-7.41 (m, 12H), 7.36 , 6.81 (d, 2H), 6.76 (d, 2H), 1.76 (s, 6H).

[ Hole injection layer Comparative Example  And Example ]

[ Comparative Example 1] Measurement of physical properties of an organic electroluminescent device using 2- TNATA as a hole injection layer for comparison with the compounds 7, 33 and 47 of the present invention

An organic electroluminescent device was fabricated according to a conventional method using 4,4 ', 4 "-Tris [2-naphthyl (phenyl) amino] -triphenylamine (2-TNATA) as a hole injection layer material. (Hole injection layer material: 2-TNATA) having a thickness of 600 Å, a hole transport layer (hole transport layer material: NPB) having a thickness of 300 Å and a BD-052X (Idemitsu Co.) having a thickness of 450 Å were formed on the ITO layer (anode) ) Was a 7% doped luminescent layer (BD-052X was a blue fluorescent dopant and 9,10-di (naphthalene-2-yl) anthracene (ADN) was used as a luminescent host material) The electron transport layer (electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), an electron injection layer (electron injection layer material: LiF) 10 Å thick and an aluminum cathode An electroluminescent device was fabricated.

The color coordinates, luminance, and luminous efficiency of the organic electroluminescent device were examined. As a result, the current density was 13.28 mA / cm ² at a DC voltage of 7.2 V, the color coordinate was (0.15, 0.15), and the luminous efficiency was 7.4 cd / A.

[ Example 1] Measurement of physical properties of an organic electroluminescent device using Compound 7 of the present invention as a hole injection layer

An organic electroluminescent device was fabricated according to a conventional method using Compound 7 as a hole injection layer material. First, a hole injecting layer (hole injecting layer material: compound 7) having a thickness of 600 Å, a hole transporting layer (hole transporting layer material: NPB) having a thickness of 300 Å and a BD-052X having a thickness of 450 Å were formed on an ITO layer (anode) (Idemitsu) used a light emitting layer doped with 7% (where BD-052X was a blue fluorescent dopant and 9,10-di (naphthalene-2-yl) anthracene (ADN) was used as a light emitting host material) (Electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), a 10 Å thick electron injection layer (electron injection layer material: LiF) and a 1500 Å thick aluminum cathode And an organic electroluminescent device was fabricated.

The color coordinates, luminance, and luminous efficiency of the organic electroluminescent device were investigated. As a result, the current density was 14.69 mA / cm ² at a direct current voltage of 5.8 V, the color coordinates were (0.15, 0.14) and the luminous efficiency was 8.8 cd / A.

[ Example 2] Measurement of physical properties of organic electroluminescent device using Compound 33 of the present invention as a hole injection layer

An organic electroluminescent device was fabricated according to a conventional method using Compound 33 as a hole injection layer material. First, a hole injection layer (hole injection layer material: compound 33) having a thickness of 600 A, a hole transport layer (hole transport layer material: NPB) having a thickness of 300 A, a BD-052X (Idemitsu) used a light emitting layer doped with 7% (where BD-052X was a blue fluorescent dopant and 9,10-di (naphthalene-2-yl) anthracene (ADN) was used as a light emitting host material) (Electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), a 10 Å thick electron injection layer (electron injection layer material: LiF) and a 1500 Å thick aluminum cathode And an organic electroluminescent device was fabricated.

The color coordinates, luminance, and luminous efficiency of the organic electroluminescent device were examined. As a result, the current density was 14.32 mA / cm ² at a DC voltage of 6.3 V, the color coordinates were (0.15, 0.154) and the luminous efficiency was 8.3 cd / A.

[ Example 3] Measurement of physical properties of an organic electroluminescent device using the compound 47 of the present invention as a hole injection layer

An organic electroluminescent device was fabricated according to a conventional method using Compound 47 as a hole injection layer material. First, a hole injection layer (hole injection layer material: compound 47) having a thickness of 600 Å, a hole transport layer (hole transport layer material: NPB) having a thickness of 300 Å, and a BD-052X having a thickness of 450 Å were formed on an ITO layer (anode) (Idemitsu) used a light emitting layer doped with 7% (where BD-052X was a blue fluorescent dopant and 9,10-di (naphthalene-2-yl) anthracene (ADN) was used as a light emitting host material) (Electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), a 10 Å thick electron injection layer (electron injection layer material: LiF) and a 1500 Å thick aluminum cathode And an organic electroluminescent device was fabricated.

The color coordinates, luminance, and luminous efficiency of the organic electroluminescent device were investigated. As a result, the current density was 13.86 mA / cm ² at a DC voltage of 7.9 V, the color coordinate was (0.15, 0.14) and the luminous efficiency was 7.9 cd / A.

The hole injection layer
material Voltage
(V) Current density
(mA / cm ² ) Luminous efficiency
(cd / A) Chromaticity coordinates
(x, y) Example 1 Compound 7 5.8 14.69 8.8 (0.15, 0.14) Example 2 Compound 33 6.3 14.32 8.3 (0.15, 0.154) Example 3 Compound 47 7.9 13.86 7.9 (0.15, 0.14) Comparative Example 1 2-TNATA 7.2 13.28 7.4 (0.15, 0.15)

[ Hole transport layer Comparative Example  And Example ]

[ Comparative Example 1] For comparison with the compounds 6, 30 and 47 of the present invention, a hole transport layer Measurement of physical properties of organic electroluminescent device using NPB

^{N 4, N 4 '-di (} naphthalen-1-yl) - N 4, N 4' organic electroluminescent device according to a conventional method using -diphenylbiphenyl-4,4'-diamine (NPB) as the hole transport layer material, Respectively. First, a hole injection layer (hole injection layer material: 2-TNATA) having a thickness of 600 Å, a hole transport layer (NPB) having a thickness of 300 Å and a hole transport layer (NPB) having a thickness of 450 Å were formed on an ITO layer (anode) 052X (Idemitsu Co.) was 7% doped with a blue fluorescent dopant and 9,10-di (naphthalene-2-yl) anthracene (ADN) (Electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )) having a thickness of 10 Å, an electron injection layer (electron injection layer material: LiF) having a thickness of 10 Å and an aluminum cathode And an organic electroluminescent device was fabricated.

The color coordinates, luminance, and luminous efficiency of the organic electroluminescent device were examined. As a result, the current density was 13.47 mA / cm ² at a DC voltage of 7.1 V, the color coordinates were (0.15, 0.15) and the luminous efficiency was 7.5 cd / A.

[ Example 1] Measurement of physical properties of an organic electroluminescent device using Compound 6 of the present invention as a hole transport layer

An organic electroluminescent device was fabricated according to a conventional method using Compound 6 as a hole transport layer material. First, a hole injecting layer (hole injecting layer material: 2-TNATA) having a thickness of 600 Å, a hole transporting layer (hole transporting layer material: compound 6) having a thickness of 300 Å, a BD having a thickness of 450 Å were formed on an ITO layer (anode) (BDN-052X) was a blue fluorescent dopant, 9,10-di (naphthalene-2-anthracene (ADN) was used as a luminescent host material), 250 Å (Electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), a 10 Å thick electron injection layer (electron injection layer material: LiF) and a 1500 Å thick aluminum cathode And an organic electroluminescent device was fabricated.

The color coordinates, luminance and luminous efficiency of the organic electroluminescence device were examined. As a result, the current density was 14.06 mA / cm ² at a direct current voltage of 5.9 V, the color coordinate was (0.15, 0.14) and the luminous efficiency was 8.2 cd / A.

[ Example 2] Measurement of physical properties of an organic electroluminescent device using Compound 30 of the present invention as a hole transport layer

An organic electroluminescent device was fabricated according to a conventional method using Compound 30 as a hole transport layer material. First, a hole injection layer (hole injection layer material: 2-TNATA) having a thickness of 600 Å, a hole transport layer (hole transport layer material: compound 30) having a thickness of 300 Å, a BD having a thickness of 450 Å, an ITO layer (anode) (BDN-052X) was a blue fluorescent dopant, 9,10-di (naphthalene-2-anthracene (ADN) was used as a luminescent host material), 250 Å (Electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), a 10 Å thick electron injection layer (electron injection layer material: LiF) and a 1500 Å thick aluminum cathode And an organic electroluminescent device was fabricated.

The color coordinates, luminance, and luminous efficiency of the organic electroluminescent device were examined. As a result, the current density was 14.38 mA / cm ² at a direct current voltage of 5.6 V, the color coordinates were (0.15, 0.15) and the luminous efficiency was 9.0 cd / A.

[ Example 3] Measurement of physical properties of an organic electroluminescent device using the compound 47 of the present invention as a hole transport layer

An organic electroluminescent device was fabricated according to a conventional method using Compound 47 as a hole transport layer material. First, a hole injection layer (hole injection layer material: 2-TNATA) having a thickness of 600 Å, a hole transport layer (hole transport layer material: compound 47) having a thickness of 300 Å, and a BD having a thickness of 450 Å were formed on an ITO layer (anode) (BDN-052X) was a blue fluorescent dopant, 9,10-di (naphthalene-2-anthracene (ADN) was used as a luminescent host material), 250 Å (Electron transport layer material: tris (8-quinolinolato) aluminum (Alq ₃ )), a 10 Å thick electron injection layer (electron injection layer material: LiF) and a 1500 Å thick aluminum cathode And an organic electroluminescent device was fabricated.

The color coordinates, brightness and luminous efficiency of the organic electroluminescent device were examined. As a result, the current density was 13.76 mA / cm ² at a DC voltage of 6.3 V, the color coordinate was (0.15, 0.15) and the luminous efficiency was 7.7 cd / A.

Hole transport layer
material Voltage
(V) Current density
(mA / cm ² ) Luminous efficiency
(cd / A) Chromaticity coordinates
(x, y) Example 1 Compound 6 5.9 14.06 8.2 (0.15, 0.14) Example 2 Compound 30 5.6 14.38 9.0 (0.15, 0.15) Example 3 Compound 47 6.3 13.76 7.7 (0.15, 0.15) Comparative Example 1 NPB 7.1 13.47 7.5 (0.15, 0.15)

As can be seen from the results of Table 1 and Table 2, the organic electroluminescent device using the organic electroluminescent device material of the present invention has high efficiency and improved color purity as well as superior current density characteristics, so that low voltage, The characteristics of the organic electroluminescent device can be remarkably improved.

It is apparent that the same effects can be obtained even when the compounds of the present invention are used for other organic layers of an organic electroluminescent device, for example, an electron injecting layer, an electron transporting layer, and a light emitting layer as well as a hole injecting layer and a hole transporting layer.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention is not limited by these embodiments.

The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of the same should be construed as being included in the scope of the present invention.

Claims (12)

A compound represented by the following formula:

In the above formulas,
(1) wherein R ₁ and R ₂ are each independently selected from the group consisting of a C _1-20 alkyl group and a C _6-30 aryl group, and each of R ₃ is independently selected from the group consisting of a hydrogen atom, C _{6 -30} aryl group, -N (R _{7) 2,} or -N (R ₇₎ and (R ₈₎ may be one selected from the group consisting of an amino group represented by the R ₄ and R ₆ is a hydrogen atom, the R ₅ are each substituted with an alkyl group, independently of each other or of a C _6-30 unsubstituted aryl group, -N (R _{7) 2,} or _{-N (R 7) (R 8} ) a C _6- amino group is substituted, represented by An aryl group having 1 to ₃₀ carbon atoms,
(2) wherein A and B is a C _6-30 arylene group, the C and E is an aryl group of C _6-30, the D and F is a C _6- substituted or unsubstituted alkyl groups each independently of the other _30-aryl, -N (R _{7) 2,} or -N (R ₇₎ and an amino group represented by (R ₈₎ may be one selected from the group consisting of aryl groups of the substituted C _6-30,
R ₇ to R ₈ each independently represent a C _4-60 aryl group substituted or unsubstituted with an alkyl group,
(3) X must be one of N, O, and S,
(4) wherein a is an integer of 0 to 4, b is an integer of 0 to 2, c is an integer of 0 to 3, and 1 to q are integers of 0 to 4, n + o + p + q? 1, and when X is O or S, p and q are 0. delete The method according to claim 1,
(1) wherein R ₁ and R ₂ are each independently one of a methyl group and a phenyl group, each of R ₃ is independently a hydrogen atom, a phenyl group, -N (R ₇ ) (R ₈ ) ₅ are each independently a phenyl group, a naphthyl group, a fluorenyl group or a phenyl group substituted with -N (R ₇ ) (R ₈ ), R ₄ and R ₆ are the same as in claim 1,
(2) the A and B are each independently one of a phenylene group and a biphenylene group, and each of C and E independently represents a phenylene group, a biphenylene group, a naphthylene group, a phenanthryl group, a fluorenylene group _{, -N (R 7) (R} 8) a is one of the phenylene groups, the D and F, phenanthryl group, fluorenyl group, -N (R ₇ each independently represent a phenyl group and a biphenyl group, a naphthyl group, each optionally substituted with ) ≪ / RTI > (R < ₈ >),
(3) The compound according to (1), wherein R ₇ to R ₈ are one of a phenyl group and a fluorenyl group. The method according to claim 1,
Wherein said compound is one selected from the following group.

A first electrode; A second electrode; And an organic material layer disposed between the first electrode and the second electrode,
Wherein the organic material layer contains the compound of any one of claims 1 to 3. 6. The method of claim 5,
Wherein the organic compound layer is formed by a solution process of the compound. 6. The method of claim 5,
Wherein the organic material layer is any one of a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer. 6. The method of claim 5,
Wherein the organic material layer is a hole injection layer or a hole transport layer. 6. The method of claim 5,
Wherein the organic layer includes a light emitting layer,
Wherein the compound is used as a phosphorescent host material in the light emitting layer. A display device including the organic electroluminescent device of claim 5;
And a control unit for driving the display device. 11. The method of claim 10,
The organic electric device may be an organic electroluminescent (OLED), an organic solar cell, an organic photoconductor (OPC) drum, an organic TFT, a photodiode, an organic laser, a laser diode The terminal being one of the plurality of terminals. delete

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