KR20130113115A - Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof - Google Patents

Abstract

PURPOSE: A compound for an organic electronic device is provided to largely improve light emitting efficiency, thermal resistance, color purity, and lifetime with low driving voltage using six-membered heterocyclic compounds containing nitrogen. CONSTITUTION: A compound for an organic electronic device contains a compound of chemical formula 1. The organic electronic device comprises one or more organic layers containing the compounds. The organic layers are formed of the compounds by a solution process. The organic electronic device comprises a first electrode, the organic layers, and a second electrode. The organic layers include one or more among a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, and an electron transport layer.

Description

Compound for organic electric device including hexagonal heterocyclic compound containing nitrogen, organic electronic device using same and electronic device thereof TECHNICAL FIELD USING THE SAME

The present invention relates to a compound for an organic electric device comprising a six-membered heterocyclic compound containing nitrogen, an organic electric device comprising the same, and an electronic device thereof.

Mr. Eastman Kodak Corporation in the 1980s. W. C. W. Tang et al. Developed a laminated structure element in which various roles were distributed to each material, thereby making organic electroluminescent elements using organic materials practical. They stacked phosphors that could transport electrons and organics that could transport holes, and injected both charges into a layer of the phosphor to emit light, so that high brightness of 1000 cd / m2 or more could be obtained at a voltage of 10 V or less. .

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 is often formed of a multilayer 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.

Materials used as the organic material layer in the organic electric element may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, electron injection materials, and the like, depending on their 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 . In addition, the light emitting material may be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to achieve a better natural color according to the light emitting color.

In particular, various studies have been conducted on organic materials inserted into the hole transport layer or the buffer layer for excellent life characteristics of the organic electric device, and for this purpose, a thin film after deposition is provided while providing high hole transport characteristics from the anode to the organic layer. There is a need for a hole injection layer material having high uniformity and low crystallinity in forming.

Delays penetration of metal oxide into the organic layer from the anode electrode (ITO), which is one of the causes of the shortening of the life of the organic electric device, and stable properties for Joule heating generated when driving the device, that is, high glass transition temperature. There is a need for development of a hole injection layer material having In addition, the low glass transition temperature of the hole transport layer material has been reported to have a significant effect on the device life, depending on the characteristics of the uniformity of the surface of the thin film when driving the device. In addition, the deposition method is the mainstream in the formation of the OLED device, a situation that requires a material that can withstand a long time, that is, a material having a strong heat resistance characteristics.

On the other hand, when only one material is used as the light emitting material, the maximum emission wavelength is shifted to a long wavelength due to the intermolecular interaction, and the color purity decreases or the efficiency of the device decreases due to the emission attenuation effect. In order to increase the light emitting efficiency through the light emitting material, a host / dopant system may be used. 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 fully exhibit the excellent characteristics of the above-described organic electroluminescent device, a material constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. Although this should be preceded, the development of a stable and efficient organic material layer for an organic electric element has not yet been made sufficiently, and therefore, the development of new materials is continuously required.

An object of the present invention is to provide a six-membered heterocyclic ring compound containing nitrogen that can improve the high luminous efficiency, low driving voltage, high heat resistance, color purity and lifetime of the device, an organic electric device using the same, and a terminal thereof .

In the present invention, the carbazole is a planar compound, while the hexagonal heterocyclic compound including nitrogen specified in the present invention has a dihedral angle of about 153 ° at the base state based on NX. In this state, the backside angle is almost 180 °, forming a plane. J. Phys. Chem. A 1999, 103, 4737-4743. This property is more stable to external energy and leads to stabilization of life in device driving as compared to a compound having a hard planar structure.

Specifically, the present invention is represented by the following formula 1 to solve the problems of the prior art described above, and to achieve the object of the present invention to improve the luminous efficiency, low driving voltage, high heat resistance, color purity, stability and life of the device To provide a compound.

또는

.Where A is

or

.

In the above formulas,

(1) X is O, S, CR'R ", SiR'R". here,

R ' and R ” each independently represent a halogen group, a C ₁ to C ₆₀ alkyl group, a C ₁ to C ₆₀ alkoxy group, a C ₁ to C ₆₀ alkylamine group, a C ₆ to C ₆₀ arylamine group, C ₁ ~ C ₆₀ Alkylthiophene group, C ₆ ~ C ₆₀ Aryl thiophene group, C ₂ ~ C ₆₀ Alkenyl group, C ₂ ~ C ₆₀ Alkynyl group, C ₃ ~ C ₆₀ Cycloalkyl group, C of ₆ ~ C ₆₀ aryl group, a C ₆ ~ C ₆₀ substituted with a heavy hydrogen of the aryl group, a C ₈ ~ C ₆₀ aryl alkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted hwandoen germanium group, and a substituted or non-substituted substituted or unsubstituted with substituents selected from the group consisting of a heterocycle of the unsubstituted C ₂ ~ C ₂₀ An aryl group of C ₆ ~ C _60;

C ₁ ~ alkenyl group of the C ₂₀ alkyl group, C ₂ ~ C ₂₀ of, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ aryl group of C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with deuterium, C ₇ C ₁ ~ C ₅₀ alkyl group unsubstituted or substituted with a substituent selected from the group consisting of-C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group ;

Halogen, CN, NO ₂ , C ₁ ~ C ₆₀ alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkylamine group, C ₆ ~ C ₆₀ arylamine group, C ₁ ~ C ₆₀ Alkylthiophene group, C ₂ ~ C ₆₀ alkenyl group, C ₂ ~ C ₆₀ alkynyl group, C ₃ ~ C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₆ ~ C ₆₀ substituted with deuterium Substituted by a substituent selected from the group consisting of an aryl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and a substituted or unsubstituted C ₂ ~ C ₂₀ heterocyclic group Or a C ₂ ~ C ₆₀ heterocyclic group which is unsubstituted and contains at least one heteroatom of O, N, or S ; And

A C ₆ ~ C ₆₀ of aliphatic rings in the aromatic ring and C ₃ ~ C ₆₀ Condensed ring group ; Is selected from the group consisting of

(2) R ₁ to R ₁₀ are each independently hydrogen; heavy hydrogen; Tritium; Halogen group ;

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C arylalkyl group of _{7 ~ C 20, C 8 ~} C 20 aryl alkenyl group, C ₂ ~ C ₂₀ of the heterocyclic group, the in nitrile group and acetylene group the group consisting of unsubstituted or substituted with substituent C ₁ ~ C ₅₀ Alkyl group ;

Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ C ₂₀ -C20 arylthiophene group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, deuterated C ₆ to C ₂₀ aryl group, a C ₈ - C ₂₀ aryl alkenyl group, a silane group, a boron group, a germanium group, a C ₂ ~ C ₂₀ unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic C ₆ to an aryl group of C _60;

Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and C ₂ ~ C ₆₀ heterocyclic group which is unsubstituted or substituted with a substituent selected from the group consisting of acetylene groups, and containing at least one hetero atom of O, N, S, Si, P ;

Hydrogen, deuterium, tritium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₂ ~ C ₆₀ unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic C ₆ ~ C ₆₀ arylamine group;

Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and with a substituent selected from the group consisting of acetylene substituted or unsubstituted C ₂ ~ C ₂₀ alkenyl;

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group group substituents a substituted or unsubstituted C ₁ ~ C ₃₀ selected from the consisting of Alkoxy group ; And

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group group substituted with substituted or unsubstituted C ₆ ~ C ₃₀ selected from the consisting of aryloxy; Is selected from the group consisting of

(3) L is composed of nitro, nitrile, halogen, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₆ -C ₂₀ aryl group, C ₂ -C ₂₀ heterocyclic group, amino group substituted with a substituent selected from the group or unsubstituted arylene group, a C ₆ ~ C _60;

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, Substituted with a substituent selected from the group consisting of C ₇ -C ₂₀ arylalkyl group, C ₈ -C ₂₀ arylalkenyl group, C ₁ -C ₅₀ alkyl group, C ₂ -C ₂₀ heterocyclic group, nitrile group and acetylene group or Unsubstituted fluorenylene group ;

A substituent selected from the group consisting of nitro, nitrile, halogen, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₆ -C ₂₀ aryl group, C ₂ -C ₂₀ heterocyclic group and amino group Substituted or unsubstituted C ₃ ~ C ₆₀ Hetero arylene group ; And

Divalent substituted or unsubstituted aliphatic hydrocarbons; Is selected from the group consisting of

(4) Ar ₁ and Ar ₂ are each independently hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₁ -C ₂₀ alkylthiophene group, C ₆ -C ₂₀ arylthiophene group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₃ -C ₂₀ cycloalkyl group, C of ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, a C ₈ ~ C ₂₀ arylalkenyl group, a silane group, a boron group, a germanium group, consisting of a heterocycle of the C ₂ ~ C ₂₀ of an aryl group unsubstituted or substituted with a substituent selected from the group C ₆ ~ C _60;

Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and C ₂ ~ C ₆₀ heterocyclic group which is unsubstituted or substituted with a substituent selected from the group consisting of acetylene groups, and containing at least one hetero atom of O, N, S, Si, P ;

Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and with a substituent selected from the group consisting of acetylene substituted or unsubstituted C ₂ ~ C ₂₀ alkenyl;

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group group substituents a substituted or unsubstituted C ₁ ~ C ₃₀ selected from the consisting of Alkoxy group ;

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C arylalkyl group of _{7 ~ C 20, C 8 ~} C 20 aryl alkenyl group, C ₂ ~ C ₂₀ of the heterocyclic group, the in nitrile group and acetylene group the group consisting of unsubstituted or substituted with substituent C ₁ ~ C ₅₀ Alkyl group ; And

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, Substituted with a substituent selected from the group consisting of C ₇ -C ₂₀ arylalkyl group, C ₈ -C ₂₀ arylalkenyl group, C ₁ -C ₅₀ alkyl group, C ₂ -C ₂₀ heterocyclic group, nitrile group and acetylene group or Unsubstituted fluorene group ; Is selected from the group consisting of

(5) R ₁ to R ₁₀ may be bonded or reacted with groups adjacent to each other to form a substituted or unsubstituted saturated or unsaturated ring. In addition, Ar ₁ , Ar ₂ It is also possible to combine or react with adjacent groups to form a substituted or unsubstituted saturated or unsaturated ring. Here, the adjacent group may be a substituent such as R ₁ to R ₁₀ , R ′, R ″, Ar ₁ , Ar _2, or the like, may be a mother nucleus (parent), or may be another substituent bonded to the mother nucleus.

In addition, the present invention provides a compound represented by any one of the following formula (2) to (5) to achieve the above object.

In Chemical Formulas 2 to 5,

R ₁ to R ₁₀ , X, Ar ₁ , Ar ₂ are the same as R ₁ to R _{10 ,} X, Ar ₁ and Ar ₂ as defined in Formula (1).

As used herein, an "aryl group" refers to a monocyclic or heterocyclic aromatic, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a spirobifluorene group.

In addition, a "heterocyclic group" means an aromatic or alicyclic monocyclic or heterocyclic ring containing a heteroatom (heteroatom) instead of a carbon forming a ring, a hetero formed by neighboring substituents participating in the bond or reaction Aromatic or cycloaliphatic rings.

More specifically, Chemical Formulas 1 to 5 may be one of the following compounds, but are not limited thereto.

The compounds represented by Formula 1 to Formula 5 may be one of the compounds shown above, but are not limited thereto. In this case, since it is practically difficult to exemplify all compounds in a wide relationship with each substituent of the compounds represented by Formulas 1 to 5, the exemplary compounds have been exemplarily described, but the compounds represented by Formulas 1 to 5 not shown Part of this specification may be constituted.

In still another aspect, the present invention provides an organic electric element using the compound represented by the above formula and an electronic device including the organic electric element.

By using the hexagonal heterocyclic compound containing nitrogen according to the present invention exhibits the effect of greatly improving the high luminous efficiency, low driving voltage, high heat resistance, color purity and life of the device.

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

Hereinafter, some embodiments of the present invention will be described in detail through exemplary drawings.

In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible 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 addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can 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."

Hereinafter, preparation examples or synthesis examples of some compounds among the compounds belonging to Chemical Formulas 1 to 5 will be described. However, since the number of compounds belonging to Formula 1 to Formula 5 is large, some of them will be exemplarily described. Those skilled in the art to which the present invention pertains, that is, those skilled in the art can prepare the compounds belonging to the present invention which are not illustrated through the preparation examples described below.

General Synthesis Example

The general synthesis methods exemplified above are all based on the Buchwald-hartwig cross coupling reaction. Among the preceding papers, Hartwig, JF Palladium-catalyzed amination of aryl halides. Mechanism and rational catalyst design. Synlett 1997 , 329-340. And Jiang, L., Buchwald, SL Palladium-catalyzed aromatic carbon-nitrogen bond formation. Metal-Catalyzed Cross-Coupling Reactions (2nd Edition) 2004 , 2, 699-760. And the like.

Sub  1,2 Synthesis Method Example

In a round bottom flask, amine compound a or b (1 equiv), Sub 1-1 (1.1 equiv), Pd ₂ (dba) ₃ (0.05 equiv), P (t-Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv) and toluene (10.5 mL / 1 mmol) were added followed by reaction at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain the product Sub 1 or Sub 2.

Examples of Sub 1-1 are as follows, but are not limited thereto.

Mass spectrometry (HRMS) was performed on the compounds Sub 1-1-1 to Sub 1-1-3, and the results are as follows.

Sub 1-1 may comprise a divalent substituted or unsubstituted aliphatic hydrocarbon in addition to the compounds given above.

On the other hand, if the Sub 1-1-1, the compound presented in the alkyl group (unsubstituted arylene group), as well as nitro, nitrile, _{halogen, C 1 ~ C 20, C} 1 ~ C 20 alkoxy group, C ₆ ~ C ₂₀ is substituted with a substituent selected from the group consisting of an aryl group, a C ₂ ~ C ₂₀ heterocyclic group, an amino group Arylene groups may also be included.

In the case of Sub 1-1-2, hydrogen, deuterium, tritium, halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, deuterium A substituted C ₆ -C ₂₀ aryl group, C ₇ -C ₂₀ arylalkyl group, C ₈ -C ₂₀ arylalkenyl group, C ₁ -C ₅₀ alkyl group, C ₂ -C ₂₀ heterocyclic group, nitrile group And a fluorenylene group substituted with a substituent selected from the group consisting of acetylene groups.

In the case of Sub 1-1-3, nitro, nitrile, halogen, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group and Substituted with a substituent selected from the group consisting of amino groups Heteroarylene groups may be included.

Sub  3 Synthesis Example

In a round bottom flask, the amine compound Ar ₁ -NH ₂ (1 equivalent), bromine compound Br-Ar ₂ (1.1 equivalent), Pd ₂ (dba) ₃ (0.05 equivalent), P (t-Bu) ₃ (0.1 equivalent), NaO t -Bu (3 equiv) and toluene (10.5 mL / 1 mmol) were added, followed by reaction at 100 ° C. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain product Sub 3.

An example of Sub 3 is as follows, but is not limited thereto.

The results of performing mass spectrometry (HRMS) on the compounds Sub 3-1 to Sub 3-22 were as in Table 2 below.

Sub 3 is hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ Arylamine group, C ₆ ~ C ₆₀ aryl group, C ₆ ~ C ₂₀ aryl group substituted with deuterium, C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ A heterocyclic group which is unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group, and includes at least one heteroatom of O, N, S, Si, and P; or

Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and Alkenyl group unsubstituted or substituted with a substituent selected from the group consisting of an acetylene group; or

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, An alkoxy group unsubstituted or substituted with a substituent selected from the group consisting of a C ₇ -C ₂₀ arylalkyl group, a C ₈ -C ₂₀ arylalkenyl group, a C ₂ -C ₂₀ heterocyclic group, a nitrile group and an acetylene group; or

Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, An alkyl group unsubstituted or substituted with a substituent selected from the group consisting of a C ₇ to C ₂₀ arylalkyl group, a C ₈ to C ₂₀ arylalkenyl group, a C ₂ to C ₂₀ heterocyclic group, a nitrile group and an acetylene group; It may be an amine compound including any one of.

On the other hand, in the case of Sub 3-1 to Sub 3-4, Sub 3-6 to Sub 3-9, Sub 3-12 to Sub 3-15, Sub 3-18, Sub3-19, Sub 3-22 In addition to (unsubstituted aryl group, aryl group substituted with C ₃ alkenyl group, aryl group substituted with C ₁ alkoxy group, aryl group substituted with C ₄ alkyl group, aryl group substituted with F), hydrogen, deuterium , Tritium, halogen group, C ₁ ~ C ₃ alkyl group, C ₅ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkyl tea Offene group, C ₆ ~ C ₂₀ arylthiophene group, C ₂ alkenyl group, C ₄ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ In the group consisting of C ₂₀ aryl group, C ₆ ~ C ₂₀ aryl group substituted with deuterium, C ₈ ~ C ₂₀ aryl alkenyl group, silane group, boron group, germanium group, C ₂ ~ C ₂₀ heterocyclic group Substituted with the selected substituent It may include an aryl group.

In addition, in the case of Sub 3-10, Sub 3-11, Sub 3-16, Sub 3-17, Sub 3-20, Sub 3-21, the above-described compound (fluorene group substituted with an alkyl group of C ₁ , C ₆ Fluorine group substituted with an aryl group), hydrogen, deuterium, tritium, halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₇ ~ C ₂₀ aryl group, deuterium A substituted C ₆ -C ₂₀ aryl group, C ₇ -C ₂₀ arylalkyl group, C ₈ -C ₂₀ arylalkenyl group, C ₂ -C ₅₀ alkyl group, C ₂ -C ₂₀ heterocyclic group, nitrile group And it may include a fluorene group unsubstituted or substituted with a substituent selected from the group consisting of an acetylene group.

In case of Sub 3-5, in addition to the compound (pyridine), hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C ₆₀ aryl group, C ₆ ~ C ₂₀ aryl group substituted with deuterium, C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group , A C ₂ ~ C ₂₀ heterocyclic group, a nitrile group and a substituted or unsubstituted with a substituent selected from the group consisting of an acetylene group, containing a heterocyclic group containing at least one heteroatom of O, N, S, Si, P can do.

final Product  Synthesis Example

Product  1 Synthetic method example

In a round bottom flask, Sub 1 (1.1 equiv), Sub 3 (1 equiv), Pd ₂ (dba) ₃ (0.05 equiv), P (t-Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv), Add toluene (10.5 mL / 1 mmol) and proceed with the reaction at 100 ° C. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain product Product 1.

1-5 Synthesis Example

4- (4'-bromobiphenyl-4-yl) -4H-benzo [b] [1,4] oxazine (8.7g, 24mmol), N-phenylpyridin-2-amine (3.4g. 20mmol) in a round bottom flask, Add Pd ₂ (dba) ₃ (0.05 equiv), P (t-Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv), toluene (10.5 mL / 1 mmol) and proceed with the reaction at 100 ° C . After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 5.7 g of the product. (Yield 63%)

3-30 Synthesis Example

4- (7-bromo-9,9-dimethyl-9H-fluoren-2-yl) -4H-benzo [b] [1,4] thiazine (10.1g, 24mmol), 4-tert-butyl in a round bottom flask -N-phenylaniline (4.5 g, 20 mmol), Pd ₂ (dba) ₃ (0.05 equiv), P (t-Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv), toluene (10.5 mL / 1 mmol ) Is added and the reaction proceeds at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 7.6 g of the product. (Yield: 67%).

Product  2 Synthesis Example

In a round bottom flask, Sub 2 (1.1 equiv), Sub 3 (1 equiv), Pd ₂ (dba) ₃ (0.05 equiv), P (t-Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv), Add toluene (10.5 mL / 1 mmol) and proceed with the reaction at 100 ° C. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain product Product 2.

2-15 Synthesis Example

10- (4'-bromobiphenyl-4-yl) -10H-phenoxazine (9.9g, 24mmol), N- (biphenyl-4-yl) naphthalen-1-amine (5.9g. 20mmol), Pd _{2 in a} round bottom flask (dba) ₃ (0.05 equiv), P (t-Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv) and toluene (10.5 mL / 1 mmol) were added and the reaction was carried out at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to obtain 8.5g of product. (Yield 68%)

2-20 Synthesis Example

10- (4'-bromobiphenyl-4-yl) -10H-phenoxazine (9.9g, 24mmol), N- (biphenyl-4-yl) -9,9-dimethyl-9H-fluoren-2-amine in a round bottom flask (7.2 g. 20 mmol), Pd ₂ (dba) ₃ (0.05 equiv), P (t-Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv), toluene (10.5 mL / 1 mmol) The reaction proceeds at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 9.7 g of the product. (Yield 70%)

2-32 Synthesis Example

10- (4'-bromobiphenyl-4-yl) -10H-phenothiazine (10.3g, 24mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (5.7g. 20mmol) in a round bottom flask Add Pd ₂ (dba) ₃ (0.05 equiv), P (t-Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv), toluene (10.5 mL / 1 mmol) and proceed with the reaction at 100 ° C do. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 8.8 g of the product. (Yield 69%)

4-34 Synthesis Example

10- (7-bromo-9,9-dimethyl-9H-fluoren-2-yl) -10H-phenothiazine (11.3g, 24mmol), N-phenyl-9,9'-spirobi [fluoren]-in a round bottom flask 2-amine (8.2 g, 20 mmol), Pd ₂ (dba) ₃ (0.05 equiv), P (t-Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv), toluene (10.5 mL / 1 mmol) After adding the reaction proceeds at 100 ℃. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 10.7g of product. (Yield: 67%).

4-41 Synthesis Example

10- (7-bromo-9,9-dimethyl-9H-fluoren-2-yl) -10H-phenothiazine (11.3g, 24mmol), dibiphenyl-4-ylamine (6.4g, 20mmol), Pd _{2 in a} round bottom flask (dba) ₃ (0.05 equiv), P (t-Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv) and toluene (10.5 mL / 1 mmol) were added and the reaction was carried out at 100 ° C. After the reaction was completed, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain 10.1 g of the product. (Yield 71%)

4-48 Synthesis Example

10- (7-bromo-9,9-dimethyl-9H-fluoren-2-yl) -9,9-dimethyl-9,10-dihydroacridine (11.5g, 24mmol), N-phenylbiphenyl-4- in a round bottom flask With amine (4.9 g, 20 mmol), Pd ₂ (dba) ₃ (0.05 equiv), P (t-Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv), toluene (10.5 mL / 1 mmol) After the reaction proceeds at 100 ℃. After completion of the reaction, the mixture was extracted with ether and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic substance was purified by silicagel column and recrystallized to obtain 8.8 g of the product. (Yield 68%)

The results of performing mass spectrometry (HRMS) on the finally synthesized compounds 1-1 to 4-66 were as shown in Table 3 below.

On the other hand, each substituent of the compounds represented by the formula (1) to formula (5) has a broad relationship, exemplarily described the synthesis examples of the representative compounds, compounds that are not illustratively described as a synthesis example may form part of the present specification. have.

Further, by introducing various substituents into the core structure having the above structure, it is possible to synthesize a compound having the intrinsic characteristics of the substituent introduced. For example, by introducing substituents used in the hole injection layer material, the hole transport layer material, the light emitting layer material, and the electron transport layer material used in the manufacture of the organic electric device, including the organic light emitting device to satisfy the conditions required for each organic material layer Materials can be prepared.

The compound according to the present invention can be used for various purposes in the organic electroluminescent device according to the type and nature of the substituent.

The compounds of the present invention can act as various layers other than the host of the phosphorescent or fluorescent light emitting layer because they are freely controlled by the core and the substituents.

The organic electric device of the present invention may be manufactured by a conventional method and material for manufacturing an organic electric device except for forming one or more organic material layers using the above-described compounds.

When the compounds of the present invention are used in other organic material layers of the organic electroluminescent device, for example, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, and a hole injection layer, it is obvious that the same effect can be obtained.

Meanwhile, the compound of the present invention can be used in a soluble process. In other words, the compound may form an organic material layer of the organic electronic device, which will be described later, by a solution process. In other words, when the compound is used as an organic material layer, the organic material layer may be formed by using various polymer materials, rather than a solution process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be produced in fewer layers by the method.

Organic electroluminescent devices in which the compounds of the present invention may be used include, for example, organic electroluminescent devices (OLEDs), organic solar cells, organic photoconductor (OPC) drums, organic transistors (organic TFTs), and the like.

As an example of the organic electroluminescent device to which the compounds of the present invention can be applied, an organic electroluminescent device (OLED) will be described. However, the present invention is not limited thereto, and the above-described compounds may be applied to various organic electroluminescent devices.

Another embodiment of the present invention is an organic electroluminescent device comprising a first electrode, a second electrode and an organic material layer disposed between the electrodes, wherein at least one of the organic material layer comprises an organic electroluminescent device comprising the compounds of the present invention to provide.

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

The organic electroluminescent device according to another embodiment of the present invention, except that at least one layer of the organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer to include the compound of the present invention. Can be prepared with a structure known in the art using conventional manufacturing methods and materials in the art.

The structure of the organic electroluminescent device according to another embodiment of the present invention is illustrated in Figures 1 to 6, but is not limited to these structures.

1 to 6, the organic electroluminescent device includes a substrate 101, 201, 301, 401, 501, 601, an anode 102, 202, 302, 402, 502, 602, a hole injection layer 103, 203, 303, hole transport layer 104, 204, 304, 404, light emitting layer 105, 205, 305, 405, 505, 605, electron transport layer 106, 206, 406, 506, electron injection layer 107 It includes, and at least one layer of the organic material layer except the light emitting layer may be omitted.

Although not shown, the organic electroluminescent device further includes a hole blocking layer (HBL) that prevents the movement of holes, an electron blocking layer (EBL) that prevents the movement of electrons, a light emitting auxiliary layer that helps or assists light emission, and a protective layer. It may be located. The protective layer may be formed to protect the organic material layer or the cathode at the uppermost layer.

In this case, the compound of the present invention may be included in one or more of an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer.

Specifically, the compound of the present invention is used in place of or in combination with one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer and a protective layer It may be used to form. Of course, the organic layer may be used not only in one layer but also in two or more layers.

In particular, it can be used as a hole injection material, a hole transport material, an electron injection material, an electron transport material, a luminescent material and a passivation (kepping) material according to the compound of the present invention, in particular a host or in a luminescent material and host / dopant alone Can be used as a dopant, can be used as a hole injection, a hole transport layer.

For example, the organic electroluminescent device according to another embodiment of the present invention is a metal having metal or conductivity on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. An oxide or an alloy thereof is deposited to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer is formed thereon, and then a material that can be used as a cathode is deposited thereon. Can be prepared.

In addition to the above method, an organic electronic device may be fabricated by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate. The organic material layer may have a multilayer 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 layer may be formed using a variety of polymer materials, but not by a deposition process or a solvent process, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be made with a small number of layers.

The organic electroluminescent device according to another embodiment of the present invention may be used in a solution process such as spin coating or ink jet process.

The substrate is a support of the organic electroluminescent device, and a silicon wafer, a quartz or glass plate, a metal plate, a plastic film or sheet, or the like can be used.

An anode is positioned over the substrate. This anode injects holes into the hole injection layer located thereon. The positive electrode material may be a material having a large work function to facilitate hole injection 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.

The hole injection layer is located on the anode. The conditions required for the material of the hole injection layer are high hole injection efficiency from the anode, it should be able to transport the injected holes efficiently. This requires a small ionization potential, high transparency to visible light, and excellent hole stability.

The hole injection material is a material that can be injected well from the anode at a low voltage, the highest occupied molecular orbital (HOMO) of the hole injection material may be between the work function of the positive electrode material and the HOMO of the surrounding organic material 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.

The hole transport layer is positioned on the hole injection layer. The hole transport layer receives holes from the hole injection layer and transports the holes to the organic light emitting layer located thereon, and serves to prevent high hole mobility, hole stability, and electrons. In addition to these general requirements, applications for vehicle body display require heat resistance to the device, and may be a material having a glass transition temperature (Tg) of 70 ° C. or higher.

Materials satisfying these conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene, silicon germanium oxide Compound, a silicon-based arylamine compound, and the like.

The organic light emitting layer is positioned on the hole transport layer. The organic light emitting layer is a layer for emitting light by recombination of holes and electrons injected from the anode and the cathode, respectively, and is made of a material having high quantum efficiency. The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and may be a material having good quantum efficiency for fluorescence or phosphorescence.

Substances or compounds that satisfy these conditions include Alq3 for green, Balq (8-hydroxyquinoline beryllium salt) for blue, DPVBi (4,4'-bis (2,2-diphenylethenyl) -1,1'- biphenyl) series, Spiro material, Spiro-DPVBi (Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenollithium salt ), Bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 '[ (1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole; DSA (distrylamine) can be used by doping in small amounts. In the case of red, DCJTB ([2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H Small amounts of doping such as -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile) can be used.

When forming a light emitting layer using a process such as inkjet printing, roll coating, or spin coating, a polymer of polyphenylene vinylene (PPV) -based polymer or poly fluorene may be used for the organic light emitting layer. .

The electron transport layer is positioned on the organic light emitting layer. The electron transport layer needs a material having high electron injection efficiency from the cathode positioned thereon and capable of efficiently transporting the injected electrons. To this end, it must be made of a material having high electron affinity and electron transfer speed and excellent stability to electrons.

Examples of the electron transport material that satisfies such conditions include Al complexes of 8-hydroxyquinoline; Complexes including Alq3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.

The electron injection layer is stacked on the electron transport layer. The electron injection layer is a metal complex compound such as Balq, Alq3, Be (bq) 2, Zn (BTZ) 2, Zn (phq) 2, PBD, spiro-PBD, TPBI, Tf-6P, aromatic compound with imidazole ring, It can be produced using a low molecular weight material containing boron compounds and the like. At this time, the electron injection layer may be formed in a thickness range of 100 ~ 300Å.

The cathode is positioned on the electron injection layer. This cathode serves to inject electrons. The material used as the cathode may use the material used for the anode, and may be a metal having a low work function for efficient electron injection. In particular, a suitable metal such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or a suitable alloy thereof can be used. In addition, an electrode having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum having a thickness of 100 μm or less may also be used.

As described above, according to the compound of the present invention, it can be used as a hole injection material, a hole transport material, a light emitting material, an electron transport material, and an electron injection material suitable for fluorescence and phosphorescent devices of all colors such as red, green, blue, and white, It can be used as a host or dopant material of various colors.

The organic electroluminescent device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.

Meanwhile, the present invention includes a display device including the organic electric element described above, 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 described above 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 control, a navigation device, a game machine, various TVs, various computers, and the like.

Evaluation of manufacturing of organic electric device

Using various compounds obtained through synthesis as a hole transport layer, an organic light emitting device was manufactured according to a conventional method. First, 4,4 ', 4 "-tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine (hereinafter referred to as 2T-NATA) as a hole injection layer on the ITO layer (anode) formed on the glass substrate The film was vacuum deposited to form a thickness of 10 nm. Subsequently, the compound according to the embodiment of the present invention as a hole transport compound was vacuum deposited to a thickness of 30 nm to form a hole transport layer. After forming the hole transporting layer, a light emitting layer doped with 7% of BD-052X (Idemitus Co., Ltd.) having a thickness of 45 nm (where BD-052X is a blue fluorescent dopant and 9,10-die (naphthalene-2) is used as a light emitting host material. Anthracene (ADN)) was used as (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) as the hole blocking layer. Vacuum deposition was carried out to a thickness of 10 nm, and then tris (8-quinolinol) aluminum (hereinafter abbreviated to Alq ₃ ) was deposited to a thickness of 40 nm with an electron injection layer. Thereafter, LiF, an alkali metal halide, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to use an Al / LiF as a cathode to prepare an organic light emitting device.

           Comparative Example (1) NPB Comparative Example (2)

For comparison, an organic electroluminescent device having the same structure as that of the test example was prepared using Comparative Example (1) (abbreviated as NPB) and Comparative Example (2) represented by the above formula as a hole transport layer material instead of the compound of the present invention. Produced.

The electroluminescent (EL) characteristics of the Example and Comparative Example organic electroluminescent devices prepared as described above were applied to the PR-650 of photoresearch by applying a forward bias DC voltage, and the measured results were measured at 300 cd / m2 reference luminance. The T90 life was measured using a life measurement instrument manufactured by McScience.

Table 4 below shows device fabrication and evaluation results of experimental examples and comparative examples to which the compound according to the present invention is applied.

As can be seen from the results of the above table, the organic light emitting device using the organic light emitting device material of the present invention is used as a hole transporting material to significantly improve the driving voltage, color purity, high luminous efficiency and lifetime lower than the comparative compound. It can be confirmed that.

Even if the compounds of the present invention are used in other organic material layers of the organic light emitting device, for example, a light emitting layer, a light emitting auxiliary layer, an electron injection layer, an electron transport layer, it is obvious that the same effect can be obtained.

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 are 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 equivalents should be construed as falling within the scope of the present invention.

Claims (11)

Compound for an organic electric device comprising a compound of formula (1).
≪ Formula 1 >

Where A is

or

In the above formulas,
(1) X is O, S, CR'R ", SiR'R". here,
R ' and R ” each independently represent a halogen group, a C ₁ to C ₆₀ alkyl group, a C ₁ to C ₆₀ alkoxy group, a C ₁ to C ₆₀ alkylamine group, a C ₆ to C ₆₀ arylamine group, C ₁ ~ C ₆₀ Alkylthiophene group, C ₆ ~ C ₆₀ Aryl thiophene group, C ₂ ~ C ₆₀ Alkenyl group, C ₂ ~ C ₆₀ Alkynyl group, C ₃ ~ C ₆₀ Cycloalkyl group, C of ₆ ~ C ₆₀ aryl group, a C ₆ ~ C ₆₀ substituted with a heavy hydrogen of the aryl group, a C ₈ ~ C ₆₀ aryl alkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted hwandoen germanium group and an aryl group, a substituted or unsubstituted with C ₂ ~ C ₂₀ substituted or non with a substituent selected from the group consisting of substituted heterocyclic C ₆ ~ C _60;
C ₁ ~ alkenyl group of the C ₂₀ alkyl group, C ₂ ~ C ₂₀ of, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ aryl group of C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with deuterium, C ₇ C ₁ ~ C ₅₀ alkyl group unsubstituted or substituted with a substituent selected from the group consisting of-C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group ;
Halogen, CN, NO ₂ , C ₁ ~ C ₆₀ alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkylamine group, C ₆ ~ C ₆₀ arylamine group, C ₁ ~ C ₆₀ Alkylthiophene group, C ₂ ~ C ₆₀ alkenyl group, C ₂ ~ C ₆₀ alkynyl group, C ₃ ~ C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₆ ~ C ₆₀ substituted with deuterium Substituted by a substituent selected from the group consisting of an aryl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and a substituted or unsubstituted C ₂ ~ C ₂₀ heterocyclic group Or a C ₂ ~ C ₆₀ heterocyclic group which is unsubstituted and contains at least one heteroatom of O, N, or S ; And
A C ₆ ~ C ₆₀ of aliphatic rings in the aromatic ring and C ₃ ~ C ₆₀ Condensed ring group ; Is selected from the group consisting of
(2) R ₁ to R ₁₀ are each independently hydrogen; heavy hydrogen; Tritium; Halogen group ;
Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C arylalkyl group of _{7 ~ C 20, C 8 ~} C 20 aryl alkenyl group, C ₂ ~ C ₂₀ of the heterocyclic group, the in nitrile group and acetylene group the group consisting of unsubstituted or substituted with substituent C ₁ ~ C ₅₀ Alkyl group ;
Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₁ ~ C ₂₀ alkylthiophene group, C ₆ C ₂₀ -C20 arylthiophene group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, deuterated C ₆ to C ₂₀ aryl group, a C ₈ - C ₂₀ aryl alkenyl group, a silane group, a boron group, a germanium group, a C ₂ ~ C ₂₀ unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic C ₆ to an aryl group of C _60;
Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and C ₂ ~ C ₆₀ heterocyclic group which is unsubstituted or substituted with a substituent selected from the group consisting of acetylene groups, and containing at least one hetero atom of O, N, S, Si, P ;
Hydrogen, deuterium, tritium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₂ ~ C ₆₀ unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic C ₆ ~ C ₆₀ arylamine group;
Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and with a substituent selected from the group consisting of acetylene substituted or unsubstituted C ₂ ~ C ₂₀ alkenyl;
Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group group substituents a substituted or unsubstituted C ₁ ~ C ₃₀ selected from the consisting of Alkoxy group ; And
Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group group substituted with substituted or unsubstituted C ₆ ~ C ₃₀ selected from the consisting of aryloxy; Is selected from the group consisting of
(3) L is composed of nitro, nitrile, halogen, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₆ -C ₂₀ aryl group, C ₂ -C ₂₀ heterocyclic group, amino group C ₆ ~ C ₆₀ arylene group unsubstituted or substituted with a substituent selected from the group ;
Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, Substituted with a substituent selected from the group consisting of C ₇ -C ₂₀ arylalkyl group, C ₈ -C ₂₀ arylalkenyl group, C ₁ -C ₅₀ alkyl group, C ₂ -C ₂₀ heterocyclic group, nitrile group and acetylene group or Unsubstituted fluorenylene group ;
A substituent selected from the group consisting of nitro, nitrile, halogen, C ₁ -C ₂₀ alkyl group, C ₁ -C ₂₀ alkoxy group, C ₆ -C ₂₀ aryl group, C ₂ -C ₂₀ heterocyclic group and amino group Substituted or unsubstituted C ₃ ~ C ₆₀ Hetero arylene group ; And
Divalent substituted or unsubstituted aliphatic hydrocarbons; Is selected from the group consisting of
(4) Ar ₁ and Ar ₂ are each independently hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkylamine group, C ₁ -C ₂₀ alkylthiophene group, C ₆ -C ₂₀ arylthiophene group, C ₂ -C ₂₀ alkenyl group, C ₂ -C ₂₀ alkynyl group, C ₃ -C ₂₀ cycloalkyl group, C of ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, a C ₈ ~ C ₂₀ arylalkenyl group, a silane group, a boron group, a germanium group, consisting of a heterocycle of the C ₂ ~ C ₂₀ of an aryl group unsubstituted or substituted with a substituent selected from the group C ₆ ~ C _60;
Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and C ₂ ~ C ₆₀ heterocyclic group which is unsubstituted or substituted with a substituent selected from the group consisting of acetylene groups, and containing at least one hetero atom of O, N, S, Si, P ;
Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and with a substituent selected from the group consisting of acetylene substituted or unsubstituted C ₂ ~ C ₂₀ alkenyl;
Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ of the hetero ring group, nitrile group and acetylene group group substituents a substituted or unsubstituted C ₁ ~ C ₃₀ selected from the consisting of Alkoxy group ;
Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C arylalkyl group of _{7 ~ C 20, C 8 ~} C 20 aryl alkenyl group, C ₂ ~ C ₂₀ of the heterocyclic group, the in nitrile group and acetylene group the group consisting of unsubstituted or substituted with substituent C ₁ ~ C ₅₀ Alkyl group ; And
Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, Substituted with a substituent selected from the group consisting of C ₇ -C ₂₀ arylalkyl group, C ₈ -C ₂₀ arylalkenyl group, C ₁ -C ₅₀ alkyl group, C ₂ -C ₂₀ heterocyclic group, nitrile group and acetylene group or Unsubstituted fluorene group ; Is selected from the group consisting of
(5) R ₁ to R ₁₀ may be bonded or reacted with groups adjacent to each other to form a substituted or unsubstituted saturated or unsaturated ring. In addition, Ar ₁ , Ar ₂ It is also possible to combine or react with adjacent groups to form a substituted or unsubstituted saturated or unsaturated ring. The method of claim 1,
The R ₁ to R ₁₀ , Ar ₁ , Ar ₂ A compound for an organic electric device, characterized in that to form a saturated or unsaturated ring by bonding or reaction with adjacent groups. The method of claim 1,
The compound is an organic electric device compound represented by any one of the following formula (2).
&Lt; Formula 2 >< EMI ID =

&Lt; Formula 4 &gt;&lt; EMI ID =

The method of claim 1,
Compound for an organic electric device, characterized in that one of the following compounds.

An organic electric device comprising at least one organic material layer comprising the compound of claim 1. 6. The method of claim 5,
An organic electric device, characterized in that to form the compound to the organic material layer by a solution process. 6. The method of claim 5,
An organic electric device comprising a first electrode, the organic material layer and a second electrode sequentially stacked. 6. The method of claim 5,
The organic material layer comprises at least one of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer. The method of claim 8,
And the compound is used as the hole transport layer material. A display device comprising the organic electroluminescent device of claim 5; And
A controller for driving the display device; &Lt; / RTI &gt; The method of claim 10,
The organic electronic device is one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT).

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