WO2011037429A2 - Compounds having 5-membered aryl-ring-condensed heterocyclic derivatives, organic electronic device using the compounds, and terminal comprising the organic electronic device - Google Patents

Abstract

The present invention relates to compounds having 5-membered aryl-ring-condensed heterocyclic derivatives, to an organic electronic device using the compounds, and to a terminal comprising the organic electronic device.

Description

A compound having a heterocyclic 5-membered ring derivative condensed with an aryl ring, an organic electric device using the same, and a terminal thereof

The present invention relates to a compound having a heterocyclic 5-membered ring derivative in which an aryl ring is condensed, an organic electric device using the same, and a terminal thereof.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. In this case, the organic material layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, for example, it may be made 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 according to molecular weight, and may be classified into a fluorescent material derived from a singlet excited state of electrons and a phosphorescent material derived from a triplet excited state of electrons according to a light emitting mechanism. Can be. 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.

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. The principle is that when a small amount of a dopant having an energy band gap smaller than that of a host forming the light emitting layer is mixed in the light emitting layer, excitons generated in the light emitting layer are transported to the dopant, thereby producing high efficiency light. At this time, since the wavelength of the host is shifted to the wavelength of the dopant, light having a desired wavelength can be obtained according to the type of dopant to be used.

In order to fully exhibit the excellent characteristics of the above-described organic electroluminescent device, a material forming 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.

Embodiments of the present invention to solve the problems of the above-described background, a compound having a heterocyclic 5-membered ring derivative condensed with an aryl ring having a novel structure has been found, and also applied to the organic electric device It has been found that the light emitting efficiency, stability and lifetime of the device can be greatly improved.

Accordingly, an object of the present invention is to provide a compound having a heterocyclic 5-membered ring derivative in which a novel aryl ring is condensed, an organic electric device using the same, and a terminal thereof.

In addition, the present inventors have found a derivative containing a novel dibenzocarbazole as one of the heterocyclic 5-membered ring derivatives in which an aryl ring is condensed, and also based on the current density characteristics of the device when the compound is applied to an organic electric device. It has been found that high efficiency, low voltage, high brightness, stability increase and long life can be achieved.

Accordingly, an object of the present invention is to provide a compound containing a novel dibenzocarbazole as one of heterocyclic 5-membered ring derivatives in which an aryl ring is condensed, an organic electric device using the same, and a terminal thereof.

In one aspect, the present invention provides a compound of the formula:

Z- (Y) n

In the above formula, Z represents a group consisting of a substituted or unsubstituted aromatic hydrocarbon group or aromatic heterocyclic group, and Y may represent a group represented by the following General Formula (2).

The present invention is a compound having a heterocyclic 5-membered ring derivative in which an aryl ring is condensed, and is useful as a hole injection, a hole transport, an electron injection, an electron transport, a light emitting material and / or a passivation (kepping) material, in particular a host or a plate alone Useful as

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

In another aspect, the present invention provides a compound of the formula

The compound applied to the organic electric device may be used as one or more of a hole injection material and a hole transport material suitable for phosphorescent devices of all colors, such as red, green, blue, and white, depending on the synthesized compound. Compounds applied to organic electroluminescent devices can be used as phosphorescent dopant host materials of various colors.

The present invention is a compound having a heterocyclic 5-membered ring derivative in which an aryl ring is condensed, and is useful as a hole injection, a hole transport, an electron injection, an electron transport, a light emitting material and / or a passivation (kepping) material, in particular a host or a plate alone Useful as

The compound of the present invention may play various roles in the organic electric device and the terminal, and when applied to the organic electric device and the terminal, the high efficiency, low voltage, high brightness, stability increase and long life can be expected.

1 to 6 show examples of the organic light emitting display 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 addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected".

The present invention provides a compound of Formula 1 below.

 [Formula 1]

Z- (Y) n

In Formula 1, Z represents a group consisting of a substituted or unsubstituted aromatic hydrocarbon group or aromatic heterocyclic group, Y represents a group represented by the following formula (2), n may represent an integer of 1-6.

 [Formula 2]

R ₁ to R ₉ are the same as or different from each other, and each independently 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, C ₁ to C ₆₀ arylamine group, C ₁ to C ₆₀ alkyl thiophene group, C ₆ to C ₆₀ aryl thiophene group, C ₂ to C ₆₀₀ alkenyl group, C ₂ to C ₆₀ alkynyl group, C ₃ to C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted by deuterium aryl group, a C ₈ ~ C ₆₀ arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted ring of C ₆ ~ C ₆₀ aryl group substituted or unsubstituted with one or more groups selected from the group consisting of a boron group, a substituted or unsubstituted germanium group, and a substituted or unsubstituted C ₅ ~ C ₆₀ heterocyclic group, halogen, CN, NO ₂ , C ₁ to C ₆₀ alkyl group, C ₁ to C ₆₀ alkoxy group, C ₁ to C ₆₀ alkylamine group, C ₁ to C ₆₀ alkylthio group, C ₂ to C ₆₀ alkenyl group, C of ₂ ~ C ₆₀ alkynyl group, C ₃ ~ C ₆₀ of An aryl group of claws alkyl group, C ₆ ~ C _60, of a C ₆ ~ C ₆₀ substituted by deuterium aryl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted or unsubstituted germanium group, and substituted or unsubstituted C ₅ ~ heterocyclic group of C ₆₀ substituted or unsubstituted by at least one group selected from the group consisting of a heterocyclic C ₅ ~ C ₆₀ or C ₆ ~ of the C ₆₀ aromatic ring and C ₄ ~ C ₆₀ A condensed cyclic group of an aliphatic ring of which may be any group independently selected from a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, and a substituted and unsubstituted heteroaryl group. have.

At this time, R ₁ ~ R ₉ may be bonded to each other adjacent positions to form a ring. For example, it may be represented by the following Chemical Formula 3.

On the other hand, X represents C, N, O, S, Si, P, Ge. One of R ₁ to R ₉ is Z.

 [Formula 3]

In Chemical Formula 3, R ₁₀ to R ₁₅ may independently have the same meaning as R ₁ to R _9, and ring A condensed to indole may be represented by the following Formula 4.

 [Formula 4]

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It includes any one selected.

When n is 1 in Z- (Y) n of Chemical Formula 1, it may be represented by Chemical Formula 5.

 [Formula 5]

In Formula 4, any one of R represents Z.

When n is 2 or more in Z- (Y) n of Chemical Formula 1, it may be represented by any one of Chemical Formula 6 below.

 [Formula 6]

,

,

Specific examples of the compounds belonging to Formulas 1 to 6, which are compounds having a heterocyclic 5-membered ring derivative in which an aryl ring is condensed according to an embodiment of the present invention, include the compounds of Formulas 7 and 8, but the present invention is limited to these It doesn't happen.

 [Formula 7]

 [Formula 8]

The compound represented by Chemical Formula 1 may be a compound including dibenzocarbazole represented by Chemical Formula 9 below.

 [Formula 9]

In Chemical Formula 9,

R ₁ to R ₁₃ are the same as or different from each other, and each independently 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, and C ₁ to C ₆₀ arylamine group, C ₁ to C ₆₀ alkyl thiophene group, C ₆ to C ₆₀ aryl thiophene group, C ₂ to C ₆₀ alkenyl group, C ₂ to C ₆₀ alkynyl group, C ₃ to C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted by deuterium aryl group, a C ₈ ~ C ₆₀ arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted ring of A C ₆ -C ₆₀ aryl group unsubstituted or substituted with one or more groups selected from the group consisting of a boron group, a substituted or unsubstituted germanium group, and a substituted or unsubstituted C ₅ -C ₆₀ heterocyclic group; Of _{halogen, CN, NO 2, C 1} ~ C 60 alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkyl amine group, C ₁ ~ C import of ₆₀ alkylthio, C ₂ ~ C ₆₀ of alkenyl group, C ₂ ~ C ₆₀ of the alkynyl group, C ₃ ~ C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted by deuterium 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 substituted or unsubstituted by at least one group selected from the group consisting of a heterocycle of the C ₅ ~ C ₆₀ unsubstituted C ₅ ~ C ₆₀ ring Heterocyclic group; Or a condensed ring group of an aromatic ring of C ₆ to C ₆₀ and an aliphatic ring of C ₄ to C ₆₀ , each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group , Any group selected from substituted and unsubstituted heteroaryl groups, and adjacent positions may be bonded to each other to form a ring.

When R ₁₄ in the above Formula 9 is hydrogen or alkyl, aryl, heteroaryl, the compound represented by Formula 1 may be represented by the following Formula 10.

 [Formula 10]

In contrast, when R ₁₆ in Formula 9 is directly connected to a substituted or unsubstituted alkylamine or arylamine, the compound represented by Formula 9 may be represented by Formula 11 below.

 [Formula 11]

On the contrary, in the above Formula 9, when R ₁₆ is a substituted or unsubstituted alkylamine or arylamine having a linking group, the compound represented by Formula 9 may be represented by the following Formula 12.

 [Formula 12]

In the above description, although the compounds of the following Chemical Formulas 13 to 15 are shown as specific examples of the compound containing dibenzocarbazole from the chemical formula, the present invention is not limited thereto.

 [Formula 13]

 [Formula 14]

 [Formula 15]

In addition, the substituents in Chemical Formulas 1 to 15 may be substituted or unsubstituted again even if not mentioned above, and the substituents may be substituted again.

Various organic electric devices exist in which compounds having a heterocyclic 5-membered ring derivative having an aryl ring condensed with reference to Formulas 1 to 15 are used as an organic material layer. Examples of the organic electroluminescent device in which compounds having a heterocyclic 5-membered ring derivative in which the aryl ring is condensed with reference to Chemical Formulas 1 to 15 may be used include, for example, an organic electroluminescent device (OLED), an organic solar cell, and an organic photoreceptor ) And organic transistors (organic TFTs).

An organic electroluminescent device (OLED) is described as an example of an organic electric device to which compounds having a heterocyclic 5-membered ring derivative in which an aryl ring is condensed with reference to Chemical Formulas 1 to 15 may be applied, but the present invention is not limited thereto. And a compound having a heterocyclic 5-membered ring derivative in which the aryl ring is condensed as described above may be applied to various organic electric devices.

Another embodiment of the present invention is an organic electric 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 of the organic electric field comprising the compounds of Formula 1 to 15 Provided is a light emitting device.

For example, an organic electric device including a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers is represented by Formulas 1 to 15: An organic electroluminescent device comprising compounds is provided.

 The organic layer may include at least one layer of a hole injection layer, a hole transport layer, and a layer for simultaneously injecting holes and transporting holes, and one of the layers may include compounds of Formulas 1 to 15.

In another aspect, the organic material layer includes a hole injection layer, a hole transport layer, and at least one layer of the hole injection and hole transport at the same time, one of the layers may include the compounds of formula 1 to 15 have.

Specifically, the organic material layer may include a light emitting layer, and the light emitting layer may include compounds of Formulas 1 to 15.

In addition, the organic material layer may include an electron transport layer, and the hole transport layer may include compounds of Formulas 1 to 15.

In addition, the organic material layer may include a light emitting auxiliary layer, and the light emitting auxiliary layer may include compounds of Formulas 1 to 15.

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

In an organic light emitting display device according to another embodiment of the present invention, at least one layer of 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 to include the compounds of Formulas 1 to 15. Except for the above, it may be manufactured in a structure known in the art using conventional manufacturing methods and materials in the art.

The structure of the organic light emitting display device according to another embodiment of the present invention is illustrated in FIGS. 1 to 6, but is not limited thereto. In this case, reference numeral 101 denotes a substrate, 102 an anode, 103 a hole injection layer (HIL), 104 a hole transport layer (HTL), 105 a light emitting layer (EML), 106 an electron injection layer (EIL), 107 an electron transport layer ( ETL), 108 represents a negative electrode. Although not shown, the organic light emitting diode may further include a hole blocking layer (HBL) for blocking the movement of holes, an electron blocking layer (EBL) for preventing the movement of electrons, and a protective layer. The protective layer may be formed to protect the organic material layer or the cathode at the uppermost layer.

In this case, the compound having a heterocyclic 5-membered ring derivative in which the aryl ring described with reference to Formulas 1 to 15 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 having a heterocyclic 5-membered ring derivative in which the aryl ring is condensed with reference to Formulas 1 to 15 may be 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, It may be used in place of one or more of the protective layers or in combination with them. Of course, the organic layer may be used not only in one layer but also in two or more layers.

In particular, the hole injection material, the hole transport material, the electron injection material, the electron transport material, the light emitting material and the passivation (kepping) material according to the compound having a heterocyclic 5-membered ring derivative condensed with the aryl ring described with reference to the formulas (1) to (15) It can be used as, and in particular can be used as a light emitting material and a host or dopant alone.

For example, the organic light emitting device according to another embodiment of the present invention is a metal having a 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 material layer may be formed by using a variety of polymer materials, and by using a process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer, rather than a deposition method. It can be prepared in layers.

The organic light emitting device according to another embodiment of the present invention is a soluble process such as spin coating or ink jet process of a compound having a heterocyclic 5-membered ring derivative condensed with the aryl ring described above May be used.

The substrate is a support of the organic light emitting device, and a silicon wafer, quartz or glass plate, metal plate, 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. As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode 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), indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.

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 capable of well injecting holes from the anode at low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene, quinacridone-based organics, perylene-based organics, Anthraquinone, polyaniline and polythiophene-based conductive polymers, 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, when applied for vehicle body display, heat resistance to the device is required, and a material having a glass transition temperature (Tg) of 70 ° C. or higher is preferable. 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 a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable.

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) -phenol lithium salt), bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complex, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 ') to increase blue light emission efficiency. [(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 the light emitting layer is formed using a process such as inkjet printing, roll coating, or spin coating, an organic light emitting layer is formed of a polymer of polyphenylene vinylene (PPV) or a polymer such as poly fluorene. Can be used for

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 Alq ₃ ; 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. As the material used as the cathode, it is possible to use the material used for the anode, and a metal having a low work function is more preferable 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 having a heterocyclic 5-membered ring derivative condensed with the aryl ring described with reference to Formulas 1 to 15, a hole injection material and hole suitable for fluorescence and phosphorescent devices of all colors such as red, green, blue, and white It can be used as a transport material, a light emitting material, an electron transport material and an electron injection material, and can be used as a host or dopant material of various colors.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type according to 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.

EXAMPLE

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

Preparation Example 1

Hereinafter, the preparation or synthesis examples of the compounds having a heterocyclic 5-membered ring derivative in which the aryl ring belonging to Chemical Formulas 1 to 8 are condensed will be described. However, one or two of the compounds having a heterocyclic 5-membered ring derivative in which the aryl ring of Formulas 1 to 8 is condensed because of the large number of compounds having a heterocyclic 5-membered ring derivative in which the aryl ring of Formula 1 to 8 is condensed Will be described as an example. Those of ordinary skill in the art, that is, those skilled in the art can prepare a compound having a heterocyclic 5-membered ring derivative condensed with an aryl ring belonging to the present invention, which is not illustrated by the preparation examples described below. have.

Synthesis Example 1

Scheme 1

In the above synthesis, when A is Phenanthrene and Ar is H, Phenyl or Methyl, Intermediate 3 and Intermediate 7 were synthesized by known methods.

Intermediate 4 Method when A is Phenanthrene

Add intermediate 3 and NBS to a 250mL 2-neck round flask and stir at 40 ° C for 12 hours. After completion of the reaction, the mixture was extracted with MC and water, dried over MgSO 4, concentrated, and recrystallized with hexane (Hexane) to obtain 7 g of a white solid (yield 81%).

Synthesis when A is Phenanthrene and Ar is Phenyl in Intermediate 5

Phenylboronic acid, Intermediate 4 and tetrakis triphenyl phosphine palladium were added to K ₂ CO ₃ in 500 ml of THF and 250 ml of water and heated to reflux for 24 hours. The obtained solid was washed with water and methanol and then separated by silica gel column chromatography to give intermediate 5 (yield 60%).

Method for synthesizing compound B-4 (material 6 of Synthesis Example 1)

Two equivalents of Intermediate 5, 1,4-Dibromobiphenyl, Pd2 (dba) 3, Triphenylphosphine, and Sodium tert-butoxide were added to a toluene solvent and stirred under reflux for 24 hours at 130 ° C. After completion of the reaction, the mixture was extracted with MC, water, dried over MgSO 4, concentrated, and the resulting compound was separated using column chromatography to obtain the desired compound B-4. (Yield 36%)

Synthesis when A is Phenanthrene and Ar is Phenyl in Intermediate 8

It is the same as the synthesis method of intermediate 4, except that intermediate 7 is substituted for intermediate 3.

Synthesis when A is Phenanthrene and Ar is Phenyl in Intermediate 9

After dissolving intermediate 8 in THF, n-BuLi was slowly added dropwise at -78 degrees, followed by stirring for a minute. Triisopropylborate was then slowly added dropwise at -78 ° C, stirred, acidified with 1N HCl, extracted with water and EA, dried over MgSO4 and recrystallized with hexane (Hexane).

Synthesis Method of Compound B-2 (Subject No. 10 of Synthesis Example 1)

Dissolve 2 equivalents of Intermediate 9 and 1,4-Dibromobiphenyl in THF, add NaOH and H2O and stir to reflux. After completion of the reaction, the mixture was extracted with water and MC, dried over MgSO 4, column was purified by silica gel chromatography, and recrystallized with hexane (Hexane) to obtain a product. (Yield 84%)

Method for synthesizing compound A-14 (material 11 of Synthesis Example 1)

It is the same as the synthesis method of compound B-2 except that 2-chloro-4,6-diphenyl-1,3,5-Triazine is added instead of 1 equivalent of intermediate 9 and 1,4-Dibromobiphenyl instead of 2 equivalents of intermediate 9.

Thianthrene was dissolved in anhydrous THF and n- BuLi (1.6 M in hexane) was added dropwise at -78 ° C, followed by stirring at room temperature for 1 hour. The temperature of the reaction was lowered to 78 ° C and Chlorotrimethylsilane was added dropwise, followed by stirring at room temperature for 12 hours. At the end of the reaction, the mixture was extracted with ethyl acetate and washed with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, the organic solvent was concentrated and the resulting product was separated using column chromatography to give the desired compound A-14 (yield 95%).

Evaluation of production of organic field devices1

Various compounds obtained through synthesis were used as light emitting host materials or hole transporting layers of the light emitting layer, respectively, to fabricate an organic light emitting device according to a conventional method. First, a copper phthalocyanine (hereinafter abbreviated as CuPc) film was vacuum-deposited on the ITO layer (anode) formed on the glass substrate to form a thickness of 10 nm.

Subsequently, when measured with a green host, 4,4-bis [ N- (1-naphthyl) -N -phenylamino] biphenyl (abbreviated as a-NPD) was used as the major transport compound on this membrane. Vacuum deposition to a thickness of nm to form a hole transport layer. After the formation of the hole transport layer, when measuring the hole transport layer, an emission layer doped with 7% of BD-052X (Idemitus) having a thickness of 45 nm on the hole transport layer (where BD-052X is a blue fluorescent dopant, is a light emitting host material) As the furnace, 9,10-di (naphthalene-2-anthracene (AND)) was used.

When measuring with a phosphorescent host material, a phosphorescent material was deposited to form a light emitting layer, and tris (2-phenylpyridine) iridium (hereinafter abbreviated as I r (ppy) ₃ ) was added as a phosphorescent Ir metal complex dopant. . At this time, the concentration of I r (ppy) _{3 in} the light emitting layer was 10% by weight. (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolinoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a hole blocking layer to a thickness of 10 nm. Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was formed into an electron injection layer to a thickness of 40 nm. 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

For comparison, an organic electroluminescent device having the same structure as the test example was manufactured using a compound represented by Formula 8 (hereinafter abbreviated as CBP) as a light emitting host material instead of the compound of the present invention.

 [Formula 16]

Table 1

	Host material of emitting layer	Voltage (V)	Current density (mA / cm 2 )	Luminous Efficiency (cd / A)	Chromaticity coordinates (x, y)
Example 1	Compound a-12	5.4	0.31	47.3	(0.31, 0.60)
Example 2	Compound a-13	5.6	0.32	46.2	(0.31, 0.60)
Example 3	Compound a-14	5.2	0.31	45.2	(0.29, 0.60)
Example 4	Compound b-3	5.8	0.32	42.4	(0.32, 0.63)
Comparative Example 1	CBP	6.1	0.31	32.6	(0.33, 0.61)

Also, when the compounds of the present invention were measured by the hole transport layer, NPB was used as the hole transport material instead of the compound of the present invention to prepare an organic light emitting display device having the same structure as the test example.

 [Formula 17]

TABLE 2

	Hole transport material	Voltage (V)	Current density (mA / cm 2 )	Luminous Efficiency (cd / A)	Chromaticity coordinates (x, y)
Example 1	Compound A-25	6.7	13.01	8.6	(0.15, 0.14)
Example 2	Compound a-26	5.8	13.11	8.2	(0.15, 0.15)
Example 3	Compound A-35	6.2	12.98	8.5	(0.15, 0.14)
Example 4	Compound a-37	5.9	12.77	8.3	(0.15, 0.14)
Comparative Example 1	NPB	7.2	13.35	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 color purity as well as green light emission of long life is obtained, so that the green of the organic light emitting device It can be used as a phosphorescent host material to significantly improve luminous efficiency and lifetime.

It is apparent that the compounds of the present invention can achieve the same effect even when used in other organic material layers of the organic light emitting device, for example, a light emitting layer, as well as an electron injection layer, an electron transport layer, a hole injection layer and a hole transport layer.

Preparation Example 2

A preparation example or a synthesis example of the compound based on dibenzocarbazole belonging to the formulas (9) to (15) will be described. For dibenzocarbazole (intermediate 1) in the synthetic scheme, the starting material is Tetrahedron Vol. 30. 2983, (1974) was synthesized in the same manner, Example A was synthesized in the same manner as the prior patent application number KR10-2009-0091482. However, one or two of the compounds containing dibenzocarbazole will be exemplarily described since the number of compounds including dibenzocarbazole belonging to Formulas 9 to 15 is large.

A person skilled in the art to which the present invention pertains may prepare a compound including dibenzocarbazole belonging to the present invention, which is not illustrated based on the preparation examples described below.

 Scheme 2

Synthesis Example 2

Synthesis of Compound C-19

Synthesis of Intermediate 2

Dibiphenyl-4-ylamine, 1-Bromo-4-iodobenzene, Pd ₂ (dba) ₃ , Triphenylphosphine and Sodium tert-butoxide are added to a toluene solvent and stirred under reflux for 24 hours at 130 ° C. After completion of the reaction, the mixture was extracted with MC, water, dried over MgSO ₄ , concentrated, and the resulting compound was separated by column chromatography to obtain Intermediate 2, a desired compound, in 63% yield.

Synthesis of Intermediate 4

After dissolving intermediate 3 in THF, n-BuLi was slowly added dropwise at -78 ° C, followed by stirring for about 1 hour. Triisopropylborate was then slowly added dropwise at -78 ° C, stirred, acidified with 1N HCl, extracted with water and EA, dried over MgSO4 and recrystallized with Hexane to give intermediate 4 in 52% yield.

Synthesis of Compound C-19 (Compound 5)

Phenylboronic acid, intermediate 4, and Pd (PPh ₃ ) ₄ were added with K ₂ CO ₃ in 500 ml of THF and 250 ml of water and refluxed for 24 hours. The obtained solid was washed with water and methanol, and then separated by silica gel column chromatography to obtain a white solid product 5 in 60% yield.

Synthesis of Compound B-20 (Compound 6)

Synthesis of Intermediate 2 except N- (biphenyl-4-yl) -9,9-dimethyl-9H-fluoren-2-amine in place of Dibiphenyl-4-ylamine and Intermediate 3 in place of 1-Bromo-4-iodobenzene It is the same as the synthesis method of intermediate 4.

Manufacturing Evaluation of Organic Electroluminescent Device 2

Various compounds obtained through the synthesis described above were used as light emitting host materials or hole transporting layers of the light emitting layer, respectively, to fabricate an organic light emitting display device according to a conventional method. First, a copper phthalocyanine (hereinafter abbreviated as CuPc) film was vacuum-deposited on the ITO layer (anode) formed on the glass substrate to form a thickness of 10 nm. Subsequently, when the compound of the present invention was measured with a green host, 4,4-bis [ N- (1-naphthyl) -N -phenylamino] biphenyl (hereinafter a-NPD) was used as the major transport compound on the membrane. Abbreviated) in vacuum to a thickness of 30 nm to form a hole transport layer. After forming the hole transport layer, when the compound of the present invention is measured by the hole transport layer, a light emitting layer doped with 7% of BD-052X (Idemitus) having a thickness of 45 nm on the hole transport layer (where BD-052X is a blue fluorescent dopant) 9,10-di (naphthalene-2-anthracene (AND)) was used as the light emitting host material.

When measuring with a phosphorescent host material, a phosphorescent material was deposited to form a light emitting layer and tris (2-phenylpyridine) iridium (hereinafter abbreviated as I r (ppy) ₃ ) was added as a phosphorescent Ir metal complex dopant. . At this time, the concentration of I r (ppy) _{3 in} the light emitting layer was 10% by weight. (1,1'bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10 nm with a hole blocking layer, followed by electrons. Tris (8-quinolinol) aluminum (hereinafter abbreviated to Alq ₃ ) was formed into an injection layer to a thickness of 40 nm. Subsequently, 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 prepare an organic light emitting display device by using this Al / LiF as a cathode.

Comparative Experiment 2

When the compounds of the present invention were measured by a host, an organic electroluminescent device having the same structure as the experimental example was manufactured by using the compound represented by Formula 16 as a light emitting host material instead of the compound of the present invention for comparison.

The physical properties of the organic light emitting device described above are summarized in Table 3 below.

TABLE 3

	Host material of emitting layer	Voltage (V)	Current density (mA / cm 2 )	Luminous Efficiency (cd / A)	Chromaticity coordinates (x, y)
Example 1	Compound A-5	5.0	0.32	48.2	(0.33, 0.61)
Example 2	Compound a-13	5.2	0.34	46.3	(0.32, 0.62)
Example 3	Compound a-14	5.3	0.36	46.5	(0.33, 0.61)
Example 4	Compound A-18	5.3	0.33	44.7	(0.32, 0.63)
Comparative Example 1	CBP	6.1	0.32	32.6	(0.33, 0.61)

In addition, when the compounds of the present invention were measured by the hole transport layer, an organic electroluminescent device having the same structure as the test example was manufactured using the compound represented by Formula 17 as a hole transport material instead of the compound of the present invention for comparison.

Table 4

	Hole transport material	Voltage (V)	Current density (mA / cm 2 )	Luminous Efficiency (cd / A)	Chromaticity coordinates (x, y)
Example 1	Compound b-19	6.9	12.88	8.3	(0.15, 0.13)
Example 2	Compound b-20	6.7	12.76	8.4	(0.15, 0.14)
Example 3	Compound C-2	6.3	13.09	8.6	(0.15, 0.14)
Example 4	Compound c-19	5.9	12.86	8.5	(0.15, 0.15)
Example 5	Compound C-26	6.0	12.87	8.4	(0.15, 0.14)
Comparative Example 1	NPB	7.2	13.35	7.5	(0.15, 0.15)

As can be seen from Tables 3 and 4, the organic electroluminescent device using the organic electroluminescent device material of the present invention is not only high efficiency and color purity but also green light emission of long life is obtained, green phosphorescence of the organic light emitting device Used as a host material can significantly improve the luminous efficiency and lifetime. In addition, it is used as a hole transporting material can significantly improve the characteristics of the organic light emitting display device with a low driving voltage and high luminous efficiency. Therefore, it can be seen that the embodiment has substantially the same color coordinates with respect to the comparative example, and the driving voltage, current density, and luminous efficiency are improved with a critical significance.

Based on the above results, the compound according to the embodiment of the present invention is an organic electroluminescent compound including dibenzocarbazole. In addition, the compound according to the embodiment has a high hole injection, hole transport ability and excellent electrical characteristics and light emission characteristics, and the material for simultaneously performing the hole injection material, hole transport material, hole injection and hole transport and red, green, blue, It is useful as a host material suitable for phosphorescent dopants of all colors such as white. Therefore, when employing an organic film using such a compound, it is possible to fabricate an organic light emitting device having high efficiency, low voltage, high brightness, increased stability, and long life based on superior current density characteristics compared to conventional materials.

Although the embodiments of the present invention have been described above with reference to the accompanying drawings, the technical configuration of the present invention described above may be modified in other specific forms without changing the technical spirit or essential features of the present invention by those skilled in the art to which the present invention pertains. It will be appreciated that it may be practiced. Therefore, the embodiments described above are to be understood as illustrative and not restrictive in all aspects. In addition, the scope of the present invention is shown by the claims below, rather than the above detailed description. Also, it is to be construed that all changes or modifications derived from the meaning and scope of the claims and their equivalent concepts are included in the scope of the present invention.

Claims (16)

1. A compound represented by the following formula (1).

   Formula 1

   Z- (Y) n

   In Formula 1, Z represents a group consisting of a substituted or unsubstituted aromatic hydrocarbon group or aromatic heterocyclic group, Y represents a group represented by the following Formula 2, and n represents an integer of 1 to 6.

   Formula 2

   

   R ₁ to R ₉ in Formula 2 are the same as or different from each other, and each independently 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, C ₁ -C ₆₀ arylamine group, C ₁ -C ₆₀ alkyl thiophene group, C ₆ -C ₆₀ aryl thiophene group, C ₂ -C ₆₀₀ alkenyl group, C ₂ -C ₆₀ alkynyl group, C ₃ ~ cycloalkyl group of C _60, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted by deuterium aryl group, a C ₈ ~ arylalkenyl group, a substituted or unsubstituted silane group, a substituted ring of C ₆₀ Or a C ₆ -C ₆₀ aryl group unsubstituted or substituted with one or more groups selected from the group consisting of an unsubstituted boron group, a substituted or unsubstituted germanium group, and a substituted or unsubstituted C ₅ -C ₆₀ heterocyclic group. of _{halogen, CN, NO 2, C 1} ~ C 60 alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkyl amine group, C ₁ ~ C import of ₆₀ alkylthio, C ₂ ~ C ₆₀ of alkenyl group, C ₂ ~ C ₆₀ Al Group, C ₃ ~ C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted by deuterium aryl group, a substituted or unsubstituted silane group, a substituted or unsubstituted boron group, a substituted Or an unsubstituted germanium group and a substituted or unsubstituted C ₅ to C ₆₀ heterocyclic group substituted or unsubstituted with a C ₅ to C ₆₀ heterocyclic group or C ₆ to C ₆₀ A condensed ring group of an aromatic ring and a C ₄ to C ₆₀ aliphatic ring, each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, a substituted and unsubstituted heteroaryl Arbitrary groups selected from the group, adjacent positions may be bonded to each other to form a ring, represented by the following formula (3),

   X represents C, N, O, S, Si, P, Ge,

   Any one of R ₁ to R ₉ is Z.

   

   In Formula 3, R ₁₀ to R ₁₅ independently have the same meanings as R ₁ to R ₉ ,

   Ring A condensed to indole is

   

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   It includes any one selected.
2. The method of claim 1,

   When n is 1 in Formula 1, a compound represented by the following formula (4).

   Formula 4

   

   One of said R represents said Z.
3. The method of claim 1,

   In the formula 1, when n is 2 or more, the compound represented by one of the following formula (5).

   Formula 5

   

   ,

   

   ,

   
4. A compound represented by Formula 6;

   Formula 6

   

   In Chemical Formula 6,

   R ₁ to R ₁₃ are the same as or different from each other, and each independently 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, and C ₁ to C ₆₀ arylamine group, C ₁ to C ₆₀ alkyl thiophene group, C ₆ to C ₆₀ aryl thiophene group, C ₂ to C ₆₀ alkenyl group, C ₂ to C ₆₀ alkynyl group, C ₃ to C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted by deuterium aryl group, a C ₈ ~ C ₆₀ arylalkenyl group, a substituted or unsubstituted silane group, a substituted or unsubstituted ring of A C ₆ -C ₆₀ aryl group unsubstituted or substituted with one or more groups selected from the group consisting of a boron group, a substituted or unsubstituted germanium group, and a substituted or unsubstituted C ₅ -C ₆₀ heterocyclic group; Of _{halogen, CN, NO 2, C 1} ~ C 60 alkyl group, C ₁ ~ C ₆₀ alkoxy group, C ₁ ~ C ₆₀ alkyl amine group, C ₁ ~ C import of ₆₀ alkylthio, C ₂ ~ C ₆₀ of alkenyl group, C ₂ ~ C ₆₀ of the alkynyl group, C ₃ ~ C ₆₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₆₀ substituted by deuterium 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 substituted or unsubstituted by at least one group selected from the group consisting of a heterocycle of the C ₅ ~ C ₆₀ unsubstituted C ₅ ~ C ₆₀ ring Heterocyclic group; Or a condensed ring group of an aromatic ring of C ₆ to C ₆₀ and an aliphatic ring of C ₄ to C ₆₀ , each independently a hydrogen atom, a halogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group , Any group selected from substituted and unsubstituted heteroaryl groups, and adjacent positions combine with each other to form a ring.
5. The method of claim 4, wherein

   When R ₁₄ is hydrogen or alkyl, aryl, heteroaryl, the compound represented by Formula 6 is represented by the following formula (7).

   Formula 7

   
6. The method of claim 4, wherein

   When R ₁₆ is directly connected to a substituted or unsubstituted alkylamine or arylamine, the compound represented by Formula 6 is represented by the formula (8).

   Formula 8

   
7. The method of claim 4, wherein

   When R ₁₆ is a substituted or unsubstituted alkylamine or arylamine having a linking group, the compound represented by Chemical Formula 6 is represented by the following Chemical Formula 9.

   Formula 9

   
8. The method according to claim 1 or 4,

   Said compound being used in a soluble process.
9. An organic electronic device comprising at least one organic material layer comprising the compound of claim 1.
10. The method of claim 9,

    The organic electronic device is an organic electroluminescent device comprising a first electrode, the organic material layer of one or more layers and the second electrode is sequentially stacked.
11. The method of claim 9,

    The organic material layer may include at least one of a hole injection layer, a hole transport layer, and a layer for simultaneously injecting holes and transporting holes, and at least one of the layers may include the compound.
12. The method of claim 9,

    The organic material layer includes an emission layer, and the emission layer comprises the compound.
13. The method of claim 9,

    The organic material layer includes a light emitting auxiliary layer, wherein the light emitting auxiliary layer comprises the compound.
14. The method according to claim 9,

    The organic electronic device includes an organic light emitting diode (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a photodiode, an organic laser, and a laser diode. Organic electronic device, characterized in that any one selected from the group consisting of.
15. The method of claim 9,

    The compound of claim 1, wherein the light emitting layer is formed by a soluble process.
16. A display device comprising the organic electric element of claim 9;

    And a control unit for driving the display device.

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