WO2013108997A1 - Compound for organic electronic device, and organic electronic device and electronic apparatus comprising same - Google Patents

Abstract

The present invention provides a novel compound comprising a five-atom heterocycle which can enhance light-emitting efficiency, stability, and life of a device, and an organic electronic device and an electronic apparatus comprising same.

Description

Compound for organic electric device, organic electric device comprising same and electronic device thereof

The present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device 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. The organic layer is often made of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electrical 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 biggest problem for organic electroluminescent devices is life and efficiency. As the display becomes larger, such efficiency and life problems must be solved. Efficiency, lifespan, and driving voltage are related to each other.As the efficiency increases, the driving voltage decreases relatively, and the crystallization of organic materials due to Joule heating generated during driving decreases as the driving voltage decreases. It shows a tendency to increase the life.

However, simply improving the organic material layer does not maximize the efficiency. This is because a long life and high efficiency can be achieved at the same time when an optimal combination of energy level and T1 value between each organic material layer and intrinsic properties (mobility, interfacial properties, etc.) of the material is achieved.

In addition, in order to solve the problem of light emission in the hole transport layer in the organic electroluminescent device, a light emitting auxiliary layer must exist between the hole transport layer and the light emitting layer, and different light emission auxiliary according to each light emitting layer (R, G, B) is required. It is time to develop the floor. In general, electrons are transferred from the electron transport layer to the light emitting layer, and holes are transferred from the hole transport layer to the light emitting layer to generate excitons by recombination. However, in the case of the material used in the hole transport layer, since it has to have a low HOMO value, most have a low T1 value, which causes the excitons generated in the light emitting layer to pass to the hole transport layer, resulting in charge unbalance in the light emitting layer. This causes light emission at the hole transport layer interface.

When light is emitted from the hole transport layer interface, color purity and efficiency of the organic electric element are lowered, and a lifespan is shortened. Accordingly, the development of a light emitting auxiliary layer having a high T1 value and a HOMO level between the hole transport layer HOMO energy level and the light emitting layer HOMO energy level is urgently required.

On the other hand, it delays the diffusion of metal oxide into the organic layer from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electronic device, and stable characteristics, that is, high glass transition even for Joule heating generated when driving the device. There is a need for development of a hole injection layer material having a temperature. 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.

In order to fully exhibit the excellent characteristics of the above-described organic electroluminescent device, materials forming the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting auxiliary layer material, a light emitting material, an electron transport material, an electron injection material, etc., are stable and efficient. Supported by the material should be preceded, but the development of a stable and efficient organic material layer for an organic electric device has not been made enough, and therefore, the development of new materials is still required.

An object of the present invention is to provide a compound containing an five-membered hetero ring capable of improving the luminous efficiency, low driving voltage, color purity, and lifetime of the device, an organic electric device using the same, and an electronic device thereof.

In one aspect, the present invention provides a compound represented by the following formula.

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

By using the compound according to the present invention, the driving voltage of the device can be lowered, and color purity, luminous efficiency and lifetime can be greatly improved.

1 is an exemplary view of an organic electroluminescent device according to an embodiment of the present invention.

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".

On the other hand, the terms "halo" or "halogen" as used herein include fluorine, chlorine, bromine, and iodine unless otherwise stated.

As used herein, the term "alkyl" or "alkyl group" has a carbon number of 1 to 60 unless otherwise specified, but is not limited thereto.

As used herein, the term "alkenyl" or "alkynyl" has a double bond or a triple bond having 2 to 60 carbon atoms, respectively, unless otherwise specified, but is not limited thereto.

The term "cycloalkyl" as used herein, unless otherwise stated, refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto.

The term "alkoxy group" used in the present invention has a carbon number of 1 to 60 unless otherwise stated, it is not limited thereto.

As used herein, the terms "aryl group" and "arylene group" have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto.

The aryl group or arylene group in the present invention means a monocyclic or heterocyclic aromatic, for example, the aryl group may be a phenyl group, biphenyl group, fluorene group, spirofluorene group.

As used herein, the term “heteroalkyl” means an alkyl including one or more heteroatoms unless otherwise indicated. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 3 to 60 carbon atoms, each of which includes one or more heteroatoms, unless otherwise specified. In addition, it includes not only a single ring but also a heterocycle, and adjacent groups may be formed by bonding.

As used herein, the terms "heterocycloalkyl" and "heterocyclic group" include one or more heteroatoms, unless otherwise specified, have a carbon number from 2 to 60, and include heterocycles as well as monocycles. Adjacent groups may be formed in combination. In addition, "heterocyclic group" may mean an alicyclic and / or aromatic including a heteroatom.

As used herein, the term “heteroatom” refers to at least one of N, O, S, P, and Si unless otherwise indicated.

Unless otherwise stated, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms, and the "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise stated, the term "saturated or unsaturated ring" as used herein means a saturated or unsaturated aliphatic ring or an aromatic ring or heterocyclic ring having 6 to 60 carbon atoms.

Other heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.

Also, unless stated otherwise, the term "substituted" in the term "substituted or unsubstituted" as used in the present invention is deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl amine group, C ₁ ~ C ₂₀ coming of the alkyl group, C ₆ ~ C ₂₀ coming aryl Ti, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ of the Alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₆ ~ C ₂₀ aryl group substituted with deuterium, C ₈ ~ C ₂₀ aryl alkenyl group, silane group, boron group, It means that it is substituted with one or more substituents selected from the group consisting of a germanium group, and a C ₅ ~ C ₂₀ heterocyclic group, and is not limited to these substituents.

1 is an exemplary view of an organic electric device according to an embodiment of the present invention.

Referring to FIG. 1, the organic electric device 100 according to the present invention includes a first electrode 120, a second electrode 180, a first electrode 110, and a second electrode 180 formed on a substrate 110. An organic material layer containing a compound represented by the formula (1) between) is provided. In this case, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

The organic layer may include a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170 on the first electrode 120 in sequence. At this time, the remaining layers except for the light emitting layer 150 may not be formed. The hole blocking layer, the electron blocking layer, the light emitting auxiliary layer 151, the buffer layer 141 may be further included, and the electron transport layer 160 may serve as the hole blocking layer.

In addition, although not shown, the organic electronic device according to the present invention may further include a protective layer formed on one surface of the first electrode and the second electrode opposite to the organic material layer.

The compound according to the present invention applied to the organic material layer is a hole injection layer 130, a hole transport layer 140, an electron transport layer 160, the electron injection layer 170, the host of the light emitting layer 150 or the material of the dopant or capping layer Can be used as Preferably, the compound of the present invention may be used as the light emitting layer 150, hole transport layer 140 and / or light emitting auxiliary layer 151.

Meanwhile, even in the same core, band gaps, electrical characteristics, and interface characteristics may vary depending on which substituents are bonded at which positions. Therefore, the selection of cores and the combination of sub-substituents bound thereto are also very significant. Importantly, long life and high efficiency can be achieved at the same time when an optimal combination of energy level and T1 value and intrinsic properties (mobility, interfacial properties, etc.) of each organic material layer is achieved.

As described above, in order to solve the light emission problem in the hole transport layer in the organic electroluminescent device, it is preferable to form a light emitting auxiliary layer between the hole transport layer and the light emitting layer, and according to each of the light emitting layers R, G, and B, It is time to develop different emission auxiliary layers. Meanwhile, in the case of the light emitting auxiliary layer, it is difficult to infer the characteristics of the organic material layer used even if a similar core is used, since the correlation between the hole transport layer and the light emitting layer (host) must be understood.

Therefore, in the present invention, by forming a light emitting layer or an auxiliary light emitting layer using a compound represented by the formula (1) by optimizing the energy level (level) and T1 value between each organic material layer, the intrinsic properties (mobility, interface characteristics, etc.) of the organic material The life and efficiency of the electric device can be improved at the same time.

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a PVD method. For example, the anode 120 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and the hole injection layer 130, the hole transport layer 140, the light emitting layer 150, and the electron transport layer are formed thereon. After forming the organic material layer including the 160 and the electron injection layer 170, it can be prepared by depositing a material that can be used as the cathode 180 thereon.

In addition, the organic layer may be prepared by 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 prepared in a number of layers. Since the organic material layer according to the present invention may be formed in various ways, the scope of the present invention is not limited by the forming method.

The organic electric element 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.

In addition, the organic electroluminescent device according to the present invention may be one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), a monochromatic or white illumination device.

Another embodiment of the present invention may include a display device including the organic electric element of the present invention described above, and an electronic device including a control unit for controlling the display device. In this case, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

Hereinafter, the compound which concerns on one aspect of this invention is demonstrated.

Hereinafter, the compound which concerns on one aspect of this invention is demonstrated.

The compound according to one aspect of the present invention is represented by the following formula (1).

Formula 1

In Chemical Formula 1,

R ₁ to R ₄ and R ₁₁ to R ₁₄ are each independently selected from hydrogen, deuterium, halogen, C ₆ ~ C ₆₀ aryl group, fluorenyl group, C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ Fused ring group of aromatic ring, C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P, -LN (R ') (R "), C ₁ ~ C _It is selected from the group consisting of an alkyl group of _50, an alkenyl group of C ₂ to C ₂₀ , an alkoxy group of C ₁ to C ₃₀ , and an aryloxy group of C ₆ to C ₃₀ .

R ₂₁ and R ₂₂ are each independently i) a hydrogen, C ₆ ~ C ₆₀ aryl group, fluorenyl group, C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring, O , C ₂ -C ₆₀ heterocyclic group including at least one hetero atom of N, S, Si and P and -LN (R ') (R "), or ii) Form a monocyclic or polycyclic ring.

However, only when R ₂₁ and R ₂₂ are bonded to each other to form a ring, R ₁ to R ₄ and R ₁₁ to R ₁₄ may both be hydrogen at the same time, and R ₂₁ and R ₂₂ may be bonded to each other to form a ring. Otherwise, at least one of R ₁ to R ₄ is not hydrogen and at least one of R ₁₁ to R ₁₄ is not hydrogen at the same time.

When R ₂₁ and R ₂₂ are bonded to each other to form a ring, it is important that they are bonded to each other to form a ring, and thus the scope of the present invention is not limited by the substituents and the reaction to form the ring. Does not.

The ring formed by combining R ₂₁ and R ₂₂ with each other may be not only an aromatic ring or a hetero ring including at least one hetero atom, but also a form in which an aromatic ring and an aliphatic ring are fused together. For example, R ₂₁ and R ₂₂ may be bonded to each other to form an aromatic ring such as benzene, naphthalene, phenanthrene, and the like. Preferably, the aromatic ring has 6 to 60 carbon atoms. In addition, R ₂₁ and R ₂₂ may be bonded to each other to form a heterocycle such as thiophene, furan, pyridine, indole, quinoline, and the like, wherein the carbon number may be 2 to 60. In the case of a polycyclic ring, the ring may be fused to each other, a plurality of rings may not be fused to each other, or a ring in which the fused and non-fused forms are mixed.

In Formula 1, X and Y are each independently S, O or SiR ₃₁ R ₃₂ . Here, R ₃₁ and R ₃₂ are independently of each other hydrogen, a C ₆ ~ C ₆₀ aryl group, C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P, Or a C ₁ to C ₅₀ alkyl group. Meanwhile, in the above formula, m and n may each be 0 or 1, except that m and n are both 0. Since m + n = 1 must be an integer, at least one of X and Y must be present.

L is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And divalent aliphatic hydrocarbon group; It is selected from the group consisting of. At this time, the arylene group, fluorenylene group, heterocyclic group and aliphatic hydrocarbon group, nitro group, cyano group, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ hetero It may be substituted with one or more substituents selected from the group consisting of a ring group, a C ₁ to C ₂₀ alkoxy group and an amino group.

Ar is a C ₂ -C ₆₀ heterocyclic group, a C ₆ -C ₆₀ aryl group or -N (R ') (R ") containing at least one heteroatom of O, N, S, Si and P. .

On the other hand, the R 'and R "defined in R ₁ ~ R ₄ and R ₁₁ ~ R ₁₄ , R ₂₁ and R ₂₂ , Ar and the like are independently of each other at least one heteroatom of O, N, S, Si and P It may include a C ₂ ~ C ₂₀ heterocyclic group, C ₆ ~ C ₂₀ An aryl group or a fluorenyl group.

Meanwhile, R_One~ R₄, R₁₁~ R₁₄, R₂₁, R₂₂, R₃₁, R₃₂When Ar, R 'and R "are aryl groups, they are deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, C_One~ C₂₀Alkylthio, C_One~ C₂₀Alkoxyl, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C₂~ C₂₀Alkynyl, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₂~ C₂₀Heterocyclic group, C₃~ C₂₀Cycloalkyl group, C₇~ C₂₀of Arylalkyl group and C₈~ C₂₀May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,

R_One~ R₄, R₁₁~ R₁₄, R₂₁, R₂₂, R₃₁, R₃₂When Ar, R 'and R "are heterocyclic groups, they are deuterium, halogen, silane, cyano, nitro, C_One~ C₂₀Alkoxyl, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₂~ C₂₀Heterocyclic group, C₃~ C₂₀Cycloalkyl group, C₇~ C₂₀of Arylalkyl group and C₈~ C₂₀May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,

When R ₁ to R ₄ , R ₁₁ to R ₁₄ , R ₂₁ , R ₂₂ , R 'and R ″ are fluorenyl groups, they are deuterium, halogen, silane group, cyano group, C ₁ to C ₂₀ alkyl group, C for ₂ ~ C ₂₀ of alkenyl groups _{(alkenyl), C 6 ~ C} 20 aryl group, a C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ substituted by deuterium May be substituted with one or more substituents selected from the group consisting of cycloalkyl groups,

R_One~ R₄, R₁₁~ R₁₄, R₂₁ And R₂₂In the case of the fused ring group, it is deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, C_One~ C₂₀Alkylthio, C_One~ C₂₀Alkoxyl, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C₂~ C₂₀Alkynyl, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₂~ C₂₀Heterocyclic group, C₃~ C₂₀Cycloalkyl group, C₇~ C₂₀of Arylalkyl group and C₈~ C₂₀May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,

R_One~ R₄, R₁₁~ R₁₄, R₃₁ And R₃₂When is an alkyl group, it is halogen, silane group, boron group, cyano group, C_One~ C₂₀Alkoxyl, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₂~ C₂₀Heterocyclic group, C₇~ C₂₀of Arylalkyl group and C₈~ C₂₀May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,

R_One~ R₄ And R₁₁~ R₁₄Is an alkenyl group, it is a deuterium, a halogen, a silane group, a cyano group, C_One~ C₂₀Alkoxyl, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₂~ C₂₀Heterocyclic group, C₃~ C₂₀Cycloalkyl group, C₇~ C₂₀of Arylalkyl group and C₈~ C₂₀May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,

When R ₁ to R ₄ and R ₁₁ to R ₁₄ are an alkoxyl group, this is deuterium, halogen, silane group, C ₁ ~ C ₂₀ alkyl group, C ₆ ~ C ₂₀ aryl group, C ₆ ~ substituted with deuterium C ₂₀ may be substituted with one or more substituents selected from the group consisting of an aryl group, C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ cycloalkyl group,

Wherein R ₁ ~ R ₄ and R ₁₁ ~ R, if ₁₄ is an aryloxy group which is substituted C with deuterium, a silane group, a cyano group, C ₁ ~ C ₂₀ alkyl group, an aryl group, a heavy hydrogen of C ₆ ~ C ₂₀ of ₆ It may be substituted with one or more substituents selected from the group consisting of an aryl group of ~ C ₂₀ , a heterocyclic group of C ₂ ~ C ₂₀ and a cycloalkyl group of C ₃ ~ C ₂₀ .

The compound represented by Chemical Formula 1 may be represented by one of the following chemical formulas.

 <Formula 2>

 <Formula 3>

 <Formula 4>

 <Formula 5>

 <Formula 6>

 <Formula 7>

 <Formula 8>

 <Formula 9>

In Formulas 2 to 9, Ar 'is hydrogen, deuterium, halogen, C ₁ ~ C ₂₀ Alkyl group, C ₂ ~ C ₂₀ Alkenyl group, C ₁ ~ C ₂₀ Alkoxy group, -LN (R') ( R "), an arylalkenyl group of C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ substituted by deuterium, C ₂ ~ C ₂₀ Is selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group,

X ₁ to X ₄ are CR ₄₁ or N. In this case, R ₄₁ may be hydrogen, deuterium, an aryl group of C ₆ ~ C ₂₀ or a heterocyclic group of C ₂ ~ C ₂₀ , R ₁ ~ R ₄ , R ₁₁ ~ R ₁₄ , R ₂₁ , R ₂₂ , R ' , R ", X, Y, L and Ar are as defined in formula (1),

More specifically, the compound represented by Formula 1 or 2 may be one of the following compounds.

Hereinafter, the synthesis examples of the compounds of the present invention represented by the above formula and the production examples of the organic electric device will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.

Synthesis Example

For example, the compound according to the present invention is prepared by reacting one of Sub 1 to Sub 4 with Sub 5, as in Scheme 1 below. In the following synthesis method, a case where X is S will be described by way of example, but when X is O or Si, it is similar to the following synthesis method and will not be described separately. In the following schemes, the symbol R ₁ is one of R ₁ to R ₄ described in Formula 1, R ₂ is R ₂₁ or R ₂₂ , and R ₃ is one of R ₁₁ to R ₁₄ .

Compounds of the present invention can be prepared by the following Scheme 1 or Scheme 2 illustratively.

<Scheme 1>

<Scheme 2>

Hereinafter, a method for preparing a compound of the present invention according to the above scheme will be described after explaining the synthesis method of Sub 1 to Sub 4, and the like.

Example of Sub 1 synthesis:

<Scheme 3>

Sub 1-1 Synthesis

Dibenzothiophene derivatives substituted with R ₁ and R ₂ were dissolved in a carbon disulfide solvent in a nitrogen atmosphere, and bromine was slowly added dropwise. After stirring at room temperature for 12 hours, when the reaction was completed, the organic solvent was concentrated using a pressure reduction apparatus and the resulting product was recrystallized using ethanol solvent to obtain the desired Sub 1-1.

Sub 1-2 synthesis

The obtained Sub 1-1 was dissolved in anhydrous THF, the reaction temperature was lowered to −78 ° C., n-BuLi (2.5 M inhexane) was slowly added dropwise, and the reaction was stirred at 0 ° C. for 1 hour. The temperature of the reaction was lowered to −78 ° C., trimethyl borate was added dropwise, followed by stirring at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. The organic layer was dried over MgSO ₄ , concentrated, and the resulting organic was recrystallized from a Silicagel column to obtain the desired Sub 1-2.

Sub 1-3 Synthesis

After dissolved the 1-bromo-2-nitrobenzene, Pd (PPh 3) 4, K 2 CO 3 Sub substituted with 1-2 R ₃ and obtained in anhydrous THF and a small amount of water and the mixture was refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting organics were separated using a Silicagel column to obtain the desired Sub 1-3.

Sub 1 Synthesis

The obtained Sub 1-3 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After completion of the reaction, the solvent was removed by distillation under reduced pressure, and the concentrated product was recrystallized from a Silicagel column to obtain desired Sub 1.

Example of Sub 2 synthesis:

<Scheme 4>

Sub 2-1 Synthesis

4-bromophenylboronic acid substituted with R ₂ , (2-iodophenyl) (methyl) sulfane substituted with R ₁ , Pd (PPh ₃ ) ₄ , K ₂ CO ₃ , THF, water were added thereto, and the synthesis method of Sub 1-3 Proceed in the same manner to obtain the desired Sub 2-1.

Sub 2-2 synthesis

Sub 2-1 was dissolved in acetic acid, and hydrogen peroxide dissolved in acetic acid was added dropwise, followed by stirring at room temperature for 6 hours. Upon completion of the reaction, acetic acid was removed using a decompression device and separated using a Silicagel column to obtain the desired Sub 2-2.

Sub 2-3 synthesis

The obtained Sub 2-2 and trifluoromethanesulfonic acid were added thereto, stirred at room temperature for 24 hours, and slowly added water and pyridine (8: 1) to reflux for 30 minutes. Lower the temperature, extract with CH ₂ Cl ₂ and wipe with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the organic solvent was concentrated. The resulting product was purified by Silicagel column and recrystallized to obtain the desired Sub 2-3.

Sub 2-4 Synthesis

The obtained Sub 2-3 was carried out similarly to the synthesis method of Sub 1-2, to obtain Sub 2-4.

Sub 2-5 synthesis

Substituted 1-bromo-2-nitrobenzene, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ , THF, water substituted Sub 2-4 and R ₃ obtained in the same manner as the synthesis method of Sub 1-3 and the desired Sub 2-5 was obtained.

Sub 2 synthesis

The obtained Sub 2-5 was processed in the same manner as in the synthesis of Sub 1 to obtain a desired Sub 2.

Example of Sub 3 synthesis:

Scheme 5

Sub 3-1 Synthesis

5-bromobenzo [b] naphtho [2,1-d] thiophene substituted with R ₁ was processed in the same manner as in the synthesis of Sub 1-2 to obtain the desired Sub 3-1.

Sub 3-2 Synthesis

1-bromo-2-nitrobenzene, Pd (PPh ₃ ) ₄ , K ₂ CO ₃ , THF, and water substituted with Sub 3-1 and R ₃ obtained in the same manner as in the synthesis of Sub 1-3 were prepared. -2 was obtained.

Sub 3 synthesis

Sub 3-2 was obtained in the same manner as in the synthesis of Sub 1, to obtain a desired sub 3.

Sub 4 synthesis example:

<Scheme 6>

Sub 4-1 Synthesis

(2-bromophenyl) (methyl) sulfane substituted with 4-bromonaphthalen-1-ylboronic acid, R ₁ , Pd (PPh ₃ ) ₄ , K ₂ CO ₃ , THF, and water were added. Proceed to obtain the desired Sub 4-1.

Sub 4-2 synthesis

Sub 4-1 was carried out in the same manner as in the synthesis of Sub 2-2, to obtain a desired Sub 4-2.

Sub 4-3 synthesis

The obtained Sub 4-2 was carried out in the same manner as the synthesis method of Sub 2-3 to obtain the desired Sub 4-3.

Sub 4-4 Synthesis

The obtained Sub 4-3 was processed in the same manner as the synthesis method of Sub 1-2 to obtain Sub 4-4.

Sub 4-5 synthesis

Substituted 1-bromo-2-nitrobenzene, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ , THF, water substituted Sub 4-4 and R ₃ obtained in the same manner as the synthesis method of Sub 1-3 and the desired Sub 2-5 was obtained.

Sub 4 synthesis

The obtained Sub 4-4 was processed in the same manner as in the synthesis of Sub 1 to obtain a desired Sub 4.

Product Synthesis Example

The compounds according to the present invention can be synthesized by Reaction Schemes 1 and 2. Examples of synthesizing the compound of the present invention in two ways are as follows.

Method 1 (Scheme 1)

After mixing Sub 1 to 4 and Sub 5 to toluene, Pd ₂ (dba) ₃ , P ( t -Bu) ₃ and NaO t -Bu were added, respectively, and the mixture was stirred under reflux at 100 ° C. for 24 hours. After extraction 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 a final product.

Method 2-1 (Scheme 2)

Sub 11-1 or Sub 11-2 (1 equiv) was dissolved in THF in a round bottom flask, then Sub 9 (1.2 equiv), Pd (PPh ₃ ) ₄ (0.03 equiv), NaOH (3 equiv) and water were added After stirring, the mixture was refluxed. 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 a product product.

Method 2-2 (Scheme 2)

In a round bottom flask, Sub 11-1 or Sub 11-2 compound (1 equiv), Sub 10 compound (1.2 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 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 silicagel column and recrystallized to obtain a product product.

Examples of Sub 5, Sub 9, and Sub 10 used in Method 1 and Method 2 are as follows, but are not limited thereto.

Sub 5 example

An example of Sub 5 is as follows, but is not limited thereto.

FD-MS values for the exemplary material of Sub 5 are shown in Table 1 below.

TABLE 1

Sub 9 example

An example of Sub 9 is as follows, but is not limited thereto.

Sub 10 example

An example of Sub 10 is as follows, but is not limited thereto.

The FD-MS values for the exemplary materials of Sub 9 and 10 are shown in Table 2 below.

TABLE 2

Product 1-1 Synthesis Example [Method 1]

Scheme 7

Pd ₂ (dba) ₃ (7.1 g, 20 mmol) and 2-bromo-4,6-diphenyl-1,3,5-triazine (7.5 g, 24 mmol) were mixed with toluene (210 mL), followed by Pd ₂ (dba) ₃ ( 0.92 g, 1 mmol), P ( t -Bu) ₃ (0.4 g, 2 mmol) and NaOt-Bu (5.8 g, 60 mmol) were added, and the mixture was stirred and refluxed at 100 ° C. for 24 hours. After extracting with methylene chloride and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to give 8.0g (68% yield) of product 1-1.

Product 1-13 Synthesis Example [Method 1]

Scheme 8

Five-membered heterocyclic compound (8.5g, 20mmol) and 2-bromo-4,6-diphenyl-1,3,5-triazine (7.5g, 24mmol), toluene (210 mL), Pd ₂ (dba) ₃ (0.92g , 1 mmol), P ( t -Bu) ₃ (0.4 g, 2 mmol) and NaOt-Bu (5.8 g, 60 mmol) were prepared in the same manner as in Synthesis of Product 1-1 to 8.4 g of product 1-13 ( Yield 64%).

Product 2-18 Synthesis Example [Method 1]

Scheme 9

Five-membered heterocyclic compound (11 g, 20 mmol) and bromobenzene (7.5 g, 24 mmol) were dissolved in toluene (210 mL), Pd ₂ (dba) ₃ (0.92 g, 1 mmol), P ( t -Bu) ₃ (0.4 g, 2 mmol) and NaOt-Bu (5.8 g, 60 mmol) were prepared in the same manner as in the synthesis of Product 1-1, to obtain 9.7 g (yield 62%) of product 2-18.

Product 2-31 Synthesis Example [Method 1]

Scheme 10

O-atomic hetero compounds (8.5 g, 20 mmol) and 4- (4-bromophenyl) -2,6-diphenylpyrimidine (9.3 g, 24 mmol), toluene (210 mL), Pd ₂ (dba) ₃ (0.92 g, 1 mmol) , P ( t -Bu) ₃ (0.4 g, 2 mmol) and NaOt-Bu (5.8 g, 60 mmol) were prepared in the same manner as in Synthesis of Product 1-1 to 9.2 g of product 2-31 (yield 63%) Got.

Product 3-7 Synthesis Example [Method 1]

Scheme 11

Heteroatomic hetero compounds (8.6 g, 20 mmol) and 2-bromo-4,6-diphenyl-1,3,5-triazine (7.5 g, 24 mmol), toluene (210 mL), Pd ₂ (dba) ₃ (0.92 g , 1 mmol), P ( t -Bu) ₃ (0.4 g, 2 mmol) and NaOt-Bu (5.8 g, 60 mmol) were prepared in the same manner as in Synthesis of Product 1-1 to 8.5 g ( Yield 64%).

Product 3-12 Synthesis Example [Method 1]

Scheme 12

Five-membered heterocyclic compound (9.1g, 20mmol) and 2-bromo-4,6-diphenyl-1,3,5-triazine (7.5g, 24mmol), toluene (210 mL), Pd ₂ (dba) ₃ (0.92g , 1 mmol), P ( t -Bu) ₃ (0.4 g, 2 mmol) and NaOt-Bu (5.8 g, 60 mmol) were prepared in the same manner as in Synthesis of Product 1-1 to 8.5 g ( Yield 62%).

Product 4-19 Synthesis Example [Method 1]

Scheme 13

O-atomic hetero compounds (9.5 g, 20 mmol) and 4-bromobiphenyl (5.6 g, 24 mmol), toluene (210 mL), Pd ₂ (dba) ₃ (0.92 g, 1 mmol), P ( t -Bu) ₃ (0.4 g, 2 mmol) and NaOt-Bu (5.8 g, 60 mmol) were prepared in the same manner as in the synthesis of Product 1-1, to obtain 8.2 g (yield 65%) of product 4-19.

Product 4-27 Synthesis Example [Method 1]

Scheme 14

Five-membered heterocyclic compound (9.5 g, 20 mmol) and 2- (4-bromophenyl) imidazo [1,2-a] pyridine (6.6 g, 24 mmol), toluene (210 mL), Pd ₂ (dba) ₃ (0.92 g, 1 mmol), P ( t -Bu) ₃ (0.4 g, 2 mmol) and NaOt-Bu (5.8 g, 60 mmol) were prepared in the same manner as in Synthesis of Product 1-1 to 8.1 g of product 4-27 (yield) 61%).

Product 3-28 Synthesis Example [Method 1]

Scheme 15

O-atomic hetero compounds (6.5 g, 20 mmol) with 2-bromo-4-phenylquinazoline (6.8 g, 24 mmol), toluene (210 mL), Pd ₂ (dba) ₃ (0.92 g, 1 mmol), P ( t -Bu) ₃ (0.4 g, 2 mmol) and NaO t -Bu (5.8 g, 60 mmol) were prepared in the same manner as in the above Product 1-1 synthesis to obtain 7.2 g (yield 68%) of Product 3-28.

Product 3-38 Synthesis Example [Method 1]

Scheme 16

O-atomic hetero compounds (6.5 g, 20 mmol) with 2-bromo-4-phenylquinazoline (10.5 g, 24 mmol), toluene (210 mL), Pd ₂ (dba) ₃ (0.92 g, 1 mmol), P ( t -Bu) ₃ (0.4 g, 2 mmol) and NaO t -Bu (5.8 g, 60 mmol) were prepared in the same manner as in the synthesis of Product 1-1, to obtain 8.7 g (yield 64%) of Product 3-38.

Product 3-44 Synthesis Example [Method 1]

Scheme 17

O-atomic hetero compounds (6.5 g, 20 mmol) and 2- (3-bromophenyl) -4-phenylquinazoline (8.7 g, 24 mmol), toluene (210 mL), Pd ₂ (dba) ₃ (0.92 g, 1 mmol) , P ( t -Bu) ₃ (0.4 g, 2 mmol) and NaO t -Bu (5.8 g, 60 mmol) were prepared in the same manner as in Synthesis of Product 1-1 to 7.4 g of Product 3-44 (yield 61%). )

Product 4-28 Synthesis Example [Method 1]

Scheme 18

O-atomic hetero compounds (6.5 g, 20 mmol) with 2-bromo-4-phenylquinazoline (6.8 g, 24 mmol), toluene (210 mL), Pd ₂ (dba) ₃ (0.92 g, 1 mmol), P ( t -Bu) ₃ (0.4 g, 2 mmol) and NaO t -Bu (5.8 g, 60 mmol) were prepared in the same manner as in the synthesis of Product 1-1, to obtain 7.1 g (yield 67%) of Product 4-28.

Product 6-1 Synthesis Example [Method 1]

Scheme 19

Five-membered heterocyclic compound (6.5 g, 20 mmol) with 2-bromo-4-phenylpyrido [2,3-d] pyrimidine (6.9 g, 24 mmol), toluene (210 mL), Pd ₂ (dba) ₃ (0.92 g , 1 mmol), P ( t -Bu) ₃ (0.4 g, 2 mmol) and NaO t -Bu (5.8 g, 60 mmol) were prepared in the same manner as in Synthesis of Product 1-1 to 6.7 g of Product 6-1. (Yield 63%) was obtained.

Product 7-4 Synthesis Example [Method 1]

Scheme 20

O-atomic hetero compounds (6.5 g, 20 mmol) and 4-([1,1'-biphenyl] -3-yl) -2-bromopyrido [3,2-d] pyrimidine (8.7 g, 24 mmol), toluene ( 210 mL), Pd ₂ (dba) ₃ (0.92 g, 1 mmol), P ( t -Bu) ₃ (0.4 g, 2 mmol), NaO t -Bu (5.8 g, 60 mmol) was obtained from Product 1-1. In the same manner as in the synthesis method of 7.5g (yield 62%) of Product 7-4 was obtained.

Product 5-14 Synthesis Example [Method 2-1]

Scheme 21

After dissolving the five-membered hetero compound (10.1 g, 20 mmol), (4- (naphthalen-1-yl (phenyl) amino) phenyl) boronic acid (8.14 g, 24 mmol) in THF, Pd (PPh ₃ ) ₄ ( 0.7 g, 0.6 mmol), NaOH (2.4 g, 60 mmol) and water were added, followed by stirring under reflux. 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 recrystallization to obtain 8.9 g (yield 62%) of product 5-14.

Product 5-23 Synthesis Example [Method 2-1]

Scheme 22

O-atomic hetero compounds (10.1 g, 20 mmol), (4-((9,9-dimethyl-9H-fluoren-2-yl) (phenyl) amino) phenyl) boronic acid (9.73 g, 24 mmol), Pd ( PPh ₃ ) ₄ (0.7 g, 0.6 mmol), NaOH (2.4 g, 60 mmol) and 9.4 g (yield 60%) of product Product 5-23 were obtained in the same manner as in the synthesis of Product 5-14.

Product 5-49 Synthesis Example [Method 2-1]

Scheme 23

Five-membered hetero compound (11.1 g, 20 mmol), (4-([1,1'-biphenyl] -4-yl (phenyl) amino) phenyl) boronic acid (8.77g, 24 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol), NaOH (2.4 g, 60 mmol) and 10 g (yield 63%) of product Product 5-49 were obtained in the same manner as in the synthesis of Product 5-14.

Product 5-5 Synthesis Example (Method 2-2)

Scheme 24

Di ([1,1'-biphenyl] -4-yl) amine (6.4 g, 20 mmol) with five-membered hetero compounds (12.1 g, 24 mmol) and toluene (210 mL), Pd ₂ (dba) ₃ (0.92 g, 1 mmol), P ( t -Bu) ₃ (0.4 g, 2 mmol) and NaOt-Bu (5.8 g, 60 mmol) were prepared in the same manner as in Synthesis of Product 1-1 to 9.39 g of product 5-5 (yield) 63%).

Product 5-6 Synthesis Example (Method 2-2)

Scheme 25

9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (5.7 g, 20 mmol) with five-membered hetero compounds (12.1 g, 24 mmol) and toluene (210 mL), Pd ₂ (dba) ₃ (0.92 g , 1 mmol), P ( t -Bu) ₃ (0.4 g, 2 mmol) and NaOt-Bu (5.8 g, 60 mmol) were prepared in the same manner as in Synthesis of Product 1-1 to 8.8 g of product 5-6 ( Yield 62%).

Product 5-19 Synthesis Example (Method 2-2)

Scheme 26

TABLE 3

Manufacturing Evaluation of Organic Electrical Device

Experimental Example 1 (phosphorescent green host)

Using the compound obtained through synthesis as a host material of the light emitting layer, an organic light emitting device was manufactured according to a conventional method. First, on the ITO layer (anode) formed on the glass substrate, N ^1- (naphthalen-2-yl) -N ⁴ , N ⁴ -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N ^1- A phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) film was vacuum deposited to form a hole injection layer having a thickness of 60 nm. Subsequently, 4,4-bis [ N- (1-naphthyl) -N -phenylamino] biphenyl (abbreviated as -NPD) was vacuum deposited to a thickness of 20 nm on the hole injection layer to form a hole transport layer. . In addition, the compound of the present invention (1-1 to 1-32, 2-1 to 2-32, 3-1 to 3-27, 4-1 to 4-27) is used as a host material on the hole transport layer, ppy) ₃ [tris (2-phenylpyridine) -iridium] was used as a dopant material and was doped at 95: 5 weight to deposit a light emitting layer having a thickness of 30 nm. Next, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm on the light emitting layer. After forming the blocking layer, tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was deposited to a thickness of 40 nm to form 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 form Al / LiF as a cathode, thereby manufacturing an organic EL device.

Comparative Example 1

The organic electroluminescent device was manufactured by the same method as Experimental Example 1, except that Comparative Compound 1 (4,4'-di (9H-carbazol-9-yl) -1,1'-biphenyl) was used as a light emitting host material. Was produced.

<Comparative Compound 1>

Comparative Example 2

Comparative Compound 2 (9- (9- (4,6-diphenylpyrimidin-2-yl) -9H-carbazol-3-yl) -12-phenyl-12H-benzo [4,5] thieno [3] as a light emitting host material , 2-a] carbazole), except that the organic electroluminescent device was manufactured in the same manner as in Experiment 1.

Comparative Compound 2

Comparative Example 3

Comparative Compound 3 (3- (9- (4,6-diphenyl-1,3,5-triazin-2-yl) -9H-carbazol-3-yl) -12-phenyl-12H-benzo as a light emitting host material An organic electroluminescent device was manufactured in the same manner as in Experiment 1, except that [4,5] thieno [2,3-a] carbazole) was used.

Comparative Compound 3

[Comparative Example 4]

Experimental Example 1, except that the following Comparative Compound 4 (12- (5-phenylpyrimidin-2-yl) -12H-benzo [4,5] thieno [3,2-a] carbazole) was used as a light emitting host material. An organic electroluminescent device was manufactured in the same manner.

Comparative Compound 4

[Comparative Example 5]

Using the following comparative compound 5 (12- (4- (4,6-diphenylpyrimidin-2-yl) phenyl) -12H-benzo [4,5] thieno [2,3-a] carbazole) as a light emitting host material Except, an organic electroluminescent device was manufactured in the same manner as in Experimental Example 1.

Comparative Compound 5

The electroluminescence (EL) characteristics of the organic electroluminescent devices prepared by Experimental Example 1 and Comparative Examples 1 to 5 were measured by PR-650 of photoresearch by applying a forward bias DC voltage. In this case, the T95 life was measured by the life measurement equipment manufactured by McScience Inc. at 300 cd / m ² reference luminance. In the table below, the organic light emitting display device manufactured according to Example 1 of the present invention is described as Examples 1 to 103.

TABLE 4

As shown in the table, the compounds of the present invention than Comparative Examples 1 to 5 were found to exhibit mostly low driving voltage, high efficiency and high lifetime. In addition, the compounds of the present invention including heterocyclic groups at the positions of R ₁ to R ₄ and R ₁₁ to R ₁₄ of the core showed relatively high driving voltages, low efficiency, and low life, as in Comparative Examples 2 and 3. When heterocyclic group is connected at R ₁ ~ R ₄ and R ₁₁ ~ R ₁₄ , it has relatively small band gap, HOMO increases, hole mobility decreases, driving voltage increases, efficiency and lifespan It seems to be lowering. In addition, in the case of Comparative Examples 4 and 5, which are compounds substituted with hydrogen at the positions of R ₁ to R ₄ and R ₁₁ to R ₁₄ of the core, it was confirmed that the lifespan was lower than that of the compound of the present invention.

Experimental Example 2 (phosphorescent red)

First, 2-TNATA was vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 60 nm, and NPD was then vacuum deposited to a thickness of 20 nm on the film to form a hole transport layer. Subsequently, the compound of the present invention (3-28 to 3-51, 4-28 to 4-51, 6-1 to 6-48, 7-1 to 7-48) as the host material on the hole transport layer, piq) ₂ Ir (acac) [bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate] as a dopant material and then doped at 95: 5 weight to deposit a 30 nm thick light emitting layer, and then vacuum BAlq to 10 nm thick The vapor deposition was performed to form a hole blocking layer, and Alq ₃ was formed to a thickness of 40 nm to form 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 form an Al / LiF cathode, thereby manufacturing an organic EL device.

Comparative Example 6

An organic electroluminescent device was manufactured according to the same method as Experimental Example 2, except that Comparative Compound 1 (4,4'-di (9H-carbazol-9-yl) -1,1'-biphenyl) was used as a light emitting host material. Produced.

Comparative Example 7

Comparative compound 2 (9- (9- (4,6-diphenylpyrimidin-2-yl) -9H-carbazol-3-yl) -12-phenyl-12H-benzo [4,5] thieno [3, as a luminescent host material An organic electroluminescent device was manufactured in the same manner as in Experiment 2, except that 2-a] carbazole) was used.

Comparative Example 8

Comparative compound 3 (3- (9- (4,6-diphenyl-1,3,5-triazin-2-yl) -9H-carbazol-3-yl) -12-phenyl-12H-benzo [3] as a light emitting host material [ 4,5] thieno [2,3-a] carbazole), except that the organic electroluminescent device was manufactured in the same manner as in Experiment 2.

Comparative Example 9

Same as Experimental Example 2, except that Comparative Compound 4 (12- (5-phenylpyrimidin-2-yl) -12H-benzo [4,5] thieno [3,2-a] carbazole) was used as a light emitting host material. An organic electroluminescent device was manufactured by the method.

Comparative Example 10

Except for using comparative compound 5 (12- (4- (4,6-diphenylpyrimidin-2-yl) phenyl) -12H-benzo [4,5] thieno [2,3-a] carbazole) as a light emitting host material In addition, an organic electroluminescent device was manufactured in the same manner as in Experimental Example 2.

The electroluminescent (EL) characteristics of the organic electroluminescent devices prepared by Experimental Example 2 and Comparative Examples 6 to 10 were measured by PR-650 of photoresearch by applying a forward bias DC voltage. In this case, the T95 life was measured by the life measurement equipment manufactured by McScience Inc. at 300 cd / m ² reference luminance. In the table below, the organic light emitting display device manufactured according to Experimental Example 2 of the present invention is described as Examples 119 to 262.

TABLE 5

As can be seen from the results of the table, the compound of the present invention used as a phosphorescent red host was found to exhibit a lower driving voltage, higher luminous efficiency, and a higher lifetime than Comparative Examples 6 to 10. In particular, Comparative Compound 4 and Comparative Compound 5 showed a higher lifespan than Comparative Compound 2 and Comparative Compound 3 when used as a phosphorescent green host, but were lower than Comparative Compound 2 and Comparative Compound 3, as can be seen from the above table used as a phosphorescent red host. It was confirmed that the efficiency and low life.

Experimental Example 3 (Hole Transport Layer)

First, by vacuum depositing 2-TNATA on an ITO layer (anode) formed on an organic substrate to form a hole injection layer having a thickness of 60 nm, the compound of the present invention (5-1 to 5-7, 5-11 to 5-14 , 5-17 to 5-31, 5-33 to 5-35) were vacuum deposited to a thickness of 20 nm to form a hole transport layer. Subsequently, 90: 1 weight of CBP [4,4'-N, N'-dicarbazole-biphenyl] was used as a host material and Ir (ppy) ₃ [tris (2-phenylpyridine) -iridium] was used as a dopant on the hole transport layer. Doped to deposit a light emitting layer of 30nm thickness. Next, BAlq was vacuum deposited to a thickness of 10 nm on the light emitting layer to form a hole blocking layer, and then Alq ₃ was formed to a thickness of 40 nm to form an electron injection layer. 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 form a cathode to prepare an organic light emitting device.

Comparative Example 11

The following Comparative Compound 6 (N4, N4'-di (naphthalen-1-yl) -N4, N4'-diphenyl- [1,1'-biphenyl] -4,4'-diamine instead of the compound of the present invention as a hole transport layer material Except for using), an organic light emitting display device was manufactured in the same manner as in Experimental Example 3.

Comparative Compound 6

Comparative Example 12

An organic electroluminescent device was manufactured in the same manner as in Experimental Example 3, except that Comparative Compound 7 (N, N, 12-triphenyl-12H-benzo [4,5] thieno [3,2-a] carbazol- was used instead of the compound of the present invention. 9-amine) to form a hole transport layer

Comparative Compound 7

Comparative Example 13

An organic electroluminescent device was manufactured in the same manner as in Experimental Example 3, except that Comparative Compound 8 (N- (9,9-dimethyl-9H-fluoren-2-yl) -N, 12-diphenyl-12H- was used instead of the compound of the present invention. A hole transport layer was formed using benzo [4,5] thieno [3,2-a] carbazol-9-amine).

<Comparative Compound 8>

Comparative Example 14

An organic electroluminescent device was manufactured in the same manner as in Experimental Example 3, except that the comparative compound 9 (N, N-di ([1,1'-biphenyl] -4-yl) -12-phenyl-12H- was used instead of the compound of the present invention. A hole transport layer was formed using benzo [4,5] thieno [2,3-a] carbazol-8-amine).

Comparative Compound 9

The electroluminescent (EL) characteristics of the organic light emitting diodes prepared by Experimental Example 3 and Comparative Example were measured by applying a positive bias DC voltage to the photoresearch company PR-650. At this time, the T95 life was measured through the life measurement equipment manufactured by McScience Inc. at 300 cd / m ² reference luminance. In the table below, the organic light emitting display device manufactured according to Experimental Example 3 was described as Examples 262 to 290.

TABLE 6

As can be seen from the results of the above table, the compounds of the present invention show a lower driving voltage and a higher efficiency, in particular, a higher lifetime than those of Comparative Examples 11 to 14. _One of R ₁ to R ₄ and R ₁₁ to R ₁₄ positions in the core is substituted with an aryl group, and in the case of a compound containing an arylamine group in the other, HOMO levels are lowered, thereby transferring holes to the light emitting layer more easily. As a result, it is judged that the service life is long.

Experimental Example 4 (light emitting auxiliary layer)

First, 2-TNATA was vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 60 nm, and then 4,4-bis [N- (1-naphthyl) on the hole injection layer. -N-phenylamino] biphenyl (Comparative Compound 6) was vacuum deposited to a thickness of 20 nm to form a hole transport layer. Next, the compound of the present invention (5-1 to 5-7, 5-11 to 5-14, 5-17 to 5-31, 5-33 to 5-35, 5-47 to 5-51) was 20 nm thick. Vacuum deposition to form a light emitting auxiliary layer. After the emission auxiliary layer was formed, CBP [4,4'-N, N'-dicarbazole-biphenyl] was used as a host material and Ir (ppy) ₃ [tris (2-phenylpyridine) -iridium] was formed on the emission auxiliary layer. A 30 nm thick light emitting layer was deposited by doping at 95: 5 weight with a dopant material. Subsequently, BAlq was vacuum-deposited to a thickness of 10 nm on the light emitting layer to form a holdoff layer, and then Alq ₃ was formed to a thickness of 40 nm to form 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 form a cathode, thereby manufacturing an organic light emitting device.

Comparative Example 15

Comparative compound 6 (N4, N4'-di (naphthalen-1-yl) -N4, N4'-diphenyl- [1,1'-biphenyl] -4,4'-diamine as a light emitting auxiliary layer material instead of the compound of the present invention Except for using), an organic light emitting display device was manufactured in the same manner as in Experimental Example 4.

[Comparative Example 16]

An organic electroluminescent device was manufactured in the same manner as in Experimental Example 4, except that Comparative Compound 7 (N, N, 12-triphenyl-12H-benzo [4,5] thieno [3,2-a] carbazol- was used instead of the compound of the present invention. 9-amine) to form a light emitting auxiliary layer.

[Comparative Example 17]

An organic electroluminescent device was manufactured in the same manner as in Experimental Example 4, except that Comparative Compound 8 (N- (9,9-dimethyl-9H-fluoren-2-yl) -N, 12-diphenyl-12H- was used instead of the compound of the present invention. A light emitting auxiliary layer was formed using benzo [4,5] thieno [3,2-a] carbazol-9-amine).

[Comparative Example 18]

An organic electroluminescent device was manufactured in the same manner as in Experimental Example 3, except that the comparative compound 9 (N, N-di ([1,1'-biphenyl] -4-yl) -12-phenyl-12H- was used instead of the compound of the present invention. A light emitting auxiliary layer was formed using benzo [4,5] thieno [2,3-a] carbazol-8-amine).

The electroluminescent (EL) characteristics of the organic electroluminescent devices manufactured by Experimental Example 4 and Comparative Example were measured by applying a forward bias DC voltage to the photoresearch company PR-650, as shown in the following table. At this time, the T95 life was measured through the life measurement equipment manufactured by McScience Inc. at 300 cd / m ² reference luminance. The organic electric device manufactured by Experimental Example 4 of the present invention is represented by Examples 291 to 324 in Table 7 below.

TABLE 7

As a result of using the compound of the present invention as a light emitting auxiliary layer between the hole transporting layer and the light emitting layer as shown in the above table, the efficiency and the lifespan were increased compared to those of the comparative compound used as the light emitting auxiliary layer. The hole is formed between the HOMO level of Comparative Compound 6 used as the hole transport layer and the HOMO level of the light emitting layer.

By using a light emitting auxiliary layer having a HOMO level that can deliver faster than can be determined to show a high efficiency and a high lifetime.

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

The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains may various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe the present invention, and the spirit and scope of the present invention are not limited thereto. The protection scope of the present invention should be interpreted by the following claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.

CROSS-REFERENCE TO RELATED APPLICATION

This patent application is related to the patent application No. 10-2012-0005545 filed with Korea on January 18, 2012 and the patent application No. 10-2012-0118629 filed with Korea on October 24, 2012. Priority is claimed under section (a) (35 USC § 119 (a)), all of which is incorporated by reference in this patent application. In addition, if this patent application claims priority for the same reason for countries other than the United States, all its contents are incorporated into this patent application by reference.

Claims (10)

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

   <Formula 1>

   

   In Chemical Formula 1,

   R ₁ to R ₄ and R ₁₁ to R ₁₄ are each independently selected from hydrogen, deuterium, halogen, C ₆ ~ C ₆₀ aryl group, fluorenyl group, C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ Fused ring group of aromatic ring, C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P, -LN (R ') (R "), C ₁ ~ C ₅₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₃₀ alkoxy group and C ₆ ~ C ₃₀ aryloxy group,

   R ₂₁ and R ₂₂ are each independently i) a hydrogen, C ₆ ~ C ₆₀ aryl group, fluorenyl group, C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring, O , C ₂ -C ₆₀ heterocyclic group including at least one hetero atom of N, S, Si and P and -LN (R ') (R "), or ii) To form a monocyclic or polycyclic ring,

   However, only when R ₂₁ and R ₂₂ are bonded to each other to form a ring, R ₁ to R ₄ and R ₁₁ to R ₁₄ may both be hydrogen at the same time, and R ₂₁ and R ₂₂ may be bonded to each other to form a ring. Otherwise, at least one of R ₁ to R ₄ is not hydrogen and at least one of R ₁₁ to R ₁₄ is not hydrogen,

   X and Y are independently of each other, S, O or SiR ₃₁ R ₃₂ (wherein R ₃₁ and R ₃₂ are independently of each other hydrogen, an aryl group of C ₆ to C ₆₀ , O, N, S, Si and P C ₂ ~ C ₆₀ heterocyclic group, or C ₁ ~ C ₅₀ Alkyl group containing at least one heteroatom, m and n are each 0 or 1 (but m + n = an integer of at least),

   L is a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene groups; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; And a divalent aliphatic hydrocarbon group; wherein the arylene group, fluorenylene group, heterocyclic group and aliphatic hydrocarbon group are nitro group, cyano group, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₆ May be substituted with one or more substituents selected from the group consisting of an aryl group of ~ C ₂₀ , a heterocyclic group of C ₂ ~ C ₂₀ , an alkoxy group of C ₁ ~ C ₂₀ , and an amino group),

   Ar is a C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P, an aryl group of C ₆ -C ₆₀ or -N (R ') (R ") ,

   R 'and R "are independently of each other O, N, S, Si and P containing at least one heteroatom of C ₂ ~ C ₆₀ heterocyclic group, C ₆ ~ C ₆₀ aryl group or fluorenyl group to be.

   (R above_One~ R₄, R₁₁~ R₁₄, R₂₁, R₂₂, R₃₁, R₃₂When Ar, R 'and R "are aryl groups, they are deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, C_One~ C₂₀Alkylthio, C_One~ C₂₀Alkoxyl, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C₂~ C₂₀Alkynyl, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₂~ C₂₀Heterocyclic group, C₃~ C₂₀Cycloalkyl group, C₇~ C₂₀of Arylalkyl group and C₈~ C₂₀May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,

   R_One~ R₄, R₁₁~ R₁₄, R₂₁, R₂₂, R₃₁, R₃₂When Ar, R 'and R "are heterocyclic groups, they are deuterium, halogen, silane, cyano, nitro, C_One~ C₂₀Alkoxyl, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₂~ C₂₀Heterocyclic group, C₃~ C₂₀Cycloalkyl group, C₇~ C₂₀of Arylalkyl group and C₈~ C₂₀May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,

   When R ₁ to R ₄ , R ₁₁ to R ₁₄ , R ₂₁ , R ₂₂ , R 'and R ″ are fluorenyl groups, they are deuterium, halogen, silane group, cyano group, C ₁ to C ₂₀ alkyl group, C for ₂ ~ C ₂₀ of alkenyl groups _{(alkenyl), C 6 ~ C} 20 aryl group, a C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ substituted by deuterium May be substituted with one or more substituents selected from the group consisting of cycloalkyl groups,

   R_One~ R₄, R₁₁~ R₁₄, R₂₁ And R₂₂In the case of the fused ring group, it is deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, C_One~ C₂₀Alkylthio, C_One~ C₂₀Alkoxyl, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C₂~ C₂₀Alkynyl, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₂~ C₂₀Heterocyclic group, C₃~ C₂₀Cycloalkyl group, C₇~ C₂₀of Arylalkyl group and C₈~ C₂₀May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,

   R_One~ R₄, R₁₁~ R₁₄, R₃₁ And R₃₂When is an alkyl group, it is halogen, silane group, boron group, cyano group, C_One~ C₂₀Alkoxyl, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₂~ C₂₀Heterocyclic group, C₇~ C₂₀of Arylalkyl group and C₈~ C₂₀May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,

   R_One~ R₄ And R₁₁~ R₁₄Is an alkenyl group, it is a deuterium, a halogen, a silane group, a cyano group, C_One~ C₂₀Alkoxyl, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₂~ C₂₀Heterocyclic group, C₃~ C₂₀Cycloalkyl group, C₇~ C₂₀of Arylalkyl group and C₈~ C₂₀May be substituted with one or more substituents selected from the group consisting of arylalkenyl groups,

   When R ₁ to R ₄ and R ₁₁ to R ₁₄ are an alkoxyl group, this is deuterium, halogen, silane group, C ₁ ~ C ₂₀ alkyl group, C ₆ ~ C ₂₀ aryl group, C ₆ ~ substituted with deuterium C ₂₀ may be substituted with one or more substituents selected from the group consisting of an aryl group, C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ cycloalkyl group,

   Wherein R ₁ ~ R ₄ and R ₁₁ ~ R, if ₁₄ is an aryloxy group which is substituted C with deuterium, a silane group, a cyano group, C ₁ ~ C ₂₀ alkyl group, an aryl group, a heavy hydrogen of C ₆ ~ C ₂₀ of ₆ May be substituted with one or more substituents selected from the group consisting of an aryl group of ~ C ₂₀ , a heterocyclic group of C ₂ ~ C ₂₀ , and a cycloalkyl group of C ₃ ~ C ₂₀ )
2. The method of claim 1,

   Compound represented by one of the following formula.

     <Formula 2>

   

     <Formula 3>

   

     <Formula 4>

   

     <Formula 5>

   ,

   

   (In the above formula, Ar 'is hydrogen, deuterium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, -LN (R') (R " ), C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C heterocyclic of ₂ ~ C ₂₀ Selected from the group consisting of a cyclic group, a nitrile group and an acetylene group, X ₁ to X ₄ are CR ₄₁ or N (wherein R ₄₁ is hydrogen, deuterium, an aryl group of C ₆ to C ₂₀ or C ₂ to C ₂₀ Heterocyclic group), R ₁ to R ₄ , R ₁₁ to R ₁₄ , R ₂₁ , R ₂₂ , R ', R ", X, L and Ar are the same as defined in Formula 1)
3. The method of claim 1,

   Compound represented by one of the following formula.

    <Formula 6>

   

    <Formula 7>

   

    <Formula 8>

   

    <Formula 9>

   

   (In the above formula, Ar 'is hydrogen, deuterium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, -LN (R') (R " ), C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, C ₇ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, C heterocyclic of ₂ ~ C ₂₀ Selected from the group consisting of a cyclic group, a nitrile group and an acetylene group, X ₁ to X ₄ are CR ₄₁ or N (wherein R ₄₁ is hydrogen, deuterium, an aryl group of C ₆ to C ₂₀ or C ₂ to C ₂₀ Heterocyclic group), R ₁ to R ₄ , R ₁₁ to R ₁₄ , R ₂₁ , R ₂₂ , R ', R ", Y, L and Ar are the same as defined in Formula 1)
4. The method of claim 1,

   Compound which is one of the following compounds.

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   
5. In an organic electric device comprising a first electrode, a second electrode, and an organic material layer positioned between the first electrode and the second electrode,

   The organic material layer is an organic electric device, characterized in that it contains a compound of any one of claims 1 to 4.
6. The method of claim 5,

   And forming the compound into the organic material layer by a soluble process.
7. The method of claim 5,

   And the organic material layer is at least one of a light emitting layer, a hole injection layer, a hole transporting layer, a light emitting auxiliary layer, an electron injection layer, and an electron transporting layer.
8. The method of claim 7, wherein

   At least one layer of the light emitting layer, the hole injection layer and the light emitting auxiliary layer is formed of the compound.
9. A display device comprising the organic electroluminescent device of claim 5; And

   A controller for driving the display device; Electronic device comprising a.
10. The method of claim 9,

    The organic electroluminescent device is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a device for monochrome or white illumination.

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