KR20150115226A - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

The present invention provides a novel compound capable of improving light-emitting efficiency, stability, and lifespan of an element, an organic electronic element using same and an electronic device thereof.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound for organic electroluminescent devices, an organic electroluminescent device using the same, and an electronic device using the same. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an organic electroluminescent (EL)

TECHNICAL FIELD The present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device therefor.

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

A material used as an organic material layer in an organic electric device may be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions.

Currently, the portable display market is increasing in size as a large-area display, which requires more power than the power consumption required by existing portable displays. Therefore, power consumption becomes a very important factor for portable displays, which have a limited power source, such as a battery, and efficiency and lifetime issues must be solved.

The efficiency, lifetime, and driving voltage are related to each other. As the efficiency increases, the driving voltage decreases. As the driving voltage decreases, the crystallization of the organic material due to Joule heating, which occurs during driving, Indicating a tendency for the lifetime to increase. However, simply improving the organic material layer can not maximize the efficiency. This is because, when the optimal combination of the energy level and T1 value between each organic material layer and the intrinsic properties (mobility, interface characteristics, etc.) of the material are achieved, long life and high efficiency can be achieved at the same time.

In order to solve the problem of light emission in the hole transporting layer in recent organic electroluminescent devices, it is necessary to have a light emitting auxiliary layer between the hole transporting layer and the light emitting layer, It is time to develop the layer.

Generally, 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, the material used for the hole transport layer has a low HOMO value and therefore has a low T 1 value. As a result, the exciton generated in the light emitting layer is transferred to the hole transport layer, resulting in a charge unbalance in the light emitting layer. And emits light at the interface of the hole transporting layer.

When light is emitted from the interface of the hole transporting layer, the color purity and efficiency of the organic electronic device are lowered and the lifetime is shortened. Therefore, it is urgently required to develop a light emitting auxiliary layer having a high T 1 value and a HOMO level between the HOMO energy level of the hole transport layer and the HOMO energy level of the light emitting layer.

On the other hand, while delaying penetration and diffusion of the metal oxide from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electronic device, to the organic layer, stable characteristics such as Joule heating, It is necessary to develop a hole injection layer material having a temperature. The low glass transition temperature of the hole transport layer material has a property of lowering the uniformity of the surface of the thin film when the device is driven, which has been reported to have a great influence on the lifetime of the device. In addition, OLED devices are mainly formed by a deposition method, and it is necessary to develop a material that can withstand a long period of time, that is, a material having high heat resistance characteristics.

That is, in order to sufficiently exhibit the excellent characteristics of the organic electronic device, a material constituting the organic material layer in the device such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, an electron injecting material, However, the development of a stable and efficient organic material layer for an organic electric device has not been sufficiently developed yet. Therefore, development of new materials is continuously required, and development of materials for the light emission-assisting layer and the hole transporting layer is urgently required.

It is an object of the present invention to provide a compound capable of improving a high luminous efficiency, a low driving voltage, a high heat resistance, a color purity and a lifetime of the device, an organic electric device using the same, and an electronic device thereof.

In one aspect, the invention provides compounds represented by the 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, it is possible to achieve a high luminous efficiency, a low driving voltage, and a high heat resistance of the device, and can greatly improve the color purity and lifetime of the device.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an illustration of an organic electroluminescent device according to the present invention. FIG.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

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

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

As used in this specification and the appended claims, unless stated otherwise, the following terms have the following meanings:

The term " halo "or" halogen ", as used herein, unless otherwise indicated, is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I).

As used herein, the term "alkyl" or "alkyl group " refers to a straight or branched Quot; means a radical of a saturated aliphatic group, including an alkyl group, a cycloalkyl-substituted alkyl group.

The term "haloalkyl group" or "halogenalkyl group" as used in the present invention means an alkyl group substituted with halogen unless otherwise stated.

The term "heteroalkyl group" as used herein means that at least one of the carbon atoms constituting the alkyl group is replaced by a heteroatom.

The term "alkenyl group" or "alkynyl group ", as used herein, unless otherwise indicated, each have a double bond or triple bond of from 2 to 60 carbon atoms and include straight chain or branched chain groups, It is not.

The term "cycloalkyl" as used herein, unless otherwise specified, means alkyl which forms a ring having from 3 to 60 carbon atoms, but is not limited thereto.

The term "alkoxyl group "," alkoxy group ", or "alkyloxy group" used in the present invention means an alkyl group to which an oxygen radical is attached and, unless otherwise stated, has a carbon number of 1 to 60, It is not.

The term "alkenoyl group "," alkenoyl group ", "alkenyloxy group ", or" alkenyloxy group "as used in the present invention means an alkenyl group to which an oxygen radical is attached, , But is not limited thereto.

As used herein, the term "aryloxyl group" or "aryloxy group" refers to an aryl group attached to an oxygen radical and, unless otherwise stated, has a carbon number of 6 to 60, but is not limited thereto.

The terms "aryl group" and "arylene group ", as used herein, unless otherwise specified, each have 6 to 60 carbon atoms, but are not limited thereto. In the present invention, an aryl group or an arylene group means a single ring or a multicyclic aromatic group, and neighboring substituents include aromatic rings formed by bonding or participating in the reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, a spirobifluorene group, or a spirobifluorene group.

The prefix "aryl" or "ar" means a radical substituted with an aryl group. For example, the arylalkyl group is an alkyl group substituted with an aryl group, the arylalkenyl group is an alkenyl group substituted with an aryl group, and the radical substituted with an aryl group has the carbon number described in the present specification.

Also, if prefixes are named consecutively, it means that the substituents are listed in the order listed first. For example, the arylalkoxy group means an alkoxy group substituted with an aryl group, the alkoxycarbonyl group means a carbonyl group substituted with an alkoxyl group, and in the case of an arylcarbonylalkenyl group, an alkenyl group substituted with an arylcarbonyl group means Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

The term "heteroalkyl ", as used herein, unless otherwise indicated, means an alkyl comprising one or more heteroatoms. The term "heteroaryl group" or "heteroarylene group" as used in the present invention means an aryl or arylene group having 2 to 60 carbon atoms each containing at least one heteroatom unless otherwise specified, And includes at least one of a single ring and a multi-ring, and neighboring functional devices may be formed in combination.

The term "heterocyclic group ", as used herein, unless otherwise specified, includes one or more heteroatoms, has from 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, Aromatic rings. Adjacent functional groups may be combined and formed.

As used herein, the term "heteroatom " refers to N, O, S, P or Si unless otherwise stated.

The "heterocyclic group" may also include a ring containing SO ₂ in place of the carbon forming the ring. For example, the "heterocyclic group" includes the following compounds.

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

Unless otherwise specified, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring of 3 to 60 carbon atoms or an aromatic ring of 6 to 60 carbon atoms or a heterocycle of 2 to 60 carbon atoms, or combinations thereof, Saturated or unsaturated ring.

Other hetero-compounds or hetero-radicals other than the above-mentioned hetero-compounds include, but are not limited to, one or more heteroatoms.

Unless otherwise specified, the term "carbonyl" as used herein refers to -COR ', wherein R' is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, A cycloalkyl group of 2 to 20 carbon atoms, an alkenyl group of 2 to 20 carbon atoms, an alkynyl group of 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise indicated, the term "ether" used in the present invention refers to -RO-R 'wherein R or R' are each independently of the other hydrogen, an alkyl group of 1-20 carbon atoms, An aryl group, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

One also no explicit description, the terms in the "unsubstituted or substituted", "substituted" is heavy hydrogen, a halogen, an amino group, a nitrile group, a nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C for use in the present invention ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl amine group, C ₁ ~ C ₂₀ alkyl thiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C of ₂₀ alkynyl, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron Means a group substituted with at least one substituent selected from the group consisting of a halogen atom, a halogen atom, a cyano group, a germanium group, and a C ₂ to C ₂₀ heterocyclic group.

Unless otherwise expressly stated, the formula used in the present invention is applied in the same manner as the definition of the substituent by the definition of the index of the following formula.

When a is an integer of 0, substituent R ¹ is absent. When a is an integer of 1, one substituent R ¹ is bonded to any one of carbon atoms forming a benzene ring, and when a is an integer of 2 or 3 each coupled as follows: and wherein R ¹ may be the same or different from each other, a is the case of 4 to 6 integer, and bonded to the carbon of the benzene ring in a similar way, while the display of the hydrogen bonded to the carbon to form a benzene ring Is omitted.

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

1, an organic electroluminescent 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, ) Comprising an organic compound layer comprising a compound according to the present invention. In this case, the first electrode 120 may be an anode and the second electrode 180 may be a cathode (cathode). In case of an inverting type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may include a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, an electron transporting layer 160, and an electron injecting layer 170 sequentially on the first electrode 120. At this time, the remaining layers except the light emitting layer 150 may not be formed. An electron blocking layer, a light emitting auxiliary layer 151, a buffer layer 141, and the like, and the electron transport layer 160 may serve as a hole blocking layer.

Also, although not shown, the organic electroluminescent device according to the present invention may further include a protective layer or a light-efficiency-improving layer formed on at least 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 may be a host or a dopant of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, It can be used as a material. Preferably, the compound of the present invention may be used as the light emitting layer 150, the hole transporting layer 140 and / or the light emitting auxiliary layer 151.

On the other hand, since the band gap, the electrical characteristics, the interface characteristics, and the like can be changed depending on which substituent is bonded at any position even in the same core, the selection of the core and the combination of the sub- Especially when the optimum combination of energy level and T1 value between the organic layers, intrinsic properties (mobility, interface characteristics, etc.) of the materials are achieved, long lifetime and high efficiency can be achieved at the same time.

As described above, in order to solve the light emission problem in the hole transporting layer in recent organic electroluminescent devices, it is preferable that the light emitting auxiliary layer is formed between the hole transporting layer and the light emitting layer. It is necessary to develop different luminescent auxiliary layers. On the other hand, in the case of the light-emission-assisting layer, it is difficult to deduce the characteristics of the organic layer to be used even if a similar core is used because the relationship between the hole-transport layer and the light-emitting layer (host)

Accordingly, in the present invention, by forming the light emitting layer or the light emitting auxiliary layer using the compound represented by the general formula (1), the energy level and T1 value between each organic material layer, the mobility of the material, It is possible to simultaneously improve the lifetime and efficiency of the electric element.

The organic electroluminescent device according to an embodiment of the present invention can be manufactured using a physical vapor deposition (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 a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, and an electron transporting layer 160 and an electron injection layer 170, and then depositing a material usable as the cathode 180 on the organic layer.

In addition, the organic material layer may be formed using a variety of polymer materials, not a vapor deposition method, or a solution process or a solvent process such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, It is possible to produce a smaller number of layers by a method such as a dipping process, a screen printing process, or a thermal transfer process. Since the organic material layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the forming method.

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

WOLED (White Organic Light Emitting Device) has advantages of high resolution realization and fairness, and can be manufactured using existing color filter technology of LCD. Various structures for a white organic light emitting device mainly used as a backlight device have been proposed and patented. Typically, a stacking method in which R (Red), G (Green) and B (Blue) light emitting parts are arranged side by side, and R, G and B light emitting layers are stacked up and down , And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light from the electroluminescent material. Can be applied to such WOLED.

The organic electroluminescent device according to the present invention may be one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, or a device for monochrome or white illumination.

Another embodiment of the present invention can include an electronic device including a display device including the above-described organic electronic device of the present invention and a control unit for controlling the display device. 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 according to one aspect of the present invention will be described.

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

          ≪ Formula 1 >

In Formula 1, A and B independently can be a a or a monocyclic or polycyclic C ₆ ~ C ₁₈ aryl each other. Here, A and B are excluded in the case of a single ring. For example, A and B may be, independently of one another, phenyl, naphthyl, phenanthrene, etc., except that A and B are simultaneously phenyl.

Ar ¹ and Ar ² are, independently of each other, a C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R ^a ) (R ^b ); For example, Ar ¹ and Ar ² are, independently from each other, phenyl, naphthyl, biphenyl, terphenyl, 9,9-dimethyl-fluorene, 9,9- Thiophene, dibenzofuran, 2-phenylpyrimidine, triazine, and the like.

m and n are each independently an integer of 0 to 4, and p and q are each independently an integer of 0 to 3.

R ¹ to R ⁴ independently of one another are deuterium; Tritium; halogen; Cyano; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R ^a ) (R ^b ); For example, R ¹ to R ⁴ independently of each other may be propene, phenyl, pyridine, dibenzothiophene and the like.

Further, adjacent groups of R ¹ to R ⁴ may combine with each other to form at least one ring. Here, R ¹ to R ⁴ which do not form a ring may be respectively defined as defined above. For example, when m and n are both 2, adjacent R ^{1 s} may combine with each other to form a ring, and R ² may be an aryl group or a heterocyclic group independently of each other even when adjacent to each other.

Of course, when m is an integer of 2 or more, a plurality of R ^{1 s} may be the same or different, and a group in which some of the neighboring groups are bonded to each other to form a ring and not form a remaining ring is selected from the above-defined substituent group . The same applies when n, p and / or q is an integer of 2 or more.

The ring formed by bonding adjacent groups may be a fused ring composed of a C ₃ to C ₆₀ aliphatic ring, a C ₆ to C ₆₀ aromatic ring, a C ₂ to C ₆₀ hetero ring, or a combination thereof, May be a single ring or multiple rings, but may also be a saturated or unsaturated ring.

L 'is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group.

R ^a and R ^b are each independently a C ₆ to C ₆₀ aryl group; A fluorenyl group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P;

Each of the aryl group, the fluorenyl group, the heterocyclic group, the fused ring group, the alkyl group, the alkenyl group, the alkynyl group, the alkoxyl group, the aryloxy group, the arylene group and the fluorenylene group may be substituted with deuterium; halogen; A silane group; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ to C ₂₀ ; A C ₁ to C ₂₀ alkoxyl group; An alkyl group having ₁ to ₂₀ carbon atoms; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; C ₆ -C ₂₀ An aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A heterocyclic group of C ₂ ~ C _20; A C ₃ to C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ to C ₂₀ ; And an arylalkenyl group having from ₈ to ₂₀ carbon atoms.

Here, the aryl group may be an aryl group having 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, and more preferably 6 to 30 carbon atoms,

The heterocyclic group may be a heterocycle having 2 to 60 carbon atoms, preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms,

The arylene group may be an arylene group having 6 to 60 carbon atoms, preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms,

In the case of the alkyl group, the alkyl group may have 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.

Specifically, the compound represented by Formula 1 may be represented by one of the following formulas.

      &Lt; Formula 2 > < EMI ID =

In Formula 2 to Formula 3, B, Ar ¹ , Ar ² , R ¹ to R ⁴ , m, n, p, and q may be defined as defined in Formula 1.

More specifically, the compounds represented by Chemical Formulas 1 to 4 may be any of the following compounds.

In another embodiment, the present invention provides a compound for an organic electroluminescent device represented by the general formula (1).

In another embodiment, the present invention provides an organic electronic device containing the compound represented by the above formula (1).

The organic electroluminescent device includes a first electrode; A second electrode; And an organic material layer disposed between the first electrode and the second electrode. The organic material layer may include a compound represented by Formula 1, wherein Formula 1 is a hole injecting layer, a hole transporting layer, Or the light-emitting layer. That is, the compound represented by the formula (1) can be used as a material for the hole injection layer, the hole transport layer, the light emission assisting layer or the light emitting layer. Specifically, the present invention provides an organic electric device including one of the compounds represented by Chemical Formulas 2 to 4 in the organic material layer, more specifically, an organic electronic device including the compound represented by the individual chemical formula in the organic material layer do.

In another embodiment of the present invention, the light efficiency improving layer is formed on at least one side of the one side of the first electrode opposite to the organic layer, or one side of the one side of the second electrode opposite to the organic layer, And an organic electroluminescent device.

Hereinafter, the synthesis examples of the compound represented by the formula (1) according to the present invention and the production examples of the organic electric device will be specifically described with reference to examples, but the present invention is not limited to the following examples.

Synthetic example

Illustratively, the compounds according to the invention (Final Products) are prepared by reacting Sub 1 and Sub 2 as shown in Scheme 1 below, but are not limited thereto.

<Reaction Scheme 1>

I. Sub  1 of Synthetic example

Sub 1 of Reaction Scheme 1 may be synthesized by a reaction route of the following Reaction Scheme 2, but is not limited thereto.

<Reaction Scheme 2>

One. Sub  1-2 Synthetic example

(One) Sub  1-2-3 of Synthetic example

To a round bottom flask Sub 1-2-1 (1 eq.), Sub 1-2-2 (1 _{eq), Pd 2 (dba) 3} (0.05 eq.), PPh ₃ (0.1 equiv), NaO t -Bu (3 , And toluene (10.5 mL / Sub 1-2-1 1 mmol) are added thereto, and the reaction is allowed to proceed at 100 ° C. After completion of the reaction, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. Subsequently, the resulting organic material was subjected to silicagel column and recrystallization to obtain Sub 1-2-3.

(2) Sub  1-2 Synthetic example

Sub 1-2-3 (1 equivalent) was dissolved in anhydrous ether, the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.5M in hexane) (1.1 eq.) Was slowly added dropwise, &Lt; / RTI &gt; The temperature of the reaction was then lowered to -78 ° C and triisopropylborate (1.5 eq.) Was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and water. The organic layer was dried over MgSO ₄ and concentrated. Subsequently, the resulting organic material was subjected to silicagel column and recrystallization to obtain Sub 1-2.

2. Sub  1-3 of Synthetic example

Sub 1-1 (1 eq.), Pd (PPh ₃ ) ₄ (0.03 eq.), NaOH (3 eq.), THF (3 mL / 1.5 mL / 1 mmol). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain Sub 1-3.

3. Sub  1 of Synthetic example

Sub 1-3 (1 eq.), Sub 1-4 (1 eq.), Pd (PPh ₃ ) ₄ (0.03 eq.), NaOH (3 eq.), THF (3 mL / 1.5 mL / 1 mmol). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain Sub 1.

Examples of the synthesis of specific compounds belonging to Sub 1 are as follows.

(One) Sub  1 (1) Synthetic example

Sub  Synthesis of 1-3 (1)

Sub-1-2 (1) (6.7 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol) and NaOH (2.4 g, 20 mmol) were placed in a round bottom flask, 60 mmol), THF (60 mL) and water (30 mL). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 7.2 g (yield: 68%) of Sub 1-3 (1).

Sub  Synthesis of 1 (1)

Sub 1-4 (1) (5.7 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol) and NaOH 2.4 g, 60 mmol), THF (60 mL) and water (30 mL). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 9.1 g of Sub 1 (1) (yield: 66%).

Examples of Sub 1 include, but are not limited to, the following FD-MSs.

[Table 1]

II . Sub  2 of Synthetic example

Examples of the synthesis of specific compounds belonging to Sub 2 are as follows.

One. Sub  2-2 Synthetic example

After adding 2- (2-nitrophenyl) naphthalene (16.7 g, 67.1 mmol), triphenylphosphine (44 g, 167.6 mmol) and o-dichlorobenzene (275 mL), the mixture was refluxed at 180 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 7.6 g (52%) of the product.

2. Sub  2-3 Synthetic example

(One) Sub  2-3-1 Synthetic example

A small amount of acetic acid was added to β-tetralone (18 g, 123 mmol) and phenyl hydrazine hydrochloride (11 g, 76 mmol) and refluxed in 150 mL of ethanol for 2 hours under nitrogen atmosphere. After completion of the reaction, the reaction product was cooled to room temperature, and the resulting product was filtered and dried to obtain 16.5 g (61%) of Compound Sub 2-3-1.

(2) Sub  2-3 Synthetic example

Sub 2-3-1 Compound (16.5 g, 75.34 mmol) and tetrachloro-1,4-benzoquinone (25.93 g, 105.5 mmol) are dissolved in 300 ml of xylene in a reaction flask. The reaction flask was refluxed in a nitrogen atmosphere for 2 hours. After completion of the reaction, the reaction flask was charged with an aqueous solution of NaOH (10%) and water, and the organic layer was extracted. The extract was concentrated and recrystallized from ethanol to obtain 15.7 g (yield: 96%) of Sub 2-3.

3. Sub  2-4 Synthetic example

Using the synthesis example of Sub 2-3, 11 g (67%) of Compound Sub 2-4 was obtained.

4. Sub  2-5 Synthetic example

2-nitro-1,1'-binaphthalene (20.1 g, 67.1 mmol), Triphenylphosphine (44 g, 167.6 mmol) and o-Dichlorobenzene (275 mL) were added. After the reaction was completed, the reaction mixture was cooled to room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 10.8 g (60%) of the product.

5. Sub  2-6 Synthetic example

Dichlorobenzene (275 mL) was added thereto, and the mixture was refluxed at 180 占 폚. After the reaction was completed, the reaction mixture was cooled to room temperature and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 11.2 g (62.5%) of the product.

6. Sub  2-11 Synthetic example

Carbazole (16.72 g, 100 mmol), NBS (59.4 g, 210 mmol), BPO (2.42 g, 10 mmol) and methylene chloride (300 mL) are added and stirred at room temperature. After the reaction was completed, the reaction mixture was extracted with methylene chloride, water and NaHCO ₃ aqueous solution. The obtained organic layer was dried with Na ₂ SO ₄ , concentrated, and recrystallized to obtain 23.73 g (73%) of the product. Pd (PPh ₃ ) ₄ , (8.44 g, 7.3 mmol), K ₂ CO ₃ (60.55 g, 438.12 mmol), THF (20.0 g) were added to the resulting product (23.73 g, 73.02 mmol), phenylboronic acid 320 mL) and water (160 mL), and the mixture is refluxed at 80 ° C. After the reaction was completed, the reaction mixture was cooled to room temperature, extracted with methylene chloride and water. The obtained organic layer was dried over MgSO ₄ , concentrated and recrystallized to obtain 15.9 g (68%) of the product.

Meanwhile, examples of Sub 2 are as follows but are not limited thereto, and their FD-MSs are shown in Table 2 below.

[Table 2]

III . The final product ( Final Products )of Synthetic example

Pd ₂ (dba) ₃ (0.05 eq.), PPh ₃ (0.1 eq.), NaO t- Bu (3 eq.), Toluene (10.5 mL / Sub 1 1 mmol) was added thereto, and the reaction was allowed to proceed at 100 ° C. After completion of the reaction, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain final product.

1. 1-1 of Synthetic example

Sub 1 (1) (13.8 g, 20 mmol), Sub 2-1 (3.3 g, 20 mmol), Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ (0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 11.0 g (yield: 71%) of 1-1.

2. 2-6 Synthetic example

Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ (0.5 g, 2 mmol), Na ₂ O (10 g) t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 12.1 g (yield: 69%) of 2-6.

3. 3-11 Synthetic example

Sub 1 (10) (15.4 g, 20 mmol), Sub 2-1 (3.3 g, 20 mmol), Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ (0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 3.3 g (yield: 66%) of 3-11.

4. 4-16 Synthetic example

Sub 1 (15) (17.9 g, 20 mmol), Sub 2-1 (3.3 g, 20 mmol), Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ (0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 12.1 g (yield: 62%) of 4-16.

5. 5-17 Synthetic example

Sub 2 (16.8 g, 20 mmol), Sub 2-1 (3.3 g, 20 mmol), Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ (0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 3.3 g (yield: 67%) of 5-17.

6. 6-22 Synthetic example

(0.6 g, 20 mmol), Sub 2-1 (3.3 g, 20 mmol), Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ (0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 14.1 g (yield: 63%) of 6-22.

7. 7-27 Synthetic example

Sub 1 (20) (15.9 g, 20 mmol), Sub 2-1 (3.3 g, 20 mmol), Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ (0.5 g, 2 mmol) t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 11.6 g (yield: 66%) of 7-27.

8. 8-1 Synthetic example

Sub 1 (16) (15.8 g, 20 mmol), Sub 2-1 (3.3 g, 20 mmol), Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ (0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 12.8 g (yield: 73%) of 8-1.

9. 9-2 Synthetic example

Sub 1 (4) (16.6 g, 20 mmol), Sub 2-1 (3.3 g, 20 mmol), Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ (0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 3.4 g (yield: 73%) of 9-2.

10. 10-3 Synthetic example

Sub 1 (8) (17.3 g, 20 mmol), Sub 2-1 (3.3 g, 20 mmol), Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ (0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 13.3 g (yield: 70%) of 10-3.

11. 11-5 Synthetic example

Sub 1 (5) (21.6 g, 20 mmol), Sub 2-1 (3.3 g, 20 mmol), Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ (0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 15.1 g (yield: 65%) of 11-5.

12. 12-6 Synthetic example

Sub 3 (17.8 g, 20 mmol), Sub 2-1 (3.3 g, 20 mmol), Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ (0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 13.5 g (yield: 69%) of 12-6.

13. 13-3 Synthetic example

Sub 1 (7) (18.4 g, 20 mmol), Sub 2-1 (3.3 g, 20 mmol), Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ (0.5 g, 2 mmol) t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 13.5 g (yield: 67%) of 13-3.

14. 14-1 Synthetic example

Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ (0.5 g, 2 mmol), Na ₂ O (20 g) t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 15.0 g (yield: 68%) of 14-1.

15. 17-2 Synthetic example

Sub-13 (15.8 g, 20 mmol), Sub 2-8 (4.9 g, 20 mmol), Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ (0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 12.6 g (yield: 66%) of 17-2.

16. 18-1 Synthetic example

Sub 1 (19) (16.8 g, 20 mmol), Sub 2-1 (3.3 g, 20 mmol), Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ (0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added thereto, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 13.0 g (yield: 70%) of 18-1.

Meanwhile, the FD-MS values of the compounds of the present invention prepared according to the above Synthesis Examples are shown in Table 3 below.

[Table 3]

Evaluation of manufacturing of organic electric device

[ Example  1] Green organic light emitting device ( Hole transport layer )

An organic electroluminescent device was prepared according to a conventional method using the compound of the present invention as a hole transport layer material. First, N ¹ on the ITO layer (anode) formed on an organic substrate - (naphthalen-2-yl) -N 4, N 4 -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N 1 (hereinafter abbreviated as " 2-TNATA ") was vacuum-deposited to a thickness of 60 nm to form a hole injecting layer, and Compound 1-1 of the present invention was coated on the hole injecting layer to a thickness of 60 nm To form a hole transporting layer. Subsequently, tris (2-phenylpyridine) -iridium (hereinafter referred to as "Ir (ppy) ₃ ") was added to the hole transport layer as a host material, and 4,4'-N, N'-dicarbazole- Quot; as a dopant material) was doped in a weight ratio of 90:10, and vacuum evaporated to a thickness of 30 nm to form a light emitting layer. Subsequently, aluminum (1,1'-biphenyl) -4-oleato) bis (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as "BAlq") was vacuum deposited on the light emitting layer to a thickness of 10 nm (8-quinolinol) aluminum (hereinafter abbreviated as "Alq ₃ &quot;) was vacuum deposited on the hole blocking layer to a thickness of 40 nm to form an electron transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode. Thus, an organic electroluminescent device was manufactured.

[ Example  2] to [ Example  31] green organic light emitting device Hole transport layer )

The compound of the present invention 1-4, 2-1, 2-4, 3-1, 3-4, 4-1, 4-4, and 5 described in the following Table 1 was used instead of Compound 1-1 of the present invention as a hole transport layer material -1, 5-4, 6-1, 6-4, 7-1, 7-4, 8-1, 8-4, 9-1, 9-4, 10-1, 10-4, 11-1 , 11-4, 12-1, 12-4, 13-1, 13-4, 14-1, 15-1, 16-1, 17-1 and 18-1. An organic electroluminescent device was prepared in the same manner as in Example 1.

[ Comparative Example  One]

An organic electroluminescent device was prepared in the same manner as in Example 1, except that the following compound A was used instead of the compound 1-1 of the present invention as a hole transport layer material.

&Lt; Comparative Compound A >

[ Comparative Example  2]

An organic electroluminescence device was prepared in the same manner as in Example 1, except that the following compound B was used instead of the compound 1-1 of the present invention as the hole transport layer material.

&Lt; Comparative Compound B >

[ Comparative Example  3]

An organic electroluminescence device was prepared in the same manner as in Example 1, except that the following compound C was used in place of the compound 1-1 of the present invention as a hole transport layer material.

<Comparative compound C>

Electruminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples 1 to 31 and Comparative Examples 1 to 3 of the present invention And T95 lifetime was measured by a life measuring device manufactured by Mac Science Inc. at a luminance of 5000 cd / m 2. The measurement results are shown in Table 4 below.

[Table 4]

As can be seen from the results of Table 4, it can be confirmed that the organic electroluminescence device using the compound of the present invention as the material of the hole transport layer has a relatively high efficiency and a long lifetime.

In particular, the driving voltage was higher than that of Comparative Examples 1 to 3, but the efficiency and lifetime of the device using the compound of the present invention were found to be higher than those of the comparative example. This means that the driving voltage increase within a certain range does not reduce the lifetime of the device due to thermal damage. Generally, it is considered that the holes move about 1000 times faster than the electrons in the OLED device, but the thermal damage due to the increase of the driving voltage decreases the moving speed of holes, thereby improving the charge balance in the light emitting layer. In addition, the fused compound of the present invention has a packing density lower than that of Comparative Example 3, and as a result, the driving voltage is increased, resulting in a slower hole transporting speed, and it is considered that the charge balance in the light emitting layer is improved.

[ Example  32] red organic light emitting device The light- )

Organic electroluminescent devices were prepared according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, 2-TNATA was vacuum deposited on the ITO layer (anode) formed on the organic substrate to a thickness of 60 nm to form a hole injection layer, and 4,4-bis [N- (1-naphthyl ) -N-phenylamino] biphenyl (hereinafter abbreviated as "NPD") was vacuum deposited to a thickness of 60 nm to form a hole transport layer. Subsequently, Compound 1-1 of the present invention was vacuum-deposited on the hole transport layer to a thickness of 20 nm to form a light-emission-assisting layer, and bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate (hereinafter abbreviated as "(piq) ₂ Ir (acac)") as a dopant was doped at a weight ratio of 95: 5 and vacuum evaporated to a thickness of 30 nm to form a light emitting layer. Subsequently, BAlq was vacuum deposited on the light emitting layer to form a hole blocking layer to form a hole blocking layer, and Alq ₃ was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transporting layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode. Thus, an organic electroluminescent device was manufactured.

[ Example  33] to [ Example  126] red organic light emitting device The light- )

The compounds 1-1 to 1-8, 1-17 to 1-23, 1-42, 1-59, 1-64, and 1-64 of the present invention described in Table 5 below were used instead of the compound 1-1 of the present invention as the light- 2-1 to 2-8, 2-17 to 2-23, 2-42, 2-59, 2-64, 3-1 to 3-6, 4-7, 4-8, 4-17 to 4- 19, 5-20 to 5-23, 5-42, 5-59, 5-64, 6-1 to 6-5, 7-6 to 7-8, 7-17, 7-18, 8-8, 9-17 to 9-19, 10-20 to 10-22, 11-23, 11-42, 11-59, 12-64, 13-1 to 13-3, 14-1, 14- 2, 15-1, 15-2, 16-1, 16-2, 17-1, 17-2, 18-1 and 18-2 were used, Thereby preparing an organic electroluminescent device.

[ Comparative Example  4]

An organic electroluminescent device was prepared in the same manner as in Example 32 except that the luminescent auxiliary layer was not formed.

[ Comparative Example  5]

An organic electroluminescent device was prepared in the same manner as in Example 32 except that the compound A was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.

[ Comparative Example  6]

An organic electroluminescent device was prepared in the same manner as in Example 32 except that the compound B was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.

[ Comparative Example  7]

An organic EL device was prepared in the same manner as in Example 32, except that the compound C was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.

Electruminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic EL devices manufactured in Examples 32 to 126 and Comparative Examples 4 to 7 of the present invention And the T95 lifetime was measured using a life measuring device manufactured by Mac Science Inc. at a luminance of 2500 cd / m 2. The measurement results are shown in Table 5 below.

[Table 5]

[ Example  127] green organic light emitting device The light- )

Organic electroluminescent devices were prepared according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, 2-TNATA was vacuum deposited on the ITO layer (anode) formed on the organic substrate to form a hole injection layer, and then a hole transport layer was formed by vacuum depositing NPD on the hole injection layer to a thickness of 60 nm . Subsequently, Compound 1-1 of the present invention was vacuum deposited on the hole transport layer to form a light emission-assisting layer, and CBP as a host material and Ir (ppy) ₃ as a dopant material To a thickness of 95: 5, and vacuum-deposited to a thickness of 30 nm to form a light emitting layer. Subsequently, BAlq was vacuum deposited on the light emitting layer to form a hole blocking layer to form a hole blocking layer, and Alq ₃ was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transporting layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode. Thus, an organic electroluminescent device was manufactured.

[ Example  128] to [ Example  221] green organic light emitting device The light- )

The compounds 1-1 to 1-8, 1-17 to 1-23, 1-42, 1-59, 1-64, and 1-64 of the present invention described in Table 6 below were used instead of the compound 1-1 of the present invention as the light- 2-1 to 2-8, 2-17 to 2-23, 2-42, 2-59, 2-64, 3-1 to 3-6, 4-7, 4-8, 4-17 to 4- 19, 5-20 to 5-23, 5-42, 5-59, 5-64, 6-1 to 6-5, 7-6 to 7-8, 7-17, 7-18, 8-8, 9-17 to 9-19, 10-20 to 10-22, 11-23, 11-42, 11-59, 12-64, 13-1 to 13-3, 14-1, 14- 2, 15-1, 15-2, 16-1, 16-2, 17-1, 17-2, 18-1 and 18-2, Thereby preparing an organic electroluminescent device.

[ Comparative Example  8]

An organic electroluminescent device was prepared in the same manner as in Example 127 except that the luminescent auxiliary layer was not formed.

[ Comparative Example  9]

An organic EL device was prepared in the same manner as in Example 127 except that the compound A was used instead of the compound 1-1 of the present invention as a light emitting auxiliary layer material.

[ Comparative Example  10]

An organic electroluminescent device was prepared in the same manner as in Example 127 except that the compound B was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.

[ Comparative Example  11]

An organic electroluminescent device was prepared in the same manner as in Example 127 except that the compound C was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.

Electruminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples 127 to 221 and Comparative Examples 8 to 11 of the present invention And T95 lifetime was measured by a life measuring device manufactured by Mac Science Inc. at a luminance of 5000 cd / m 2. The measurement results are shown in Table 6 below.

[Table 6]

[ Example  222] blue organic light emitting device The light- )

Organic electroluminescent devices were prepared according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, 2-TNATA was vacuum deposited on the ITO layer (anode) formed on the organic substrate to form a hole injection layer, and then a hole transport layer was formed by vacuum depositing NPD on the hole injection layer to a thickness of 60 nm . Next, a compound of the present invention is vacuum-deposited on the hole transport layer to a thickness of 20 nm to form a light emitting auxiliary layer, and 9,10-di (naphthalen-2-yl) anthracene is used as a host material on the light emitting auxiliary layer. A light emitting layer was formed by doping with a thickness of 93: 7 by using BD-052X (manufactured by Idemitsu Kosan Co., Ltd.) as a dopant and vacuum-depositing it to a thickness of 30 nm. Subsequently, BAlq was vacuum deposited on the light emitting layer to form a hole blocking layer to form a hole blocking layer, and Alq ₃ was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transporting layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode. Thus, an organic electroluminescent device was manufactured.

[ Example  223] to [ Example  316] blue organic light emitting device ( The light- )

The compounds 1-1 to 1-8, 1-17 to 1-23, 1-42, 1-59, 1-64, and 1-64 of the present invention described in the following Table 7 were used instead of the compound 1-1 of the present invention as the light- 2-1 to 2-8, 2-17 to 2-23, 2-42, 2-59, 2-64, 3-1 to 3-6, 4-7, 4-8, 4-17 to 4- 19, 5-20 to 5-23, 5-42, 5-59, 5-64, 6-1 to 6-5, 7-6 to 7-8, 7-17, 7-18, 8-8, 9-17 to 9-19, 10-20 to 10-22, 11-23, 11-42, 11-59, 12-64, 13-1 to 13-3, 14-1, 14- 2, 15-1, 15-2, 16-1, 16-2, 17-1, 17-2, 18-1 and 18-2, Thereby preparing an organic electroluminescent device.

[ Comparative Example  12]

An organic EL device was prepared in the same manner as in Example 222 except that no light-emitting auxiliary layer was formed.

[ Comparative Example  13]

An organic EL device was prepared in the same manner as in Example 222, except that the compound A was used in place of the compound 1-1 of the present invention as the luminescent auxiliary layer material.

[ Comparative Example  14]

An organic electroluminescent device was prepared in the same manner as in Example 222 except that the compound B was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.

[ Comparative Example  15]

An organic EL device was prepared in the same manner as in Example 222, except that the compound C was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.

Electruminescence (EL) characteristics were measured with photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples 222 to 316 and Comparative Examples 12 to 15, And the T95 lifetime was measured using a life measuring device manufactured by Mac Science Inc. at a luminance of 500 cd / m 2. The measurement results are shown in Table 7 below.

[Table 7]

As can be seen from Tables 5 to 7, the organic electroluminescence device using the compound of the present invention as a material for the light-emission-assisting layer has remarkably improved luminous efficiency and lifetime.

In other words, it can be confirmed that the efficiency and lifetime are improved when the light-emitting auxiliary layer is formed and used than when the light-emission-assisting layer is not formed. It can be confirmed that the fused Carbazole ) Of the present invention exhibited higher efficiency and longer life.

This is because the compound of the present invention in which at least one fused Carbazole is substituted with carbazole substituted compounds B and C is judged to have a higher T1 and a deeper HOMO level, The electron blocking ability and the charge balance in the light emitting layer of holes and electrons are increased to maximize the efficiency and lifespan of the light emitting layer due to good light emission in the light emitting layer rather than at the interface of the hole transporting layer.

In general, when the light-emitting auxiliary layer is used as in Comparative Examples 5 to 7, 9 to 11 and 13 to 15 in which the comparative compounds A to C are used as the light-emitting auxiliary layer, the efficiency and lifetime of the light- The phenomenon that the driving voltage becomes high can be confirmed. However, the results of the device using the compound of the present invention as the material of the light-emitting auxiliary layer showed that the driving voltage was increased to be equal or slightly increased while improving the efficiency and lifetime, but being lower than that of the comparative compound. That is, the device using the compound of the present invention as the material of the light-emitting auxiliary layer improves the efficiency and the lifetime, and exhibits the best result that the driving voltage becomes equal or slightly higher. This is because the compounds of the present invention substituted with fused carbazole such as benzo-carbazole, dibenzo-carbazole and the like are substituted with carbazole, This can be a significant difference.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of the same should be construed as being included in the scope of the present invention.

100: organic electric element 110: substrate
120: first electrode 130: hole injection layer
140: Hole transport layer 141: Buffer layer
150: light emitting layer 151: light emitting auxiliary layer
160: electron transport layer 170: electron injection layer
180: second electrode

Claims (10)

A compound represented by the following formula (1).
&Lt; Formula 1 >

[In the above formula (1)
A and B independently of one another are a monocyclic or polycyclic C ₆ -C ₁₈ aryl group, wherein A and B are both monocyclic,
Ar ¹ and Ar ² are, independently of each other, a C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R ^a ) (R ^b );
m and n are each independently an integer of 0 to 4,
p and q are each independently an integer of 0 to 3,
R ¹ to R ⁴ are, independently of each other, i) deuterium; Tritium; halogen; Cyano; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R ^a ) (R ^b ); or ii) adjacent groups may combine with each other to form at least one ring (provided that at least one of R ¹ to R ⁴ are the same as defined in i) above,
L 'is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group,
R ^a and R ^b are each independently a C ₆ to C ₆₀ aryl group; A fluorenyl group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si and P;
Each of the aryl group, the fluorenyl group, the heterocyclic group, the fused ring group, the alkyl group, the alkenyl group, the alkynyl group, the alkoxyl group, the aryloxy group, the arylene group and the fluorenylene group may be substituted with deuterium; halogen; A silane group; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ to C ₂₀ ; A C ₁ to C ₂₀ alkoxyl group; An alkyl group having ₁ to ₂₀ carbon atoms; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; C ₆ -C ₂₀ An aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A heterocyclic group of C ₂ ~ C _20; A C ₃ to C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ to C ₂₀ ; And an arylalkenyl group having from ₈ to ₂₀ carbon atoms. The method according to claim 1,
Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;
&Lt; Formula 2 &gt;&lt; EMI ID =

(Wherein B, Ar ¹ , Ar ² , R ¹ to R ⁴ , m, n, p and q are as defined in claim 1) The method according to claim 1,
Lt; / RTI &gt; is one of the following compounds.

An organic electric device comprising a compound according to any one of claims 1 to 3. 5. The method of claim 4,
A first electrode; A second electrode; And an organic material layer disposed between the first electrode and the second electrode and containing the compound. 6. The method of claim 5,
Wherein the compound is contained in at least one of the hole injection layer, the hole transport layer, the light emission assisting layer and the light emitting layer of the organic material layer. 6. The method of claim 5,
Further comprising a light-efficiency-improvement layer formed on at least one side of the one surface of the first electrode and the second electrode opposite to the organic material layer. 6. The method of claim 5,
Wherein the organic material layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process. A display device including the organic electroluminescent device of claim 4; And
And a control unit for driving the display device. 10. The method of claim 9,
Wherein the organic electroluminescent device is at least one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, and a monochromatic or white illumination device.

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