KR20150124000A - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

The present invention provides a compound with high light-emitting efficiency of an element, low driving voltage, and improved durability, an organic electronic element using the same, and an electronic device thereof. The compound is represented by chemical formula 1.

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.

One of the biggest problems in organic electronic devices is the lifetime and the efficiency. As the display becomes larger, such efficiency and lifetime problems must be solved.

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 occurring during driving is reduced. As a result, And the like. However, simply improving the organic material layer can not maximize the efficiency. This is because the energy level and T ₁ value between each organic layer, the intrinsic properties (mobility, interfacial properties, etc.) of the materials, etc., Because.

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 holes move faster than the electrons, so that the excitons generated in the light emitting layer are transferred to the electron transporting layer, resulting in charge unbalance in the light emitting layer and light emission at the interface of the electron transporting layer.

When light is emitted from the interface of the electron transport layer, the color purity and efficiency of the organic electroluminescent device are lowered. In particular, when the organic electroluminescent device is manufactured, the stability of the organic electroluminescent device is deteriorated and the lifetime of the organic electroluminescent device is shortened. Therefore, it is necessary to develop an electron transporting material which has a high temperature stability and a high electron mobility and has a high T1 value to improve the hole blocking ability.

An object of the present invention is to provide a compound capable of lowering the driving voltage of the device, and greatly improving the luminous efficiency and lifetime, and an organic electronic 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, a low driving voltage and a high luminous efficiency of the device can be achieved, and the lifetime of the device can be greatly improved.

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 numerals even though they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

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

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 Alkyl " means a radical of a saturated aliphatic group, including alkyl, cycloalkyl-substituted alkyl groups.

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 having 1 to 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 electron transporting layer 160.

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.

Accordingly, in the present invention, by forming an electron transporting layer using the compound represented by the general formula (1), it is possible to optimize the energy level and T1 value between the organic layers, the mobility of the material, Life and efficiency can be improved at the same time.

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 (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a monochromatic or white illumination device.

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,

X ¹ To X < ⁵ > independently from each other are CR ' or N, X ^& To X ⁵ At least three of them are N.

R is hydrogen; _An alkyl group having ₁ to ₆₀ carbon atoms; A C ₆ to C ₆₀ aryl group, and m is an integer of 0 to 2.

L may be a single bond or a C ₆ to C ₆₀ arylene group. Herein, the term "single bond" means that L does not exist, and compounds represented by the formulas (9-1) to (9-8) which may be included in the formula (1) of the present invention are described in which L is a single bond.

R ¹ to R ⁵ are bonded to each other to form a heterocycle containing at least one aromatic ring or at least one heteroatom selected from O, N, S, Si and P. The aromatic ring or the group which does not form a heterocycle are, independently of each other, hydrogen; heavy hydrogen; 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; A C ₆ to C ₃₀ aryloxy group, and the like. for example, R ¹ To R ⁵ is Are independently from each other hydrogen, fluorine (F), a phenyl group substituted with deuterium, a naphthyl group, a biphenyl group, and the like anthracene group, R ¹ to R ⁵ may be the same or different.

R 'is hydrogen; heavy hydrogen; 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; A C ₆ to C ₃₀ aryloxy group, and the like.

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 and the arylene group are each independently selected from 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, among the compounds represented by the above formula (1), A may be represented by one of the following formulas.

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

&Lt; Formula 2 > < EMI ID =

&Lt; Formula 6 > < EMI ID =

R, m and L in the above Chemical Formulas 2 to 9 may be defined as defined in Chemical Formula 1 above.

More specifically, the compounds represented by Chemical Formulas 1 to 9 may be any one 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, , The light emitting layer, the electron transporting layer, and the electron injecting layer. That is, the compound represented by the formula (1) can be used as a material for the hole injecting layer, the hole transporting layer, the light emitting auxiliary layer, the light emitting layer, the electron transporting layer or the electron injecting layer. Specifically, an organic electroluminescent device including one of the compounds represented by the above Chemical Formulas 2 to 9 in the organic material layer is provided. More specifically, The organic compound layer may be prepared by adding the organic compounds (1-1 to 1-16, 2-1 to 2-16, 3-1 to 3-16, 4-1 to 4-16, 5-1 to 5-16, 6-16, 7-1 to 7-16, 8-1 to 8-16, 9-1 to 9-8).

In still another embodiment, the compound is contained singly in at least one layer of the hole injection layer, the hole transport layer, the light emission assisting layer, the light emitting layer, the electron transport layer, and the electron injection layer of the organic material layer, Wherein the compound is contained in combination of two or more different compounds, or the compound is contained in combination with two or more kinds of other compounds. In other words, the respective layers may contain the compounds corresponding to claims 1 to 4 alone, and may comprise two or more compounds of the compounds of claims 1 to 4, and the compounds of claims 1 to 4, And mixtures with compounds not falling within the scope of the present invention. Herein, the compound not corresponding to the present invention may be a single compound or may be two or more compounds. When the compound is contained in combination with two or more kinds of other compounds, the other compound may be a known compound of each organic layer or a compound to be developed in the future.

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 final products of the present invention are prepared by reacting Sub 1 and Sub 2 as shown in Scheme 1 below.

<Reaction Scheme 1>

I. Sub  1 and Sub  2 of Synthetic example

One. Sub  1 of Synthetic example

Sub 1 of Scheme 1 can be synthesized by the reaction path of Scheme 2 below, but is not limited thereto.

<Reaction Scheme 2>

Sub 1-1 (1 eq.) Was dissolved in anhydrous ether, the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.5 M in hexane) (1.1 eq.) Was slowly added dropwise and the reaction was stirred for 30 minutes . 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 with MgSO ₄ and concentrated. Subsequently, the organic matter was purified by silicagel column and recrystallized to obtain Sub 1.

(One) Sub  Synthesis of 1 (2)

<Reaction Scheme 3>

(6.2 g, 20 mmol) was dissolved in anhydrous ether, the temperature of the reaction solution was lowered to -78 ° C, and a solution of n-BuLi (2.5 M in hexane) (1.4 g, 22 mmol) was slowly added dropwise and the reaction was stirred for 30 minutes. The temperature of the reaction mixture was then lowered to -78 ° C and triisopropyl borate (5.64 g, 30 mmol) 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. The resulting organic material was subjected to silicagel column and recrystallization to obtain 4.3 g of Sub 1 (2). (Yield: 78%).

(2) Sub  Synthesis of 1 (4)

<Reaction Scheme 4>

(7.8 g, 20 mmol) was dissolved in anhydrous ether, the temperature of the reaction was lowered to -78 ° C, and n-BuLi (2.5 M in hexane) (1.4 g, 22 mmol) was slowly added dropwise, and then the reaction was stirred for 30 minutes. The temperature of the reaction mixture was then lowered to -78 ° C and triisopropyl borate (5.64 g, 30 mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After the reaction was completed, the reaction mixture was extracted with ethyl acetate and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic matter was subjected to silicagel column and recrystallization to obtain 5.7 g of Sub 1 (4). (Yield: 80%).

Examples of the compounds belonging to Sub 1 include, but are not limited to, the following FD-MS values.

[Table 1]

2. Sub  Example of 2

Examples of compounds belonging to Sub 2 include, but are not limited to, FD-MS values for these are shown in Tables 2 and 3.

[Table 2]

[Table 3]

The CAS Registry Number in Table 2 is the number of the commercially available substances, and Table 3 shows the FD-MS values for the non-marketed substances.

II . The final product ( Final products )of Synthetic example

Sub 1 (1 eq), Pd (PPh ₃ ) ₄ (0.03 eq), NaOH (3 eq), THF (3 mL / 1 mmol) and water (1.5 mL) were added to a round bottom flask. / 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 final products.

One. Product  1-2 Synthetic example

<Reaction Scheme 5>

To a round bottom flask was put into a Sub 1 (2) (5.5g, 20mmol), Sub 2-9 (5.2g, 20mmol), Pd (PPh 3) 4 (0.7g, 0.6mmol), NaOH (2.4g, 60mmol) , 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 6.1 g of 1-2. (Yield: 74%).

2. Product  2-4 Synthetic example

<Reaction Scheme 6>

To a round bottom flask Sub 1 (4) (7.1g, 20mmol) were dissolved, Sub 2-10 (5.2g, 20mmol) , Pd (PPh 3) 4 (0.7g, 0.6mmol), NaOH (2.4g, 60mmol) , 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 6.1 g of 2-4. (Yield: 76%).

3. Product  3-3 Synthetic example

<Reaction Scheme 7>

To a round bottom flask Sub 1 (3) (4.6g, 20mmol) were dissolved, Sub 2-20 (5.2g, 20mmol) , Pd (PPh 3) 4 (0.7g, 0.6mmol), NaOH (2.4g, 60mmol) , 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 5.4 g of 3-3. (Yield: 75%).

4. Product  4-6 Synthetic example

<Reaction Scheme 8>

Into the Sub 1 (6) (7.1g, 20mmol) in a round bottom flask, Sub 2-37 (5.2g, 20mmol) , Pd (PPh 3) 4 (0.7g, 0.6mmol), NaOH (2.4g, 60mmol) , 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 7.7 g of 4-6. (Yield: 79%).

5. Product  5-4 Synthetic example

<Reaction Scheme 9>

To a round bottom flask Sub 1 (4) (7.1g, 20mmol) were dissolved, Sub 2-41 (5.2g, 20mmol) , Pd (PPh 3) 4 (0.7g, 0.6mmol), NaOH (2.4g, 60mmol) , 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 7.8 g of 5-4. (Yield: 80%).

6. Product  6-12 Synthetic example

<Reaction formula 10>

To a round bottom flask Sub 1 (4) (7.1g, 20mmol) were dissolved, Sub 2-46 (5.2g, 20mmol) , Pd (PPh 3) 4 (0.7g, 0.6mmol), NaOH (2.4g, 60mmol) , 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 7.5 g of 6-12. (Yield: 77%)

7. Product  7-13 Synthetic example

<Reaction Scheme 11>

To a round bottom flask Sub 1 (5) (5.0g, 20mmol) into a, Sub 2-71 (7.2g, 20mmol) , Pd (PPh 3) 4 (0.7g, 0.6mmol), NaOH (2.4g, 60mmol) , 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 7.3 g of 7-13. (Yield: 75%).

8. Product  8-2 Synthetic example

<Reaction Scheme 12>

Into the Sub 1 (2) (5.5g, 20mmol) in a round bottom flask, Sub 2-56 (6.2g, 20mmol) , Pd (PPh 3) 4 (0.7g, 0.6mmol), NaOH (2.4g, 60mmol) , 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 of 8-2. (Yield: 78%).

9. Product  9-8 Synthetic example

<Reaction Scheme 13>

Sub 2 (56 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol) and NaOH (2.4 g, 60 mmol) were placed in a round bottom flask, , 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 9-8. (Yield: 74%).

On the other hand, the compounds 1-1 to 1-16, 2-1 to 2-16, 3-1 to 3-16, 4-1 to 4-16 and 5-1 of the present invention prepared according to the above- To 5-16, 6-1 to 6-16, 7-1 to 7-16, 8-1 to 8-16 and 9-1 to 9-8 are shown in Table 4 below.

[Table 4]

Evaluation of manufacturing of organic electric device

[Example 1] Green organic electroluminescent device (electron transport layer)

First, 4,4 ', 4 "-tris [2-naphthyl (phenyl) amino] triphenylamine (hereinafter abbreviated as 2-TNATA) was vacuum deposited on the ITO layer (anode) After forming the injection layer, 4,4-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as NPD) was vacuum deposited on the hole injection layer to a thickness of 60 nm, . Next, CBP [4,4'-N, N'-dicarbazole-biphenyl] was used as a host material and Ir (ppy) ₃ [tris (2-phenylpyridine) -iridium] 5 by weight to form a light emitting layer having a thickness of 30 nm. Subsequently, aluminum (1,1'bisphenyl) -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, Layer, and Compound 1-1 of the present invention was vacuum-deposited to a thickness of 40 nm on the hole blocking layer to form an electron transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited on the electron transport layer 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 electroluminescence device was manufactured.

[Examples 2 to 13] Green organic electroluminescent devices (electron transporting layers)

The compound 1-2 to 1-16, 2-1 to 2-16, 3-1 to 3-16, 4-1 to 4-16, and 5-11 of the present invention may be used instead of the compound 1-1 of the present invention as the electron transport layer material, 1 to 5-16, 6-1 to 6-16, 7-1 to 7-16, 8-1 to 8-16 and 9-1 to 9-8, An organic electroluminescent device was prepared.

[Comparative Example 1]

An organic electroluminescent device was prepared in the same manner as in Example 1, except that the following compound 1 (Alq ₃ ) was used instead of the compound 1-1 of the present invention as the electron transport layer material.

&Lt; Comparative Compound 1 > Alq ₃

[Comparative Example 2]

An organic electroluminescent device was prepared in the same manner as in Example 1, except that Comparative Compound 2 was used instead of Compound 1-1 of the present invention as an electron transport layer material.

 &Lt; Comparative Compound 2 >

[Comparative Example 3]

An organic electroluminescence device was prepared in the same manner as in Example 1, except that Comparative Compound 3 was used instead of Compound 1-1 of the present invention as an electron transport layer material.

&Lt; Comparative Compound 3 >

[Comparative Example 4]

An organic electroluminescence device was prepared in the same manner as in Example 1, except that Comparative Compound 4 was used instead of Compound 1-1 of the present invention as an electron transport layer material.

<Comparative Compound 4>

[Comparative Example 5]

An organic electroluminescent device was prepared in the same manner as in Example 1, except that Comparative Compound 5 was used instead of Compound 1-1 of the present invention as an electron transport layer material.

&Lt; Comparative Compound 5 >

Electruminescence (EL) characteristics were measured with photoresearch PR-650 by applying a forward bias DC voltage to the organic EL devices manufactured in Examples 1 to 136 and Comparative Examples 1 to 5 of the present invention And the T95 lifetime was measured using a lifetime measuring device manufactured by Mac Science Inc. at a luminance of 5000 cd / m 2. The measurement results are shown in Table 5 below.

[Table 5]

As the element measurement results of Table 5, the organic electroluminescence device (OLED) using the compound of the present invention is a low driving voltage and high efficiency is used as the electron transport material than Alq ₃ in the comparative compound 1 was widely used from old And high lifespan. This is the case of the compounds of the hand, indicate the dopant T ₁ value (2.0 eV) of the Alq ₃ is significantly lower T ₁ values using as an electron transporting layer than the Ir (ppy) ₃ of the T ₁ value (2.4 eV) used in the light emitting layer invention, Ir (ppy) ₃ of the T ₁ value (2.4 eV) than the generally high T ₁ value (2.5 ev ~ 2.6 ev) exhibits a hole-blocking ability (hole blocking ability) as well as be improved, and exciton (exciton) in the light emitting layer The probability of staying well is relatively high.

Next, a comparison of the results of organic electroluminescent devices of the present invention with Comparative Compound 2, Comparative Compound 3, Comparative Compound 4 and Comparative Compound 5 reveals that Comparative Compound 2 to which triazine is substituted rather than Alq ₃ , Compound 5 showed superior device results with lower driving voltage, higher efficiency and longer lifetime, and Comparative Compound 3 to Comparative Compound 5 in which the heterocyclic group was substituted with Comparative Compound 2 in which triazine was substituted with a general aryl group showed better device results Respectively. This can be explained as a result of having a higher electron mobility than the comparative compound 2 in which a general aryl group is substituted by substituting a heterocyclic group having an ET tendency.

When the organic electroluminescent device is driven, holes having a higher mobility than electrons act as majority carriers, and holes are accumulated in the light emitting layer, which adversely affects the device results. Therefore, in order to control the balance of holes and electrons, materials of electron transport layer having fast electron mobility are required.

Therefore, it was judged that Comparative Compounds 3 to 5, which had higher electron mobility than Comparative Compound 2, exhibited better results for this reason. The results of the inventive compounds show that the results of the compounds 6-1 to 6-16 in which phenanthroline substituted with two N having an ET tendency in the triazine are different from those of the other compounds And the results are shown.

In addition, the inventive compounds wherein benzoquinoline, phenanthroline, acridine, benzoacridine, and dibenzoacridine are substituted for triazine rather than compounds 3 to 5 in which triazine is substituted with heterocyclic groups such as pyridine, quinoline, and triazin has the lowest driving voltage and the highest efficiency And device results with a lifetime. This suggests that the characteristics of the heterocyclic group, which is a substituent of triazine, are different, and that the compound of the present invention in which benzoquinoline, phenanthroline, acridine, benzoacridine and dibenzoacridine are substituted is substituted with other heterocyclic rings such as pyridine, quinoline and triazine It is more rigid than the comparative compound and has fast electron mobility and thermal stability is improved. Thus, it is judged that the device having the lowest driving voltage and the highest efficiency and lifetime is shown.

On the other hand, in the case of compounds containing a plurality of heteroatoms such as triazine, the band gap, electrical characteristics, interface characteristics, or HOMO / LUMO levels may vary depending on the position, type, and number of heteroatoms, The tendency to inject or transport electrons or holes may vary. Compounds according to the present invention exhibit superior electrical properties, interfacial characteristics, and the like, compared with compounds containing other heteroatoms or compounds containing other numbers of heteroatoms.

Although the device characteristics have been described from the viewpoint of the electron transport layer in the above-described evaluation results of the device fabrication, the materials used for the electron transport layer are usually organic electronic devices such as the electron injection layer, the hole injection layer, the hole transport layer, And may be used alone or in combination with other materials. Therefore, the compound of the present invention can be used in combination with other organic materials other than the electron transporting layer such as the electron injecting layer and the hole injecting layer, the hole transporting layer, the light emitting layer, and the light emitting auxiliary layer.

The foregoing description is merely illustrative of the present invention, and various modifications may be made without departing from the essential characteristics of the present invention. 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 present invention 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 (12)

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

[In the above formula (1)
X ¹ To X &lt; ⁵ &gt; independently from each other are CR &apos; or N, X ^& To X ⁵ At least three of which are N,
R is hydrogen; _An alkyl group having ₁ to ₆₀ carbon atoms; A C ₆ to C ₆₀ aryl group, m is an integer of 0 to 2,
L is a single bond or a C ₆ to C ₆₀ arylene group,
R ¹ to R ⁵ are each a group selected from the group consisting of i) adjacent groups are bonded to each other to form a heterocycle containing at least one aromatic ring or at least one hetero atom selected from O, N, S, Si and P, ii) Or a group which does not form a heterocycle are, independently of each other, hydrogen; heavy hydrogen; 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; A C ₆ to C ₃₀ aryloxy group,
R 'is hydrogen; heavy hydrogen; 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; A C ₆ to C ₃₀ aryloxy group,
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 and the arylene group are each independently selected from 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,
Wherein A is selected from the following structures:

The method according to claim 1,
A compound represented by one of the following formulas:
&Lt; Formula 2 >< EMI ID =

&Lt; Formula 6 &gt;&lt; EMI ID =

(Wherein R, m and L in the above Chemical Formulas 2 to 9 are defined as defined in claim 1) The method according to claim 1,
A compound represented by formula

5. An organic electroluminescent device comprising a compound according to any one of claims 1 to 4. 6. The method of claim 5,
A first electrode; A second electrode; And an organic material layer disposed between the first electrode and the second electrode and containing the compound. The method according to claim 6,
Wherein the compound is contained in at least one of the hole injection layer, the hole transporting layer, the light emission assisting layer, the light emitting layer, the electron transporting layer and the electron injection layer of the organic material layer. 8. The method of claim 7,
Wherein the compound is contained singly in at least one of the hole injection layer, the hole transport layer, the light emission assisting layer, the light emitting layer, the electron transport layer and the electron injection layer of the organic material layer, Or an organic electroluminescent device, wherein the compound is contained in combination with at least two other compounds. The method according to claim 6,
And an optical efficiency improving layer formed on at least one surface of the first electrode and the second electrode opposite to the organic layer. The method according to claim 6,
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 comprising the organic electroluminescent device of claim 5; And
And a control unit for driving the display device. 12. The method of claim 11,
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 device for monochromatic or white illumination.

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