KR20160005430A - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

The purpose of the present invention is to provide a compound which is capable of having high light-emitting efficiency of an element, having low driving voltage, and improving durability, to provide an organic electronic element using the same, and to provide 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.

The light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight and may be classified into a fluorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons according to an emission mechanism . Further, the light emitting material can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural color depending on the luminescent color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system may be used as a light emitting material for the purpose of increasing the light emitting efficiency. When the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with a small amount of the light emitting layer, the excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength of the dopant, light of the desired wavelength can be obtained according to the type of the dopant used.

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 of each organic material layer, the intrinsic properties (mobility, interface characteristics, etc.) of the materials are achieved, the long life and high efficiency can be achieved at the same time.

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 a host material for a light emitting layer is urgently required.

It is an object of the present invention to provide a compound capable of improving the light emitting efficiency, the driving voltage and the lifetime of the device, the organic electric device using the same, and the electronic device.

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 high luminous efficiency and a low driving voltage 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 whenever 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 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 terphenyl group, a naphthyl group, an anthracenyl 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 light emitting layer 150.

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- In particular, when the optimal combination of the energy level and T1 value and the intrinsic properties (mobility, interfacial characteristics, etc.) between the organic layers are achieved, it is possible to achieve long life and high efficiency at the same time.

Accordingly, in the present invention, by forming the light emitting layer using the compound represented by the general formula (1), it is possible to optimize the energy level and the Tl value between the respective organic layers, the mobility of the material, 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,

A and B 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 );

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;

Y ₁ to Y ₈ are each independently CR or N, and at least one of Y ₁ to Y ₈ is N.

At least one of the Rs is connected to the neighboring carbazole, and the unconnected R is hydrogen.

For example, when A, B, L ', R _a and R _b are aryl groups, A, B, L', R _a and R _b may independently be phenyl, biphenyl or naphthyl.

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; A C ₆ to C ₂₀ 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 =

&Lt; Formula 5 > < EMI ID =

&Lt; Formula 8 > < EMI ID =

In formulas (2) to (9)

Y ₁ to Y ₈ , A and B may be the same as Y ₁ to Y ₈ , A and B defined in the above formula (1).

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

&Lt; Formula 10 > < EMI ID =

&Lt; Formula 12 > < EMI ID =

In formulas (10) to (13)

Y ₁ to Y ₈ are each independently CH or N, and at least one of them is N, and A and B may be the same as A and B defined in the above formula (1).

More specifically, the compounds represented by Chemical Formulas 1 to 13 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, and the compound represented by Formula 1 may include a hole injecting layer, a hole transporting layer, , The light emitting auxiliary layer, the light emitting layer, the electron transporting layer, and the electron injecting layer. Particularly, the compound represented by the formula (1) can be included in the light emitting 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. In particular, the compound represented by the formula (1) can be used as a material for the light emitting layer. Specifically, it is preferable that the organic material layer includes one of the compounds represented by Chemical Formulas 2 to 13, and more specifically, The compound represented by the above-mentioned individual formulas (1-1 to 1-28, 2-1 to 2-128, 3-1 to 3-128, 4-1 to 4-28, and 5-1 to 5-4) And an organic electroluminescent device.

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, each of the layers may contain a compound corresponding to Formulas 1 to 13 alone, and may include two or more compounds of Formulas (1) to (13) A mixture with a compound not corresponding to the invention may be included. 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. At this time, the compound contained in the organic material layer may be composed of the same kind of compound, but it may be a mixture of two or more different kinds of compounds represented by the general formula (1).

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

The compound represented by Formula 1 according to the present invention is prepared by reacting Sub 1 with Sub 2 as shown in Reaction Scheme 1 below, but is not limited thereto.

<Reaction Scheme 1>

Ⅰ. Synthesis example of Sub 1

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 Synthesis

Cu (764 mg, 12 mmol), 18-Crown-6 (6.3 g, 24 mmol) and NaO t- Bu (20 mmol) were added to 800 mL of toluene after bromo-9H- 57.6 g, 600 mmol) were added, and the mixture was refluxed with stirring at 100 DEG C for 24 hours. ether and water. The organic layer is dried over MgSO ₄ and concentrated. The resulting organic material is purified by silicagel column and recrystallized to obtain an intermediate.

[Synthesis of Sub 1-1 (1)] [

<Reaction Scheme 3>

Cu (764 mg, 12 mmol) and 18-Crown-6 (6.3 g, 24 mmol) were mixed in a mixture of bromo-9H-carbazole (50 g, 203 mmol) and iodobenzene (49 g, NaO t- Bu (57.6 g, 600 mmol) was 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 36.6 g of Sub 1-1 (1). (Yield: 57%).

Examples of Sub 1-1 are as follows, but are not limited thereto, and their FD-MS values are as shown in Table 1 below.

[Table 1]

Sub 1 synthesis

Place the dropping funnel in a two-neck RBF and dissolve in 500 ml THF and keep the temperature at -78 ° C. After stirring for 1 hour, drop the trimethoxyborate slowly and stir again for 1 hour. After completion of the reaction, 500 ml of 5% hydrochloric acid was added, and the mixture was stirred at room temperature for 1 hour. The mixture was extracted with water and ethyl acetate, concentrated, and recrystallized from MC and hexane to obtain Sub 1.

[Synthesis of Sub 1 (1)] [

<Reaction Scheme 4>

A dropping funnel is installed in the two-neck RBF and Sub 1-1 (1) (38 g, 118 mmol) is dissolved in 500 ml THF and the temperature is maintained at -78 ° C. After stirring for 1 hour, trimethoxyborate (18.4g, 177mmol) was slowly dropwise added and stirred for another 1 hour. After completion of the reaction, 500 ml of 5% hydrochloric acid was added, and the mixture was stirred at room temperature for 1 hour. The mixture was extracted with water and ethyl acetate, concentrated, and recrystallized from MC and hexane to obtain 20.3 g of Sub 1 (1). (Yield: 60%).

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

[Table 2]

Ⅱ. Sub 2 synthesis example

Sub 2 of Scheme 1 may be synthesized by the reaction path of Scheme 5 below, but is not limited thereto.

<Reaction Scheme 5>

[Synthesis of Sub 2-1 (1)] [

<Reaction Scheme 6>

Cu (764 mg, 12 mmol) and 18-crown were mixed in a mixture of 8-bromo-9H-pyrido [2,3-b] indole (50.2 g, 203 mmol), iodobenzene (49.0 g, -6 (6.3 g, 24 mmol) and NaO t- Bu (57.6 g, 600 mmol) were added, 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 28.2 g of 8-bromo-9-phenyl-9H-pyrido [2,3-b] indole. (Yield: 43%).

Examples of Sub 2 include, but are not limited to, the following FD-MS values.

[Table 3]

Ⅲ. Synthesis Example of Final Products

Sub 1 compound (1.1 eq.), Pd (PPh ₃ ) ₄ (0.03-0.05 eq.), NaOH (3 eq.), THF (3 mL / 1 mmol) were placed in a round bottom flask, , And water (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 the product.

1. Synthesis Example of Compound 1-1

<Reaction Scheme 7>

Bromo-9-phenyl-9H-pyrido [2,3-b] indole (12.2 g, 22 mmol) was added to a round-bottomed flask with a solution of 9-phenyl-9H-carbazol- ), put the _{Pd (PPh 3) 4 (0.5g} , 0.6mmol), K 2 CO 3 (8.3g, 60mmol), THF (60 mL), water (30mL). 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 5.6 g (yield: 58%) of the product.

2. Synthesis Example of Compound 2-38

<Reaction Scheme 8>

9-phenyl-9H-carbazol-4-yl) boronic acid (5.7 g, 20 mmol) was added to a round bottom flask and 7-bromo-9- 2-yl) phenyl) -9H-pyrido [2,3-b] indole (12.2 g, 22 mmol), Pd (PPh ₃ ) ₄ (0.03-0.05 eq.), K ₂ CO ₃ 10 mL) and water (5 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 8.2 g (yield: 57%) of the product.

3. Synthesis Example of Compound 2-70

<Reaction Scheme 9>

To a round bottom flask was added 7-bromo-9- (3- (4,6-diphenylpyrimidin-2-yl) -9H-carbazol- -diphenyl-1,3,5-triazin-2- yl) phenyl) -9H-pyrido [2,3-b] indole (12.2g, 22mmol), Pd (PPh 3) 4 (0.03 ~ 0.05 eq.), K ₂ CO ₃ (3 eq.), THF (10 mL) and water (5 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 8.0 g of the product (yield: 62%).

4. Synthesis Example of Compound 3-10

<Reaction formula 10>

A solution of 6-bromo-9-phenyl-9H-pyrido [2, 3-dihydroxy-9H-carbazol-1-yl) boronic acid (8.8 g, 20 mmol) , 3-b] indole (7.1 g, 22 mmol), Pd (PPh ₃ ) ₄ (0.03-0.05 equivalent), K ₂ CO ₃ (3 eq.), THF (10 mL) and water (5 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 (yield: 57%) of the product.

5. Synthesis Example of Compound 3-68

<Reaction Scheme 11>

To a round-bottomed flask was added 8- bromo-5 (5,6-diphenyl-1,3,5-triazin-2-yl) -9H-carbazol- -phenyl-5H-pyrido [3,2- b] indole (7.1g, 22mmol), Pd (PPh 3) 4 (0.03 ~ 0.05 eq.), K ₂ CO _{3 (3} equiv.), THF (10 mL), water (5 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 7.0 g (yield: 54%) of the product.

6. Synthesis Example of Compound 3-76

<Reaction Scheme 12>

(9- (3- (4,6-diphenyl-1,3,5-triazin-2-yl) phenyl) -9H-carbazol-4-yl) boronic acid (10.4 g, 20 mmol) was added to a round bottom flask 8-bromo-5-phenyl- 5H-pyrido [3,2-b] indole (7.1g, 22mmol), Pd (PPh 3) 4 (0.03 ~ 0.05 eq.), K ₂ CO _{3 (3} equiv.), THF ( 10 mL) and water (5 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 10.5 g (yield: 73%) of the product.

7. Synthesis Example of Compound 4-23

<Reaction Scheme 13>

9H-carbazol-4-yl) boronic acid (7.2 g, 20 mmol) was added to a round bottom flask and 4-bromo-9-phenyl-9H- pyrido [3,4-b] indole ( 7.1g, 22mmol), Pd (PPh 3) 4 (0.03 ~ 0.05 eq.), K ₂ CO _{3 (3} equiv.), THF (10 mL), water (5 mL) to . 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 (yield: 69%) of the product.

On the other hand, the compounds 1-1 to 1-28, 2-1 to 2-128, 3-1 to 3-128, 4-1 to 4-28, and 5-1 The FD-MS values of 5-4 are shown in Table 4 below.

[Table 4]

Evaluation of manufacturing of organic electric device

Ⅰ. Fabrication and test of green organic electroluminescent device (phosphorescent host)

[Example 1] Green organic electroluminescent device (phosphorescent host)

An organic electroluminescent device was fabricated according to a conventional method using a compound obtained through synthesis as a host material in a light emitting layer. First, on the ITO layer (anode) formed on the glass substrate, N ¹ - (naphthalen-2-yl) -N ⁴ and N ⁴ -bis (4- (naphthalen- ) -N ¹ -phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) was formed by vacuum deposition to a thickness of 60 nm. Subsequently, 4,4-bis [ N - (1-naphthyl) -N -phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vapor-deposited as a hole transport compound on the film to a thickness of 60 nm to form a hole transport layer . The compound 1-1 of the present invention was used as a host on the hole transport layer and doped with Ir (ppy) ₃ [tris (2-phenylpyridine) -iridium] as a dopant to a thickness of 30 nm A light emitting layer was deposited. (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm as a hole blocking layer, and electron injection Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was deposited to a thickness of 40 nm. Thereafter, LiF as an alkali metal halide was deposited to a thickness of 0.2 nm, Al was subsequently deposited to a thickness of 150 nm, and this Al / LiF was used as a cathode to produce an organic electroluminescent device.

[Example 2] to [Example 312] A green organic electroluminescent device (phosphorescent host)

As the phosphorescent host material of the light emitting layer, instead of Compound 1-1 of the present invention, the compounds 1-2 to 1-28, 2-1 to 2-128, 3-1 to 3-128, and 4-1 To 4-28 were used in place of the organic electroluminescent device.

[Comparative Example 1]

Except that the following compound A [CBP (4,4'-N, N'-dicarbazole-biphenyl)] was used instead of the compound 1-1 of the present invention as a phosphorescent host material in the light emitting layer To prepare an organic electroluminescent device.

&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 a phosphorescent host material in the light emitting layer.

&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 phosphorescent host material in the light emitting layer.

<Comparative compound C>

[Comparative Example 4]

An organic EL device was prepared in the same manner as in Example 1, except that the following compound D was used in place of the compound 1-1 of the present invention as a phosphorescent host material in the light emitting layer.

<Comparative compound D>

Electruminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured by Examples 1 to 312 and Comparative Examples 1 to 4 of the present invention And the T95 lifetime was measured using a life measuring device manufactured by Mac Science Inc. at a luminance of 5000 cd / m 2. Table 5 shows the results of device fabrication and evaluation.

[Table 5]

Ⅱ. Preparation and test of red organic electroluminescent device (phosphorescent host)

[Example 313] Red organic electroluminescence device (phosphorescent host)

An organic electroluminescent device was fabricated by a conventional method using a compound obtained through synthesis as a luminescent host material in a light emitting layer. First, N ¹ on the ITO layer (anode) formed on the glass substrate - (naphthalen-2-yl) -N 4, N 4 -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N 1 phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) was vacuum-deposited to form a hole injection layer having a thickness of 60 nm. Then, 4,4-bis [N- -Naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum deposited to a thickness of 60 nm to form a hole transport layer. (Piq) ₂ Ir (acac) [bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate] as a dopant was doped at a weight ratio of 95: 5 To form a light emitting layer with a thickness of 30 nm. Subsequently, aluminum (1,1'-biphenyl) -4-oleato) bis (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as BAlq) was vacuum deposited as a hole blocking layer to a thickness of 10 nm, Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was deposited to a thickness of 40 nm as a transport layer. Then, LiF, an alkali metal halide serving as an electron injecting layer, was deposited to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm to form an organic electroluminescent device.

[Examples 314 to 336] Red organic electroluminescent devices (phosphorescent host)

Except for using one of the compounds 2-42 to 2-52 and 3-41 to 3-52 of the present invention described in the following Table 6 instead of the compound 2-41 of the present invention as the phosphorescent host material of the light emitting layer, 313, an organic electroluminescent device was prepared.

[Comparative Example 5]

The same method as in Example 313 was used except that the compound A [CBP (4,4'-N, N'-dicarbazole-biphenyl)] was used instead of the compound 2-41 of the present invention as a phosphorescent host material in the light emitting layer To prepare an organic electroluminescent device.

[Comparative Example 6]

An organic electroluminescent device was prepared in the same manner as in Example 313, except that the compound B was used instead of the compound 2-41 of the present invention as a phosphorescent host material in the light emitting layer.

[Comparative Example 7]

An organic electroluminescence device was prepared in the same manner as in Example 313, except that the compound C was used instead of the compound 2-41 of the present invention as a phosphorescent host material in the light emitting layer.

[Comparative Example 8]

An organic EL device was prepared in the same manner as in Example 313, except that the compound D was used instead of the compound 2-41 of the present invention as a phosphorescent host material in the light emitting layer.

Electroluminescence (EL) characteristics were measured with PR-650 manufactured by photoresearch by applying a forward bias DC voltage to the organic electroluminescence devices prepared in the Examples and Comparative Examples. The measurement results showed that the luminance was 2500 cd / The T95 lifetime was measured using a life time measuring instrument manufactured by Mac Science. Table 6 below shows the results of device fabrication and evaluation.

[Table 6]

As can be seen from the results of Tables 5 and 6, the organic electroluminescence device using the organic electroluminescence device material of the present invention as a phosphorescent host showed low driving voltage, high luminous efficiency and long life.

In other words, Comparative Compounds B, C and D, in which Bis-carbazole is a core, exhibited excellent device results, and Comparative Compounds B, C and D The compound of the present invention in which carbazole and carboline are bonded showed the best results in terms of driving voltage, efficiency and lifetime.

The compound of the present invention is composed of carbazole and carboline and thus has bipolar characteristics. Therefore, the charge balance in the light emitting layer can be improved compared to the comparative compounds B, C and D, and it is considered that the efficiency is increased, and the accumulation of holes in the light emitting layer is smaller than the comparative compounds B, C and D, . (When a OLED device is driven, holes generally have a mobility that is about 1000 times faster than electrons)

In addition, the compound of the present invention has a T 1 value similar to that of Comparative Compounds B, C, and D, but has a lower LUMO, resulting in easy acceptance of electrons from the electron transport layer and hence low driving voltage and thermal stability Which is caused by thermal damage).

Although the device characteristics have been described from the viewpoint of the light emitting layer in the evaluation results of the above-described device fabrication, the materials commonly used for the light emitting layer include organic electronic devices such as the electron transport layer, electron injection layer, hole injection 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 a single or different materials in addition to the light emitting layer, for example, an electron transporting layer, an electron injecting layer, a hole injecting layer, a hole transporting layer and a 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 (9)

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

[In the above formula (1)
A and B 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 );
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 ; Is selected from the group consisting of; and O, N, S, Si, and a heterocyclic group of C ₂ ~ C ₆₀ containing at least one hetero atom of the P
Y ₁ to Y ₈ are each independently CR or N, at least one of Y ₁ to Y ₈ is N,
Wherein at least one of the Rs is connected to the neighboring carbazole, the unconnected R is hydrogen,
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; A C ₆ to C ₂₀ 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; Formula 2 >< EMI ID =

&Lt; Formula 5 &gt;&lt; EMI ID =

&Lt; Formula 8 >< EMI ID =

(Wherein Y ₁ to Y ₈ , A and B are the same as Y ₁ to Y ₈ , A and B defined in Chemical Formula 1) The method according to claim 1,
Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;
&Lt; Formula 10 &gt;&lt; EMI ID =

&Lt; Formula 12 >&lt; EMI ID =

(Wherein Y ₁ to Y ₈ are independently of each other CH or N, and Y ₁ to Y ₈ At least one is N, and A and B are the same as A and B defined in the above formula (1) The method according to claim 1,
Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;

A first electrode;
A second electrode; And
An organic material layer disposed between the first electrode and the second electrode, the organic material layer containing a compound according to any one of claims 1 to 4. 6. The method of claim 5,
Wherein the organic material layer comprises a light emitting layer, and the light emitting layer contains the compound alone or in a mixture. 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 comprising the organic electroluminescent device of claim 5; And
And a control unit for driving the display device. 9. The method of claim 8,
Wherein the organic electroluminescent device is 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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