KR20150039136A - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

The present invention provides a novel compound capable of improving light emitting efficiency, stability, and lifespan of an element, an organic electronic element using the same, and an electronic device thereof. The organic electronic element comprises a first electrode, a second electrode, and an organic material layer located between the first electrode and the second electrode, wherein the organic material layer comprises the compound.

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 electroluminescence device using an organic light emitting phenomenon generally has a structure including an anode, an anode, and an organic layer between the anode and the cathode. Here, in order to increase the efficiency and stability of the organic electroluminescent device, the organic material layer may have a multi-layered structure composed of different materials and may include 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 electroluminescent device can be classified into a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, and an electron injecting material depending on its function.

In organic electroluminescent devices, the most problematic is the lifetime and the efficiency. As the display becomes large-sized, such efficiency and lifetime problems 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, And the lifetime tends 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, interfacial properties, etc.) of the material, etc. are achieved, long life and high efficiency can be achieved at the same time to be.

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 the organic electroluminescent device is irradiated with light at the interface, the color purity and efficiency of the organic electroluminescent device deteriorate. In particular, the organic electroluminescent device has poor stability at high temperature and shortens the lifetime of the organic electroluminescent device . Therefore, it is necessary to develop an electron transporting material having high temperature stability, high T1 value, fast electron mobility and effective hole blocking ability.

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

That is, in order to sufficiently exhibit the excellent characteristics of the organic electroluminescent device, materials 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, The organic material layer for an organic electroluminescence device has not yet been developed sufficiently. Therefore, development of new materials is continuously required, and development of a combination of materials such as a hole transporting layer, an electron transporting layer, and the like is urgently required.

In recent years, not only researches to improve the device characteristics by changing the performance of each material, but also to improve the color purity by optimizing the optical thickness between the anode and the cathode in the top element of the resonance structure, Is one of the important factors in improving the performance of the device. Compared with the bottom element structure of the non-resonance structure, the top element structure has a large optical energy loss due to SPP (surface plasmon polariton) because the formed light reflects to the anode which is the reflection film and emits light toward the cathode. Therefore, one of the important ways to improve the appearance and efficiency of the EL spectra is to use a capping layer on the top cathode. In general, the electron emission of SPP is mainly composed of four metals such as Al, Pt, Ag and Au, and surface plasmon is generated on the surface of the metal electrode. For example, when the cathode is made of Ag, the light emitted by the Ag of the cathode is quenching (light energy loss due to Ag) by the SPP, and the efficiency is reduced. On the other hand, when a capping layer is used, SPP is generated at the interface between the MgAg electrode and the high-refractive-index organic material, and the TE polarized light is annihilated from the CPL plane in the vertical direction by the evanescent wave , Transverse magnetic (TM) polarized light moving along a cathode and a capping layer is amplified by surface plasma resonance so that the intensity of the peak is increased Thereby enabling high efficiency and effective color purity control.

An organic electroluminescent device having high efficiency, high lifetime and high color purity, and an electronic device using the same, which has high electron mobility and high temperature stability and has a hole blocking ability at a high T1 value, The purpose is to provide.

In one aspect, the invention provides compounds represented by the formula:

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

By using the compound according to the present invention, it is possible to achieve a high luminous efficiency, a low driving voltage, and a high heat resistance of the device, and can greatly improve the color purity and lifetime of the device.

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

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

It should be noted that, in adding reference numerals to the constituent elements of the drawings, the same constituent elements are denoted by the same reference 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 Quot; means a radical of a saturated aliphatic group, including an alkyl group, a cycloalkyl-substituted alkyl group.

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

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

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

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

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

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

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

The terms "aryl group" and "arylene group ", as used herein, unless otherwise specified, each have 6 to 60 carbon atoms, but are not limited thereto. In the present invention, an aryl group or an arylene group means a single ring or a multicyclic aromatic group, and neighboring substituents include aromatic rings formed by bonding or participating in the reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, 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 indicated, includes one or more heteroatoms, has from 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings and includes a heteroaliphatic ring and hetero 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 having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocyclic ring having 2 to 60 carbon atoms, or a combination thereof, Saturated or unsaturated ring.

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

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

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

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

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

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

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

1, an organic electroluminescent device 100 according to the present invention includes a first electrode 120, a second electrode 180, a first electrode 110, and a second electrode 180 formed on a substrate 110, ) Comprising an organic compound layer comprising a compound according to the present invention. In this case, the first electrode 120 may be an anode and the second electrode 180 may be a cathode (cathode). In case of an inverting type, the first electrode may be a cathode and the second electrode may be an anode.

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

Also, although not shown, the organic electroluminescent device according to the present invention may further include a protective layer or a light-efficiency-improving layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer.

The compound according to the present invention applied to the organic material layer may be a host or dopant of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, the light emitting layer 150, It can be used as a material.

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 >

Wherein R ¹ to R ¹² are independently selected from the group consisting of (i) independently of one another hydrogen; heavy hydrogen; halogen; 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 ; Or -LN (R _a ) (R _b ); or ii) R ¹ and R ² , R ³ and R ⁴ , R ⁴ and R ⁵ , R ⁵ and R ⁶ , R ⁷ and R ^8, R ⁹ and R ^10, R ¹⁰ and R ¹¹ and R ¹¹ and R ¹² may form at least one ring by combining to each other, wherein the "ring" is a C ₃ ~ C ₆₀ alicyclic, C ₆ ~ Refers to a fused ring consisting of an aromatic ring of C ₆₀ , a C ₂ to C ₆₀ hetero ring, or a combination thereof, and includes a saturated or unsaturated ring.

n is an integer of 1 or 2, Het is a heterocyclic group of C ₂ ~ C ₆₀ comprising at least one nitrogen. Illustratively, Het can be pyridyl, pyrimidinyl, triazine, quinazolinyl, and the like, excluding indole and carbazole.

L ¹ , L ² and L may be, independently of each other, a single bond or a divalent linking group. Wherein the divalent linking group is a C ₆ to C ₆₀ arylene group; 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 containing at least one heteroatom selected from O, N, S, Si and P;

And L < ³ > is a linking group capable of changing the valency depending on n, and when n is 1, it is a divalent linking group, and when n is 2, it is a trivalent linking group. For example, L ³ is a divalent or trivalent aryl of C ₆ to C ₆₀ ; A divalent or trivalent fluorene; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from the group consisting of O, N, S, Si and P, and further L ³ may be a single bond. Provided that when n is 2, L < ³ > can not be a single bond.

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

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 aryloxyl group, the arylene group, and the fluorenylene group are respectively deuterium; halogen; A silane group; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; -LN (R < _a >) (R < _b >); 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 having ₇ to ₂₀ carbon atoms, an arylalkyl group having ₇ to ₂₀ carbon atoms, and an arylalkenyl group having ₈ to ₂₀ carbon atoms, and these substituents may be bonded to each other to form a ring, The term "ring" refers to a fused ring consisting of a C ₃ to C ₆₀ aliphatic ring, a C ₆ to C ₆₀ aromatic ring, a C ₂ to C ₆₀ hetero ring, or a combination thereof, and includes a saturated or unsaturated ring.

Specifically, the compound represented by the formula (1) may be represented by the following formula (2) or (3).

&Lt; Formula 2 > < EMI ID =

In Formula 2 and Formula 3, R ¹ to R ¹² , L ¹ to L ^3, and Het are the same as defined in Formula 1, and Het ¹ and Het ² are defined as in Formula 1.

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

In another embodiment of the present invention, the present invention provides a liquid crystal display comprising: a first electrode; A second electrode; And an organic material layer disposed between the first electrode and the second electrode, wherein the organic material layer comprises the compound represented by Formula 1. Specifically, the present invention provides an organic electrical device comprising the compound represented by Chemical Formula 2 or 3 in the organic material layer. More specifically, the present invention provides an organic electrical device comprising the compound represented by the above-mentioned individual formula in the organic material layer.

In another embodiment of the present invention, the present invention provides an organic electronic device comprising at least an electron transport layer in the organic material layer, and the electron transport layer containing the compound.

In another aspect of the present invention, there is provided a light-emitting device including a light-efficiency improvement layer formed on at least one side of the one side of the first electrode opposite to the organic material layer or one side of the one side of the second electrode opposite to the organic material layer, And an organic electroluminescent device.

In yet another embodiment of the present invention, the present invention provides an organic electroluminescent device in which the organic material layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process and a roll- do.

In another embodiment of the present invention, the present invention provides a display device comprising an organic electronic device including the organic material layer; And a control unit for driving the display device.

In yet another embodiment of the present invention, an organic electronic device according to the present invention includes at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT) It can be one.

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

Synthesis of the compound was carried out as follows.

Ⅰ. Synthesis of formula (1)

The compound represented by the formula (1) according to the present invention can be synthesized by the reaction path of the following reaction formula (1), but is not limited thereto.

<Reaction Scheme 1>

1. Synthesis of Sub 1

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

<Reaction Scheme 2>

(1) Sub 1-2 Synthesis

(1 eq.), 1,3,5-tribromobenzene (1 eq.), Pd (PPh ₃₎ ) ₄ (0.03 eq.) And K ₂ CO ₃ (3 eq.) Were dissolved in anhydrous THF and a small amount of water, and then refluxed for 24 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ , filtered, and the organic solvent was concentrated. The resulting product was separated by column chromatography to obtain 1- (3,5-dibromophenyl) -1H-indole.

(2) Sub 1-4 synthesis

1 - (3,5-dibromophenyl) -1H-indole (1 eq.) And 1- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- _{), Pd (PPh 3) 4} (0.03 eq), K ₂ CO ₃ was (3 equiv.) at reflux for I, 24 hours after dissolved in anhydrous THF and a small amount of water. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. A small amount of water was removed with anhydrous MgSO ₄ and the filtrate was concentrated under reduced pressure. The resulting product was purified by column chromatography to obtain 1,1 '- (5-bromo-1,3-phenylene) bis ).

(3) Sub 1 synthesis

After dissolving 1,1 '- (5-bromo-1,3-phenylene) bis (1H-indole) (1 eq) in a round bottom flask with DMF, Bis (pinacolato) diboron (1.1 eq.), Pd Cl ₂ (0.03 eq.), KOAc (3 eq.) Was added and stirred at 90 &lt; 0 &gt; C. When the reaction was complete, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to give 1,1 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3-phenylene) bis (1H-indole).

Meanwhile, examples of Sub 1 are as follows but are not limited thereto, and their FD / MS are shown in Table 1 below.

[Table 1]

2. Example of Sub 2

Examples of Sub 2 in the above Reaction Scheme 1 are as follows but are not limited thereto, and their FD / MS are shown in Table 2 below.

[Table 2]

3. Synthesis of Final Product of Formula 1

Sub 1 (1 eq.) Is dissolved in THF, Sub 2 (1.1 eq.), Pd (PPh ₃ ) ₄ (0.03 eq.), NaOH (3 eq.) And water are added. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain final product.

(1) Synthesis of 1-1

(1H-indole) (8.7 g, 20 mmol) was added to a solution of 1,1 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- after the was dissolved in THF, 2-bromo-4,6- diphenyl-1,3,5-triazine (7.5g, 24mmol), Pd (PPh 3) 4 (0.7g, 0.6mmol), NaOH (2.4g, 60mmol ), Water is added, and the mixture is refluxed with stirring. After completion of the reaction, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 8.0 g of the final product (yield: 74%).

(2) 1-15 Synthesis

1,1 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3-phenylene) bis (2,3- (9.8 g, 20mmol) was dissolved in a THF, 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine (9.3g, 24mmol), Pd (PPh 3) 4 (0.7g, 0.6 mmol), NaOH (2.4 g, 60 mmol) and water are added, and the mixture is refluxed with stirring. After the reaction was completed, the reaction mixture was extracted with 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 9.7 g (yield: 72%) of final product.

(3) 1-24 Synthesis

1, 1 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3-phenylene) bis (2-phenyl- g, 20 mmol) was dissolved in THF, and then 2,2 '- (5-bromo-1,3-phenylene) dipyridine (7.5 g, 24 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol) 2.4 g, 60 mmol), water was added, and the mixture was refluxed with stirring. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 10.4 g (yield: 75%) of final product.

(4) 1-30 Synthesis

(1H-indole) (8.7 g, 20 mmol) was added to a solution of 1,1 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- after the was dissolved in THF, 2-chloro-4- phenylquinazoline (5.8g, 24mmol), Pd (PPh 3) 4 (0.7g, 0.6mmol), NaOH (2.4g, 60mmol), followed by the addition of water, stirred at reflux . After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 8.0 g (yield: 78%) of final product.

(5) 1-59 Synthesis

1, 1 '- (5- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -1,3-phenylene) bis (2-phenyl- 4-yl) -2- (4-bromophenyl) quinazoline (10.5 g, 24 mmol) and Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol), NaOH (2.4 g, 60 mmol) and water, and the mixture was refluxed with stirring. After the reaction was completed, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 12.3 g (yield: 75%) of final product.

Meanwhile, the FD-MS values of the final product of Formula 1 prepared according to the above Synthesis Example are shown in Table 3 below.

[Table 3]

Evaluation of manufacturing of organic electric device

[Experimental Example] A green organic light emitting device (electron transporting layer)

First, 4,4 ', 4 "-tris [2-naphthyl (phenyl) amino] triphenylamine (hereinafter abbreviated as 2-TNATA) was vapor-deposited to a thickness of 60 nm on the ITO layer (anode) Nd-phenylamino] biphenyl (hereinafter abbreviated as NPD) was vacuum-deposited to a thickness of 60 nm on the hole injection layer to form a hole Then, 4,4'-N, N'-dicarbazole-biphenyl (hereinafter abbreviated as CBP) was used as a host and tris (2-phenylpyridine) -iridium (ppy) ₃ ) as a dopant was doped in a ratio of 95: 5 by weight to form a light emitting layer having a thickness of 30 nm. A light emitting layer was formed on the light emitting layer by using a (1,1'-biphenyl) -4- (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm to form a hole blocking layer. On the hole blocking layer, felled Then, an electron injection layer was formed by depositing LiF, which is a halogenated alkali metal, on the electron transport layer to a thickness of 0.2 nm, and then Al was deposited to a thickness of 150 nm To form a cathode. Thus, an organic electroluminescence device was prepared.

[Comparative Example]

Comparative Example (1)

An organic electronic device was prepared in the same manner as in Experimental Example except for using the following Comparative Compound 1 instead of the compound represented by Formula 1 of the present invention as the electron transport layer material.

&Lt; Comparative Compound 1 > Alq ₃

Comparative Example (2)

An organic electronic device was prepared in the same manner as in Experimental Example except that the following compound 2 was used in place of the compound represented by Formula 1 of the present invention as the electron transport layer material.

&Lt; Comparative Compound 2 >

Comparative Example (3)

An organic electronic device was prepared in the same manner as in Experimental Example except for using the following Comparative Compound 3 instead of the compound represented by Formula 1 of the present invention as the electron transport layer material.

&Lt; Comparative Compound 3 >

A forward bias DC voltage was applied to the organic electroluminescence devices manufactured by the thus produced experimental examples (Experimental Examples (1) to (59)) and Comparative Examples (Comparative Examples (1) to (3) Electroluminescence (EL) characteristics were measured with photoresearch PR-650, and T95 lifetime was measured using a lifetime measuring device manufactured by Mac Science Inc. at a luminance of 5000 cd / m 2.

[Table 4] shows the results of the fabrication of a device for the experimental examples (Experimental Examples (1) to (59)) and Comparative Examples (Comparative Examples (1) to (3)) to which the compound according to the present invention was applied, Evaluation results are shown.

[Table 4]

As can be seen from the results of the above Table 4, the organic electroluminescent device (OLED) using the compounds of the present invention is used as an electron transporting layer material and has lower driving voltage and higher efficiency than the conventional compound Alq ₃ And high lifespan. This indicates that the T1 value (2.0 eV) of Alq ₃ used as the electron transport layer is significantly lower than the T 1 value (2.4 eV) of Ir (ppy) ₃ used as a dopant in the light emitting layer, whereas in the case of the compounds of the present invention, Ir ) exhibits a generally high T1 value (2.5eV ~ 2.6eV) than the value T1 (2.4eV) of ₃ not only improves the hole-blocking ability (hole blocking ability), where the exciton (exciton) in the light emitting layer can stay well This is because the probability is relatively increased.

Next, comparing the results of the organic EL devices of the present invention with the comparative compound 2 and the comparative compound 3, it was confirmed that the compounds of the present invention exhibited remarkably improved driving voltage, efficiency and life span have. It can be explained that the compound of the present invention improves the performance of the device by better charge balance of holes and electrons in the light emitting layer than the comparative compound 2 and the comparative compound 3.

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

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

Claims (9)

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

[In the above formula (1)
R ¹ to R ¹² are independently selected from the group consisting of: i) independently of one another hydrogen; heavy hydrogen; halogen; 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 -LN (R _a ) (R _b ); or ii) R ³ to R ⁶ and R ⁹ to R ¹² are bonded to each other to form at least one ring,
n is an integer of 1 or 2,
Het is at least one of a C ₂ ~ C ₆₀ heterocyclic group containing nitrogen (but excluding indole, carbazole silver),
L ¹ to L ³ and L each independently represent a single bond; A C ₆ to C ₆₀ aryl group; A fluorene group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si and P;
R _a and R _b are each independently a C ₆ to C ₆₀ aryl group; A fluorenyl group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P;
(Wherein the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group, A boron group, a germanium group, a cyano group, a nitro group, -LN (R _a ) (R _b ); 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,
A compound represented by the following formula (2) or (3).
&Lt; Formula 2 >< EMI ID =

[In the formulas (2) and (3)
R ¹ to R ¹² , L ¹ to L ³ and Het are the same as defined in claim ^1, and Het ¹ and Het ² are defined as Het defined in claim 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,
Wherein the organic material layer comprises a compound according to any one of claims 1 to 3. 5. The method of claim 4,
Wherein the organic material layer comprises an electron transporting layer containing the compound. 5. The method of claim 4,
Further comprising a light-efficiency-improvement layer formed on at least one side of the one side of the first electrode opposite to the organic material layer or one side of the one side of the second electrode opposite to the organic material layer. 5. The method of claim 4,
Wherein the organic material layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, and a roll-to-roll process. A display device including the organic electroluminescent device of claim 4; And
And a control unit for driving the display device. 9. The method of claim 8,
Wherein the organic electronic device is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a monochromatic or white illumination device.

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