KR20150011904A - 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 which can improve light emitting efficiency, stability, and life of an element, an organic electronic element using the same, and an electronic device thereof. The organic electronic element of the present invention comprises: a first electrode; a second electrode; and an organic matter layer located between the first electrode and the second electrode, wherein the organic matter layer consists of a light emitting auxiliary layer and a hole transport layer containing the compound of the present invention.

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 most problematic aspects of organic electroluminescent devices are their lifetime and efficiency. As the display becomes larger, 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 drops and the driving voltage drops. As a result, 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 between each organic material layer and the intrinsic properties (mobility, interface characteristics, etc.) of the material are achieved, long life and high efficiency can be achieved at the same time.

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

Generally, electrons are transferred from the electron transport layer to the light emitting layer, and holes are transferred from the hole transport layer to the light emitting layer to generate excitons by recombination.

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

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

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

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

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

In one aspect, the present invention provides a compound represented by the following formula (1).

(1)

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 indicated, the term "saturated or unsaturated ring" as used herein refers to a saturated or unsaturated aliphatic ring or an aromatic ring or hetero ring having 6 to 60 carbon atoms.

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

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

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

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

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

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

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

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

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

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

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

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

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

Accordingly, in the present invention, by forming the light emitting layer or the light emitting auxiliary layer by using the compound represented by the formula (1), the energy level and the T1 value between each organic layer, the mobility of the material, The lifetime and the efficiency of the organic electronic device 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).

(1)

In the above formula (1)

X is O or S,

R ¹ and R ² are independently of each other a C ₁ to C ₅₀ alkyl group; A C ₆ to C ₆₀ aryl group; 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, or R ² and R ² are bonded to each other to form a carbon and / Together they can form compounds with spy,

R ³ to R ⁵ independently from each other are 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 L ^a -N (R _a ) (R _b ), wherein L ^a is a single bond, a C ₆ -C ₆₀ arylene group, a fluorenylene group, a C ₃ -C ₆₀ divalent fused ring of an aromatic ring of an aliphatic ring and a C ₆ ~ C _60; a; and O, N, S, Si and P, at least one hetero atom 2 of C ₂ ~ C ₆₀ heterocyclic ring containing a group R _a and R _b are independently selected from the group consisting of a C ₆ to C ₆₀ aryl group, a fluorenyl group, a fused ring group of a C ₃ to C ₆₀ aliphatic ring and a C ₆ to C ₆₀ aromatic ring group 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; or R ³ and R ⁴ are bonded to each other to form a Together with the carbon to form an aromatic ring,

L is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A divalent fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; May be selected from the group consisting of; and O, N, S, a divalent C ₂ ~ C ₆₀ containing at least one hetero atom of Si and P heterocyclic group

Ar ¹ and Ar ² are each independently 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 b -N (R c) (}} R d); selected from the group consisting of or (wherein L ^b, R _c and R _d are as defined in the L ^a, R _a and R _b, respectively), Or Ar < ^{1 >} and Ar < ^{2 >} may bond to each other to form a ring,

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; -L ^c -N (R _e ) (R _f ) wherein L ^c , R _e and R _f are each as defined above for L ^a , R _a and 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. These substituents may be further bonded to each other to form a ring.

In another embodiment of the present invention, the compound represented by the formula (1) may be any one represented by the following formulas (2) to (5).

Formula (2)

Formula (4)

In the formulas (2) to (5), R ¹ to R ⁵ , Ar ¹ , Ar ² and L are the same as defined for R ¹ to R ⁵ , Ar ¹ , Ar ² and L in the above formula (1) Do.

In another embodiment of the present invention, the compound represented by the formula (1) may be any one represented by the following formula.

In another embodiment of the present invention, there is provided a method of fabricating a semiconductor device, 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 the formula (1).

In another embodiment of the present invention, a light-efficiency-improvement layer is 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 Thereby providing an organic electric device.

In another embodiment of the present invention, 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 do.

In another embodiment of the present invention, the organic layer includes a light-emission-assisting layer, and the light-emission-assisting layer comprises the compound.

In another embodiment of the present invention, the organic material layer includes a hole transporting layer, and the hole transporting layer comprises the compound.

In another embodiment of the present invention, an organic electronic device according to the present invention comprises 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 represented by the formula (1); And a control unit for driving the display device.

In 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 example of the organic electric device will be specifically described with reference to examples, but the present invention is not limited to the following examples.

Synthetic example

Illustratively, the compound according to the present invention is prepared by reacting Sub 1 and Sub 2 in the following Reaction Scheme 1, but is not limited thereto.

<Reaction Scheme 1>

Ⅰ. Sub  1 Synthetic Example

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

<Reaction Scheme 2>

Sub  1-2 synthesis

thiophen-2-ylboronic acid (1 eq.) was dissolved in toluene in a round bottom flask and ethyl 2-bromothiophene-3-carboxylate (1 eq.) was added and stirred. When the reaction was complete, the toluene 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 obtain ethyl [2,2'-bithiophene] -3-carboxylate (yield: 79%).

Sub  1-3 synthesis

ethyl [2,2'-bithiophene] -3-carboxylate (1 eq.) was dissolved in THF in a round bottom flask, then bromobenzene (2 eq.) was added and stirred. When the reaction was complete, the THF 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 obtain [2,2'-bithiophen] -3-yldiphenylmethanol (yield: 75%).

Sub  1-4 Synthesis

[2,2'-bithiophen] -3-yldiphenylmethanol (1 eq.) Was added to a round bottom flask with H ₂ SO ₄ , Acetic acid, Octane and stirred. When the reaction was complete, the solvent was removed via 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 obtain 4,4-diphenyl-4H-cyclopenta [1,2-b: 5,4-b '] dithiophene (yield: 81% ).

Sub  1 (A) Synthesis

(1 equivalent) of 4,4-diphenyl-4H-cyclopenta [1,2-b: 5,4-b '] dithiophene obtained in the above synthesis was dissolved in methylene chloride, and NBS (N-bromosuccimide) And the mixture was stirred at room temperature for 24 hours. At the end of the reaction, 5% strength HCl was added and water was added to remove residual NBS. The 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 2-bromo-4,4-diphenyl-4H-cyclopenta [ b '] dithiophene (yield: 84%).

Sub  1-5 Synthesis

After dissolving 2-bromo-4,4-diphenyl-4H-cyclopenta [1,2-b: 5,4-b '] dithiophene (1 eq) in DMF in a round bottom flask, bis (pinacolato) diboron ), Pd (dppf) Cl ₂ (0.03 eq.) And KOAc (3 eq.) Were added and stirred at 90 ° 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 obtain 2- (4,4-diphenyl-4H-cyclopenta [1,2-b: 5,4-b '] dithiophen-2-yl ) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (yield: 86%).

Sub 1 (B) Synthesis

2- (4,4-diphenyl-4H-cyclopenta [1,2-b: 5,4-b] dithiophen-2-yl) -4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1 equivalent), 1-bromo-4-iodobenzene (1 equivalent), 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, Lt; / RTI &gt; 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 under reduced pressure, and the organic solvent was concentrated. The resulting product was separated by column chromatography to obtain the desired 2- (4-bromophenyl) -4,4-diphenyl-4H-cyclopenta [ 2-b: 5,4-b '] dithiophene (yield: 83%).

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

[Table 1]

Ⅱ. Sub  2 Synthetic Example

Sub 2 in the above Reaction Scheme 1 may be synthesized by the reaction path of Reaction Scheme 3 below, but is not limited thereto.

<Reaction Scheme 3>

bromobenzene (1.1 equiv.) was dissolved in toluene in a round bottom flask, 4-aminobenzene-1-ylium (1 _{eq), Pd 2 (dba) 3} (0.3 equiv), 50% P (t -Bu ) 3 (9 eq. ) And NaO t- Bu (3 eq.) Were added and stirred at 40 &lt; 0 &gt; C. After completion of the reaction, the reaction mixture was 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 obtain diphenylamine (yield: 96%).

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

[Table 2]

Ⅲ. The final product ( Product ) Synthesis of

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

1. Synthesis of 1-5

<Reaction Scheme 4>

4-diphenyl-4H-cyclopenta [1,2-b: 5,4-b '] dithiophene (9.8 g, 24 mmol), di ([1,1'- biphenyl] - 4-yl) amine (6.4g, 20mmol), Pd 2 (dba) 3 (0.03 ~ 0.05 mmol), P (t-Bu) 3 (0.1 equiv), NaO t -Bu (3 eq.), toluene (10.5mL / 1 mmol), and the reaction was allowed to proceed at 100 占 폚. 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 10.9 g (yield: 84%) of the product.

2. Synthesis of 1-43

<Reaction Scheme 5>

4-diphenyl-4H-cyclopenta [1,2-b: 5,4-b '] dithiophene (11.7 g, 24 mmol), di ([ -biphenyl] -4-yl) amine ( 6.4g, 20mmol), Pd 2 (dba) 3 (0.03 ~ 0.05 mmol), P (t-Bu) 3 (0.1 equiv), NaO t -Bu (3 eq.), toluene (10.5 mL / 1 mmol) was added thereto, and the reaction was allowed to proceed at 100 ° C. 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 12.5 g (yield: 86%) of the product.

3. Synthetic examples of 2-5

<Reaction Scheme 6>

4-diphenyl-4H-thieno [3 ', 2': 4,5] cyclopenta [1,2-b] benzothiophene (11.0 g, 24 mmol), di '-biphenyl] -4-yl) amine (6.4g, 20mmol), Pd 2 (dba) 3 (0.03 ~ 0.05 mmol), P (t-Bu) 3 (0.1 equiv), NaO t -Bu (3 equivalents) , toluene (10.5 mL / 1 mmol), and the reaction was allowed to proceed at 100 ° C. 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 10.9 g (yield: 78%).

4. Synthetic examples of 2-46

<Reaction Scheme 7>

4'-diphenyl-4H-thieno [3 ', 2': 4,5] cyclopenta [1,2-b] benzofuran (12.5 g, 24 mmol), N- 2-amine (7.0 g, 20 mmol), Pd ₂ (dba) ₃ (0.03-0.05 mmol), P (t-Bu ) ₃ (0.1 eq.), NaO t- Bu (3 eq.) And toluene (10.5 mL / 1 mmol). 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 11.2 g (yield: 71%) of the product.

Meanwhile, the FD-MS values of the compounds 1-1 to 2-56 of the present invention prepared according to the above Synthesis Examples are shown in Table 3 below.

[Table 3]

Evaluation of manufacturing of organic electric device

[ Experimental Example  I] Red Organic Light Emitting Device ( The light- )

ITO layer (anode) formed on the glass substrate over the N ¹ - (naphthalen-2-yl) -N 4, N 4 -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N 1 -phenylbenzene- 1,4-diamine (hereinafter abbreviated as 2-TNATA) was vacuum-deposited to a thickness of 60 nm to form a hole injection layer. Then, 4,4-bis [N- (1-naphthyl) -N -Phenylamino] biphenyl (hereinafter abbreviated as NPD) was vacuum-deposited to a thickness of 60 nm to form a hole transporting layer. Subsequently, a compound of the present invention (one of 1-1 to 2-56) was vacuum deposited on the hole transport layer to a thickness of 20 nm as a light emitting auxiliary layer material to form a light emitting auxiliary layer. Then, CBP [4,4'-N, N'-dicarbazole-biphenyl] as a host material and (piq) ₂ Ir (acac) [bis- (1-phenylisoquinolyl) iridium III) acetylacetonate] was doped at a weight ratio of 95: 5 to deposit 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 on the light emitting layer to a thickness of 10 nm, Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) was formed on the hole blocking layer to a thickness of 40 nm to form an electron transport layer. Then, LiF, an alkali metal halide, was deposited on the electron transport layer to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode. Thus, an organic electroluminescent device was manufactured.

The organic electronic devices prepared in accordance with Experimental Example I are shown in Table 4 as Experimental Examples (1) to (112).

[ Comparative Example  I]

An organic electroluminescent device was fabricated in the same manner as in [Experiment I] except that the luminescent auxiliary layer was not used.

The organic electronic device manufactured according to Comparative Example I is shown in Table 4 as Comparative Example (1).

[ Comparative Example  II]

An organic EL device was prepared in the same manner as in [Experimental Example I], except that the following compounds (A) to (D) were used as the material of the luminescent auxiliary layer.

The organic electronic devices manufactured according to [Comparative Example II] are shown in Table 4 below as Comparative Examples (2) to (5).

[Comparative Example I] (Comparative Example (1)) and [Comparative Example II] (Comparative Example (2) to Comparative Example (1) (5)), electroluminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescence devices by a scanning electron microscope Lt; RTI ID = 0.0 &gt; T95 &lt; / RTI &gt;

The results are shown in Table 4. The results are shown in Table 4. The results are shown in Table 4. The results are shown in Table 4. The results are shown in Table 4 below. (Comparative Examples (2) to (5)).

[Table 4]

As can be seen from the results of Table 4, when a red organic electroluminescent device was manufactured using the organic electroluminescent device material of the present invention as a light emitting auxiliary layer material, Comparative Example I wherein no light emitting auxiliary layer was used, And the compound (A) to the compound (D) were used as the light emitting auxiliary layer, the driving voltage of the organic electroluminescent device could be lowered and the luminous efficiency and lifetime could be remarkably improved.

When the compound of the present invention is used alone as a luminescent auxiliary layer, it has a high T1 energy level and a deep HOMO energy level, and thus the hole and electron have a charge balance and emit light in the light- Which maximizes efficiency and life span.

[ Experimental Example  II] green organic light emitting device ( Hole transport layer )

2-TNATA was vacuum-deposited on the ITO layer (anode) formed on the organic substrate to a thickness of 60 nm to form a hole injection layer. Then, the compound of the present invention was vacuum deposited on the hole injection layer to a thickness of 60 nm to form a hole transport layer. Subsequently, CBP [4,4'-N, N'-dicarbazole-biphenyl] as a host material and Ir (ppy) ₃ [tris (2-phenylpyridine) -iridium as a dopant material) And a 30 nm thick light emitting layer was deposited by doping. Subsequently, the vacuum to the BAlq to 10nm thickness deposited on the EML to form a hole blocking layer, Alq ₃ was deposited on the hole blocking layer as an electron transport layer 40nm thick. Thereafter, LiF, an alkali metal halide, was deposited on the electron transport layer to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode. Thus, an organic electroluminescent device was manufactured.

The organic electronic devices manufactured in accordance with [Experimental Example II] are shown in [Table 5] as Experimental Examples (113) to (119).

[ Comparative Example  III]

An organic electroluminescent device was fabricated in the same manner as in [Experimental Example II] except that the compounds (A) to (D) were used as the hole transport layer.

The organic electronic devices manufactured according to [Comparative Example III] are shown in Table 5 below as Comparative Examples (6) to (9).

The organic electroluminescent devices according to the thus-produced [Experimental Example II] (Experimental Examples (113) to (119)) and [Comparative Example III] (Comparative Examples (6) to The electroluminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a bias DC voltage, and the T95 lifetime was measured using a lifetime measuring device manufactured by Mac Science Inc. at a luminance of 5000 cd / m 2 .

The results are shown in Table 4 below. [Table 4] shows the results of Experimental Example II (Experimental Examples 113 to 119) and Comparative Examples III (Comparative Examples 6 to 9) to which the compounds according to the present invention were applied. And the result of the evaluation.

[Table 5]

As can be seen from the results of the above Table 5, when a green organic electroluminescent device is manufactured by using the material for an organic electroluminescent device of the present invention as a material for a hole transport layer, the hulls (A) to (D) It can be seen that the luminous efficiency of the organic electroluminescent device can be increased, the driving voltage can be unknown, and the lifetime can be remarkably improved, compared with [Comparative Example III] used in the transport layer.

This is because the compound of the present invention has a proper HOMO and LUMO value, maintains a good charge balance with neighboring layers, increases the mobility of holes, lowers the driving voltage, and improves the lifetime of the device .

It is obvious that the same effects can be obtained even when the compounds of the present invention are used in other organic layers of an organic electroluminescent device, for example, a hole injecting layer, an electron injecting layer, and an electron transporting layer.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention is not limited by these embodiments.

The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of the same should be construed as being included in the scope of the present invention.

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

Claims (10)

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

[In the above formula (1)
X is O or S,
R ¹ and R ² are independently of each other a C ₁ to C ₅₀ alkyl group; A C ₆ to C ₆₀ aryl group; 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, or R ² and R ² are bonded to each other to form a carbon and / Together they can form compounds with spy,
R ³ to R ⁵ independently from each other are 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 L ^a -N (R _a ) (R _b ), wherein L ^a is a single bond, a C ₆ to C ₆₀ arylene group, a fluorenylene group, a C ₃ to C ₆₀ divalent fused ring of an aromatic ring of an aliphatic ring and a C ₆ ~ C _60; a; and O, N, S, Si and P, at least one hetero atom 2 of C ₂ ~ C ₆₀ heterocyclic ring containing a group R _a and R _b are independently selected from the group consisting of a C ₆ to C ₆₀ aryl group, a fluorenyl group, a fused ring group of a C ₃ to C ₆₀ aliphatic ring and a C ₆ to C ₆₀ aromatic ring group 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; or R ³ and R ⁴ are bonded to each other to form a Together with the carbon to form an aromatic ring,
L is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A divalent fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; May be selected from the group consisting of; and O, N, S, a divalent C ₂ ~ C ₆₀ containing at least one hetero atom of Si and P heterocyclic group
Ar ¹ and Ar ² are each independently 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 b -N (R c) (}} R d); selected from the group consisting of or (wherein L ^b, R _c and R _d are as defined in the L ^a, R _a and R _b, respectively), Or Ar &lt; ^{1 &gt;} and Ar &lt; ^{2 &gt;} may bond to each other to form a ring,
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; -L ^c -N (R _e ) (R _f ) wherein L ^c , R _e and R _f are each as defined above for L ^a , R _a and 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 and an arylalkenyl group having ₈ to ₂₀ carbon atoms, and these substituents may also be bonded to each other to form a ring] The method according to claim 1,
The compound represented by the above formula (1) is any one of the following formulas (2) to (5).
Formula (2)

Formula (4)

[In the above formulas (2) to (5)
R ¹ to R ^5, Ar ^1, Ar ² and L are the same as R ¹ to R ^5, Ar ^1, Ar ² and the definition of L in the formula (1), respectively; The method according to claim 1,
The compound represented by the formula (1) is any one represented by the following formula.

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 contains the compound according to any one of claims 1 to 3. 5. The method of claim 4,
And an optical efficiency improving 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. 5. The method of claim 4,
Wherein the organic layer includes a light-emission-assisting layer, and the light-emission-assisting layer comprises the compound. 5. The method of claim 4,
Wherein the organic material layer comprises a hole transporting layer, and the hole transporting layer comprises the compound. A display device including the organic electroluminescent device of claim 4; And
And a control unit for driving the display device. 10. The method of claim 9,
Wherein the organic 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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