KR20140099759A - Compound for organic electronic element, organic electronic element using the same, and a electronic device thereof - Google Patents

Abstract

In the present invention, provided is a novel compound capable of improving luminance efficiency, stability, and service life of an element, an organic electronic element using the same, and an electronic device thereof. By using the compound of the present invention, high luminance efficiency, low driving voltage, and high heat resistance of the element can be achieved, and color purity and service life of the element can be greatly improved.

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 the T1 value between each organic material layer and the intrinsic properties (mobility, interface characteristics, etc.) of the materials 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 transporting 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 invention provides compounds represented by the formula:

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

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

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

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

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

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

The term " halo "or" halogen "as used herein, on the other hand, includes fluorine, chlorine, bromine, and iodine unless otherwise specified.

The term "alkyl" or "alkyl group ", as used herein, unless otherwise specified, has from 1 to 60 carbon atoms, but is not limited thereto.

The term "alkenyl" or "alkynyl ", as used herein, unless otherwise indicated, each have a double bond or triple bond of from 2 to 60 carbon atoms,

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 "alkoxy group" as used in the present invention has, unless otherwise stated, 1 to 60 carbon atoms, 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 an aromatic group having a single ring or a heterocyclic ring, and the neighboring substituent includes an aromatic ring 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 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 3 to 60 carbon atoms each containing at least one heteroatom, But includes a single ring as well as a heterocyclic ring and may be formed by bonding adjacent groups.

The term " heterocycloalkyl ", "heterocyclic group ", as used herein, unless otherwise indicated, includes one or more heteroatoms, has from 2 to 60 carbon atoms, , And neighboring groups may be combined with each other. Furthermore, the "heterocyclic group" may mean an alicyclic group and / or an aromatic group including a hetero atom.

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

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.

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 alkoxy group, C ₁ ~ C ₂₀ alkyl amine group of _20, C ₁ ~ C ₂₀ alkyl thiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ arylalkenyl group, a silane group, a boron of Means a group substituted with at least one substituent selected from the group consisting of a halogen atom, a cyano group, a germanium group, and a C ₅ to C ₂₀ heterocyclic group, and is not limited to these substituents.

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, ) Having an organic compound layer containing a compound represented by the general formula (1). 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 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 used as 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, . Preferably, the compound of the present invention may be used as 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 energy level and T1 value between each organic material layer, and the intrinsic characteristics (mobility, interfacial characteristics, etc.) of the material are optimized, long life and high efficiency can be achieved at the same time.

As described above, in order to solve the emission problem in the hole transporting layer in recent organic electroluminescent devices, it is preferable that a light emitting auxiliary layer is formed between the hole transporting layer and the light emitting layer, and the light emitting layer (R, G, B) 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 hole transporting layer or the light-emitting auxiliary layer using the compound represented by the formula (1), the energy level and T1 value between the organic layers, the mobility of the material, It is possible to simultaneously improve the lifetime and efficiency of the organic electronic device.

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 can be formed using a variety of polymer materials by a solution process other than a vapor deposition process or a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, It can be made of a number of layers. 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.

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).

In the above formulas,

X is independently of each other O, S or CR'R ", wherein R 'and R "are independently selected from the group consisting of: i) independently of one another hydrogen; A C ₁ to C ₅₀ alkyl group or a C ₆ to C ₆₀ aryl group; Or ii) they may combine with each other to form a spiro compound.

And L are independently of each other a direct bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; And a divalent aliphatic hydrocarbon group, wherein the arylene group, the fluorenylene group, the heterocyclic group and the aliphatic hydrocarbon group are selected from the group consisting of a nitro group, a cyano group, a halogen group, a C ₁ to C ₂₀ alkyl group, a C ₆ - heterocyclic group of C ₂₀ aryl group, C ₂ ~ C _20, and may be substituted with one or more substituents selected from the group consisting of an alkoxy group and an amino group of C ₁ ~ C _20.

The direct bonding means that L is absent. Here, direct defect means that L is absent. Referring to Formulas 1-1, 1-17 and 1-28 of the present invention, L is absent.

Ar ₁ , Ar ₂ and Ar ₃ are independently of each other a C ₆ to C ₆₀ aryl group; A C ₃ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; _{-N (Ar 4) (Ar 5} ); A fused ring group of an aromatic ring of C ₆ to C ₆₀ and an aliphatic ring of C ₃ to C ₆₀ ; And a fluorenyl group; and R < 2 >

Ar ₄ and Ar ₅ are each independently a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A C ₆ to C ₆₀ aryl group; An alkenyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₅₀ alkyl group; Or a fluorenyl group.

On the other hand, Ar ₁ to Ar ₅ may be further substituted with other substituents.

When the Ar ₁ to Ar ₅ aryl group, which is hydrogen, deuterium, a halogen, a silane group, a boron group, a germanium group, a cyano group, a nitro group, C ₁ ~ C ₂₀ coming of the alkylthio, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ of alkenyl groups _{(alkenyl), C 2 ~ C} 20 of the alkynyl group (alkynyl), a C ₆ substituted with an aryl group, a heavy hydrogen of C ₆ ~ C ₂₀ of - of C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ of the An arylalkyl group, and an arylalkenyl group having ₈ to ₂₀ carbon atoms,

If the Ar ₁ to Ar ₅ is a heterocyclic group, which is hydrogen, deuterium, a halogen, a silane group, a cyano group, an alkyl group of a nitro group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ of, C ₂ ~ C ₂₀ A C ₆ to C ₂₀ aryl group, a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₂ to C ₂₀ heterocyclic group, a C ₃ to C ₂₀ cycloalkyl group, a C ₇ to C ₂₀ aralkyl group, ~ C ₂₀ An arylalkyl group and an arylalkenyl group having from ₈ to ₂₀ carbon atoms.

When the Ar ₁ to Ar ₅ fluorene group in which hydrogen, an alkenyl group (alkenyl) of deuterium, a halogen, a silane group, a cyano group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ of, C ₆ ~ C can be optionally substituted with one or more substituents selected from the group consisting of _20, an aryl group, a cycloalkyl group of C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ substituted by deuterium,

When Ar ₁ and Ar ₃ are fused rings, they may be substituted with one or more substituents selected from the group consisting of deuterium, halogen, silane, boron, germanium, cyano, nitro, C ₁ to C ₂₀ alkylthio, C ₁ to C ₂₀ alkoxyl , C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ of alkenyl groups (alkenyl), C ₂ ~ C ₂₀ of the alkynyl group (alkynyl), C ₆ to C ₂₀ aryl group, a substituted C by deuterium ₆ to the for C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ of the An arylalkyl group and an arylalkenyl group having from ₈ to ₂₀ carbon atoms.

When Ar ₁ to Ar ₅ are an alkyl group, it is preferably a halogen, a silane group, a boron group, a cyano group, a C ₁ to C ₂₀ alkoxyl group, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group A C ₆ to C ₂₀ aryl group, a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₂ to C ₂₀ heterocyclic group, a C ₇ to C ₂₀ An arylalkyl group, and an arylalkenyl group having ₈ to ₂₀ carbon atoms,

When Ar ₁ to Ar ₅ are alkenyl groups, they may be replaced by hydrogen, deuterium, halogen, a silane group, a cyano group, a C ₁ to C ₂₀ alkoxyl group, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenylene group a C ₆ to C ₂₀ aryl group, a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₂ to C ₂₀ heterocyclic group, a C ₃ to C ₂₀ cycloalkyl group, a C ₇ to C ₂₀ alkenyl group, of An arylalkyl group and an arylalkenyl group having from ₈ to ₂₀ carbon atoms.

The formula (1) may be represented by one of the following formulas.

 [Chemical Formula 2] < EMI ID =

 [Chemical Formula 4]

Ar ₁ , Ar ₂ , Ar ₃ , L, R 'and R "in the general formulas (2) to (4) are the same as those in the general formula (1).

Meanwhile, the formula (1) may be represented by the following compounds.

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

Synthetic example

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

<Reaction Scheme 1>

Sub  1 of Synthetic example

Sub 1 can be synthesized by the reaction path of the following reaction formula (2).

<Reaction Scheme 2>

(One) Sub  1-2 synthesis

Sub 1-1 (1 eq.) Was dissolved in DMF in a round bottom flask followed by addition of Bis (pinacolato) diboron (1.1 eq.), Pd (dppf) Cl ₂ (0.03 eq.) And KOAc Lt; / RTI &gt; 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 Sub 1-2.

(2) Sub  One- 3 synthesis

Sub 1-2 and 1-iodo-2-nitrobenzene, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ obtained in the above synthesis were dissolved in anhydrous THF and a small amount of water, and 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 under reduced pressure, the organic solvent was concentrated, and the resulting product was separated by column chromatography to obtain the desired Sub 1-3.

(3) Sub  One- 4 Synthesis

Sub 1-3 obtained in the above synthesis under nitrogen was dissolved in a carbon disulfide solvent, and then bromine was gradually added dropwise. After stirring for 12 hours at room temperature, the organic solvent was concentrated by using a pressure reducing device and the resulting product was recrystallized using an ethanol solvent to obtain desired Sub 1-4.

(4) Sub  1-5 Synthesis

Sub 1-4 and triphenylphosphine obtained in the above synthesis were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and the concentrated product was separated by column chromatography to obtain desired Sub 1-5.

(5) Sub  1-6 synthesis

(1 eq.), Ar ₁ -Br compound (1.1 eq.), Pd ₂ (dba) ₃ (0.05 eq.) And P (t-Bu) ₃ (0.1 eq.) Obtained in the above synthesis were added to a round bottom flask. , NaO t- Bu (3 eq.) And toluene (10.5 mL / 1 mmol) were added to the reaction mixture, followed by reaction at 100 ° C. After completion of the reaction, the reaction mixture was extracted with ether and water. The organic layer was dried over MgSO ₄ and concentrated. Subsequently, the resulting organic material was subjected to silicagel column and recrystallization to obtain Sub 1-6.

(6) Sub  One- 7 synthesis

Sub 1-6 (1 eq.) Obtained in the above synthesis was dissolved in DMF in a round bottom flask followed by the addition of Bis (pinacolato) diboron (1.1 eq), Pd (dppf) Cl ₂ (0.03 eq) and KOAc And stirred at 90 [deg.] C. After completion of the reaction, DMF was removed by distillation, and the mixture was extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was subjected to silicagel column and recrystallization to obtain Sub 1-7.

(7) Sub 1 synthesis

(1.5 eq.), Pd (PPh ₃ ) ₄ (0.05 eq.), K ₂ CO ₃ (3 eq.), And the like were dissolved in THF in a round bottom flask. , Water was added and stirred at 80 ° C. After the reaction was completed, 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 Sub 1.

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

[Table 1]

Sub  2 Synthetic example

Sub 2 of Scheme 1 can be synthesized by the reaction path of Scheme 3 below.

<Reaction Scheme 3>

After the Ar ₂ (1.1 eq.) Of Br-substituted dissolved in toluene in a round bottom flask, Ar ₃ (1 eq.) With NH ₂ is _{substituted, Pd 2 (dba) 3 (} 0.3 equiv), 50% P (t - Bu) ₃ (9 eq), NaO t- Bu (3 eq) and stir at 40 ° 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 subjected to silicagel column and recrystallization to obtain Sub 2.

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

[Table 2]

The final product ( Final Product )

(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 is carried out 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 final product was obtained by silicagel column and recrystallization.

(One) Product  1-19 Synthesis

A round bottomed flask was charged with 2-bromo-14,14-dimethyl-13-phenyl-13,14-dihydrobenzo [c] indeno [2,1-a] carbazole (11.7 g, 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), and the reaction is 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 9.9 g (yield: 68%) of the product.

(2) Product  1-23 synthesis

A round bottom flask was charged with 2-bromo-13,14,14-triphenyl-13,14-dihydrobenzo [c] indeno [2,1-a] carbazole (14.7 g, -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), and the reaction is 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 10.6 g (yield: 62%) of the product.

(3) Product  1-47 Synthesis

A round bottomed flask was charged with 2- (4-bromophenyl) -14,14-dimethyl-13-phenyl-13,14-dihydrobenzo [c] indeno [2,1-a] carbazole (13.5 g, , 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 And toluene (10.5 mL / 1 mmol), followed by reaction 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 10.9 g (yield: 68%) of the product.

(4) Product  2-48 Synthesis

Benzo [c] benzofuro [2,3-a] carbazole (12.9 g, 24 mmol), N - ([1,1'-biphenyl] - 4-yl) -9,9-dimethyl- 9H-fluoren-2-amine (7.2g, 20mmol), 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) were added thereto, followed by reaction 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 10.0 g (yield: 61%) of the product.

(5) Product  2-56 synthesis

A solution of 10- (8-bromodibenzo [b, d] thiophen-2-yl) -14-phenyl-14H-benzo [c] benzofuro [2,3- a] carbazole (15.5 g, [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 equivalents) and toluene (10.5 mL / 1 mmol), followed by reaction 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 10.6 g (yield: 60%) of the product.

(6) Product  3-19 synthesis

Benzo [c] benzo [4,5] thieno [2,3-a] carbazole (11.5 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 (10.5 mL / 1 mmol), and the reaction is 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 9.3 g (yield: 65%) of the product.

(7) Product  3-47 Synthesis

A round bottom flask was charged with 10- (4-bromophenyl) -14-phenyl-14H-benzo [c] benzo [4,5] thieno [2,3- '-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 proceeds 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 10.7 g (yield: 67%) of the product.

[Table 3]

Evaluation of manufacturing of organic electric device

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

An organic electroluminescent device was fabricated according to a conventional method using a compound obtained through synthesis as a hole transport layer material.

First, N ¹ on the ITO layer (anode) formed on an organic substrate - (naphthalen-2-yl) -N 4, N 4 -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N 1 - phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) was vacuum-deposited to form a hole injection layer having a thickness of 60 nm. Then, the compound of the present invention was vacuum-deposited to a thickness of 20 nm on the hole injection layer to form a hole transport layer . Then, CBP [4,4'-N, N'-dicarbazole-biphenyl] was used as a light emitting layer host and Ir (ppy) ₃ [tris (2-phenylpyridine) -iridium was used as a dopant on the hole transport layer. And the light emitting layer was deposited to a thickness of 30 nm. (1, 1'-biphenyl) -4-oleato) bis (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as BAlq) was deposited on the hole transport layer to a thickness of 10 nm Vacuum evaporated, and an electron transport layer was formed to a thickness of 40 nm on tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ). Thereafter, LiF as an alkali metal halide was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode, thereby fabricating an organic electroluminescent device.

[ Comparative Example  One]

An organic electroluminescent device was prepared in the same manner as in Experimental Example 1, except that the following Comparative Compound 1 was used instead of the compound of the present invention in forming the hole transport layer.

&Lt; Comparative Compound 1 > NPB

[ Comparative Example  2]

An organic electroluminescent device was fabricated in the same manner as in Experimental Example 1, except that the compound of the present invention was used instead of the compound of the present invention in forming the hole transport layer.

&Lt; Comparative Compound 2 >

[ Comparative Example  3]

An organic electroluminescent device was prepared in the same manner as in Experimental Example 1, except that the following Comparative Compound 1 was used instead of the compound of the present invention in forming the hole transport layer.

&Lt; Comparative Compound 3 >

[Table 4]

As can be seen from the results of Table 4, the organic electroluminescence device using the organic electroluminescence device material of the present invention can be used as a hole transporting layer material, thereby remarkably improving the luminous efficiency, the low driving voltage and the life span.

The comparative compound 2 and the comparative compound 3 in which the heterocyclic compound is core were found to show better results than the comparative compound 1 in which the bisarylamine compound is the comparative compound 1. Comparing the comparative compound 2 and the comparative compound 3, It is confirmed that the comparative compound 3 in which the diarylamine group is substituted with 2 shows high efficiency, long life, and low driving voltage.

Comparing the results of the compound of the present invention with that of the compound of the present invention, it can be seen that N and CR'R ", N and O, N and S, which are different from each other, Compounds showed higher efficiency and it was confirmed that the compound of the present invention having a diarylamine group on one side of the comparative compound 3 in which the diarylamine group was located on both sides showed lower driving voltage and higher lifetime. When the same heteroatom is contained in one molecule, T1 (triplet) is lowered, which results in the inability to block electrons, resulting in a decrease in efficiency. When the diarylamine group is on both sides The difference of the HOMO value from the light emitting layer becomes large and the hole mobility is lowered. As a result, a high driving voltage is required, Due to the voltage it can be described as showing a low lifetime of the device.

[ Experimental Example  2] Green organic light emitting device ( The light- )

An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention obtained through synthesis as a light emitting auxiliary layer material.

First, a 2-TNATA film was vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 60 nm, and then a hole transport layer was formed by vacuum depositing NPD on the hole injection layer to a thickness of 20 nm . Thereafter, the compound of the present invention was vacuum-deposited on the hole transporting layer to a thickness of 20 nm to form a light emitting auxiliary layer. Ir (ppy) ₃ [tris (2-phenylpyridine) -iridium] was used as a host material and CBP [4,4'-N, N'-dicarbazole-biphenyl] And doped with 95: 5 by weight as a dopant material to deposit a 30 nm thick light emitting layer. Subsequently, BAlq was vacuum-deposited on the light emitting layer to a thickness of 10 nm to form a hole blocking layer, and Alq ₃ was formed to a thickness of 40 nm to form an electron transporting layer. Thereafter, LiF as an alkali metal halide was deposited to a thickness of 0.2 nm to form an electron injecting layer, and Al was deposited to a thickness of 150 nm to form a cathode, thereby preparing an organic electroluminescent device.

[Comparative Example 4]

An organic electroluminescent device was fabricated in the same manner as in Experimental Example 2, except that the luminescent auxiliary layer was not formed.

[Comparative Example 5]

An organic electroluminescent device was fabricated in the same manner as in Experimental Example 2, except that the compound of the present invention was used as the luminescent auxiliary layer material.

[Comparative Example 6]

An organic electroluminescent device was fabricated in the same manner as in Experimental Example 2, except that the compound of the present invention was used as the luminescent auxiliary layer material.

[Table 5]

As can be seen from the results of Table 5, when the compound of the present invention is used as the light-emitting auxiliary layer material as compared with the case where the light-emitting layer is not used, the comparative compound 2 and the comparative compound 3 are used as the light- The driving voltage of the organic EL device can be further lowered, and the luminous efficiency and lifetime can be remarkably improved. This can be explained as having a high T1 energy level when the compound of the present invention is used alone as a light-emitting auxiliary layer, and improving the low voltage, high luminous efficiency and device lifetime of an organic electroluminescent device due to a deep HOMO energy level.

It is obvious that similar effects can be obtained when the compounds of the present invention are used in other organic layers of an organic electroluminescent device, for example, a hole injection layer, an electron injection layer, an electron transport 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 (9)

A compound represented by the formula:
[Chemical Formula 1]

In the above formulas,
Wherein X is O, S or CR'R &quot;, wherein R 'and R "are independently of each other a C ₆ to C ₆₀ aryl group, a fluorenyl group, at least one heteroatom selected from O, N, S, , A C ₂ to C ₆₀ heterocyclic group, a C ₁ to C ₅₀ alkyl group and -LN (Ar ₁ ) (Ar ₂ )
L are, independently of one another, a direct bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; And a divalent aliphatic hydrocarbon group, wherein the arylene group, the fluorenylene group, the heterocyclic group and the aliphatic hydrocarbon group are selected from the group consisting of a nitro group, a cyano group, a halogen group, a C ₁ to C ₂₀ alkyl group, a C ₆ ~ C ₂₀ aryl group, may be substituted with one or more substituents selected from the group consisting of an alkoxy group and an amino group of C ₂ ~ a heterocyclic group of _{C 20, C 1 ~ C 20} ) , the
Ar ₁ , Ar ₂ and Ar ₃ are, independently of each other, a C ₆ to C ₆₀ aryl group; A C ₃ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; _{-N (Ar 4) (Ar 5} ); A fused ring group of an aromatic ring of C ₆ to C ₆₀ and an aliphatic ring of C ₃ to C ₆₀ ; And a fluorenyl group; and R &lt; 2 &gt;
Ar ₄ and Ar ₅ are each independently a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si and P; A C ₆ to C ₆₀ aryl group; An alkenyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₅₀ alkyl group; Or a fluorenyl group.
(If the Ar ₁ to Ar ₅ aryl group, which is hydrogen, deuterium, a halogen, a silane group, a boron group, a germanium group, a cyano group, a nitro group, C ₁ ~ C ₂₀ coming of the alkylthio, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ of alkenyl groups _{(alkenyl), C 2 ~ C} 20 of the alkynyl group (alkynyl), a C ₆ substituted with an aryl group, a heavy hydrogen of C ₆ ~ C ₂₀ of - of C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ of the An arylalkyl group, and an arylalkenyl group having ₈ to ₂₀ carbon atoms,
When Ar ₁ to Ar ₅ are heterocyclic groups, they may be substituted with a substituent selected from the group consisting of hydrogen, deuterium, halogen, silane, cyano, nitro, C ₁ to C ₂₀ alkoxyl, C ₁ to C ₂₀ alkyl, C ₂ to C ₂₀ alkenyl group _{(alkenyl), C 6 ~ C} 20 aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a heterocyclic group of C ₂ ~ C _20, a cycloalkyl group of _{C 3 ~ C 20, C 7} ~ C ₂₀ An arylalkyl group, and an arylalkenyl group having ₈ to ₂₀ carbon atoms,
When the Ar ₁ to Ar ₅ fluorene group in which hydrogen, an alkenyl group (alkenyl) of deuterium, a halogen, a silane group, a cyano group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ of, C ₆ ~ C can be optionally substituted with one or more substituents selected from the group consisting of _20, an aryl group, a cycloalkyl group of C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ substituted by deuterium,
When Ar ₁ and Ar ₃ are fused rings, they may be substituted with one or more substituents selected from the group consisting of deuterium, halogen, silane, boron, germanium, cyano, nitro, C ₁ to C ₂₀ alkylthio, C ₁ to C ₂₀ alkoxyl , C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ of alkenyl groups (alkenyl), C ₂ ~ C ₂₀ of the alkynyl group (alkynyl), C ₆ to C ₂₀ aryl group, a substituted C by deuterium ₆ to the for C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ of the An arylalkyl group, and an arylalkenyl group having ₈ to ₂₀ carbon atoms,
When Ar ₁ to Ar ₅ are an alkyl group, it is preferably a halogen, a silane group, a boron group, a cyano group, a C ₁ to C ₂₀ alkoxyl group, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group A C ₆ to C ₂₀ aryl group, a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₂ to C ₂₀ heterocyclic group, a C ₇ to C ₂₀ An arylalkyl group, and an arylalkenyl group having ₈ to ₂₀ carbon atoms,
When Ar ₁ to Ar ₅ are alkenyl groups, they may be replaced by hydrogen, deuterium, halogen, a silane group, a cyano group, a C ₁ to C ₂₀ alkoxyl group, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenylene group alkenyl, C ₆ -C ₂₀ aryl, C ₆ -C ₂₀ aryl, C ₂ -C ₂₀ heterocycle, C ₃ -C ₂₀ cycloalkyl, C ₇ -C ₂₀ An arylalkyl group and an arylalkenyl group having ₈ to ₂₀ carbon atoms) The method according to claim 1,
Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;
[Chemical Formula 2] &lt; EMI ID =

[Chemical Formula 4]

(Wherein Ar ₁ , Ar ₂ , Ar ₃ , L, R 'and R "are the same as defined in the above formula (1) The method according to claim 1,
Lt; / RTI &gt; is one of the following compounds.

An organic electroluminescent 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 contains the compound of any one of claims 1 to 3. 5. The method of claim 4,
Wherein said compound is formed into said organic material layer by a soluble process. 5. The method of claim 4,
Wherein the organic material layer comprises at least one of a light emitting layer, a hole injecting layer, a hole transporting layer, an electron injecting layer, an electron transporting layer, and a light emitting auxiliary layer. The method according to claim 6,
Wherein the hole transporting layer or the light emitting auxiliary layer is formed of the compound. A display device including the organic electroluminescent device of claim 4; And
A controller for driving the display device; &Lt; / RTI &gt; 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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