KR101503734B1 - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

Provided in the present invention are a novel compound which can improve light emitting efficiency, stability, and life, an organic electronic element using the same, and an electronic device thereof. The organic electronic element is characterized by comprising a first electrode; a second electrode; and an organic substance layer located between the first electrode and the second electrode, wherein the compound is contained in the organic substance layer. The organic electronic element is characterized by having the compound contained in at least one layer among a hole injection layer, a hole transfer layer, an light emitting auxiliary layer, or a light emitting layer of an organic substance layer.

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.

Currently, the portable display market is increasing in size as a large-area display, which requires more power than the power consumption required by existing portable displays. Therefore, power consumption becomes a very important factor for portable displays, which have a limited power source, such as a battery, and efficiency and lifetime issues must be solved.

The efficiency, lifetime, and driving voltage are related to each other. As the efficiency increases, the driving voltage decreases. As the driving voltage decreases, the crystallization of the organic material due to Joule heating, which occurs during driving, Indicating a tendency for the lifetime to increase. However, simply improving the organic material layer can not maximize the efficiency. This is because, when the optimal combination of the energy level and T1 value 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, development of new materials is continuously required, and development of materials for the light emission-assisting layer and the hole transporting layer is urgently required.

BACKGROUND ART [0002] Techniques that serve as the background of the present invention are disclosed in the following publications.

U.S. Patent Publication No. 6,242,115 (June 5, 2001) Japanese Patent Application Laid-Open No. 2000-302756 (October 31, 2000)

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

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

As used in this specification and the appended claims, unless stated otherwise, the following terms have the following meanings:

The term " halo "or" halogen ", as used herein, unless otherwise indicated, is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I).

As used herein, the term "alkyl" or "alkyl group " refers to a straight or branched Quot; means a radical of a saturated aliphatic group, including an alkyl group, a cycloalkyl-substituted alkyl group.

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

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

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

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

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

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

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

The terms "aryl group" and "arylene group ", as used herein, unless otherwise specified, each have 6 to 60 carbon atoms, but are not limited thereto. In the present invention, an aryl group or an arylene group means a single ring or a multicyclic aromatic group, and neighboring substituents include aromatic rings formed by bonding or participating in the reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a spirobifluorene group.

The prefix "aryl" or "ar" means a radical substituted with an aryl group. For example, the arylalkyl group is an alkyl group substituted with an aryl group, the arylalkenyl group is an alkenyl group substituted with an aryl group, and the radical substituted with an aryl group has the carbon number described in the present specification.

Also, if prefixes are named consecutively, it means that the substituents are listed in the order listed first. For example, the arylalkoxy group means an alkoxy group substituted with an aryl group, the alkoxycarbonyl group means a carbonyl group substituted with an alkoxyl group, and in the case of an arylcarbonylalkenyl group, an alkenyl group substituted with an arylcarbonyl group means Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

The term "heteroalkyl ", as used herein, unless otherwise indicated, means an alkyl comprising one or more heteroatoms. The term "heteroaryl group" or "heteroarylene group" as used in the present invention means an aryl or arylene group having 2 to 60 carbon atoms each containing at least one heteroatom unless otherwise specified, And includes at least one of a single ring and a multi-ring, and neighboring functional devices may be formed in combination.

The term "heterocyclic group ", as used herein, unless otherwise indicated, includes one or more heteroatoms, has from 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings and includes a heteroaliphatic ring and hetero Aromatic rings. Adjacent functional groups may be combined and formed.

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

The "heterocyclic group" may also include a ring containing SO ₂ in place of the carbon forming the ring. For example, the "heterocyclic group" includes the following compounds.

Unless otherwise stated, the term "aliphatic" as used herein means an aliphatic hydrocarbon having 1 to 60 carbon atoms and an "aliphatic ring" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise specified, the term "ring" as used herein refers to a fused ring consisting of an aliphatic ring of 3 to 60 carbon atoms or an aromatic ring of 6 to 60 carbon atoms or a heterocycle of 2 to 60 carbon atoms, or combinations thereof, Saturated or unsaturated ring.

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

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

Unless otherwise indicated, the term "ether" used in the present invention refers to -RO-R 'wherein R or R' are each independently of the other hydrogen, an alkyl group 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 using the compound represented by the general formula (1), the energy level and T1 value between each organic material layer, the mobility of the material, It is possible to simultaneously improve the lifetime and efficiency of the electric element.

The organic electroluminescent device according to an embodiment of the present invention can be manufactured using a physical vapor deposition (PVD) method. For example, the anode 120 is formed by depositing a metal or a conductive metal oxide or an alloy thereof on a substrate, and a hole injecting layer 130, a hole transporting layer 140, a light emitting layer 150, and an electron transporting layer 160 and an electron injection layer 170, and then depositing a material usable as the cathode 180 on the organic layer.

In addition, the organic material layer may be formed using a variety of polymer materials, not a vapor deposition method, or a solution process or a solvent process such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, It is possible to produce a smaller number of layers by a method such as a dipping process, a screen printing process, or a thermal transfer process. Since the organic material layer according to the present invention can be formed by various methods, the scope of the present invention is not limited by the forming method.

The organic electroluminescent device according to the present invention may be of a top emission type, a back emission type, or a both-sided emission type, depending on the material used.

WOLED (White Organic Light Emitting Device) has advantages of high resolution realization and fairness, and can be manufactured using existing color filter technology of LCD. Various structures for a white organic light emitting device mainly used as a backlight device have been proposed and patented. Typically, a stacking method in which R (Red), G (Green) and B (Blue) light emitting parts are arranged side by side, and R, G and B light emitting layers are stacked up and down , And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light from the electroluminescent material. Can be applied to such WOLED.

The organic electroluminescent device according to the present invention may be one of an organic electroluminescent (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a monochromatic or white illumination device.

Another embodiment of the present invention can include an electronic device including a display device including the above-described organic electronic device of the present invention and a control unit for controlling the display device. The electronic device may be a current or future wired or wireless communication terminal and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

Hereinafter, the compound according to one aspect of the present invention will be described.

A compound according to one aspect of the present invention is represented by the following formula (1).

      ≪ Formula 1 >

In Formula 1,

Ar ¹ to Ar ³ independently represent 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 Ar ¹ and Ar ² are independently selected from the group consisting of phenyl, biphenyl, naphthyl, 9,9- Dimethyl-fluorene, 9,9-diphenyl-fluorene, spirofluorene, pyridine, pyrimidine, carbazole or dibenzothiophene.

In addition, Ar ¹ and Ar ² may combine with each other to form a ring. Specifically, Ar < ^{1 >} and Ar < ^{2 >} may combine to form a carbazole together with N bonded thereto.

a, c and d are each an integer of 0 to 4, and b is an integer of 0 to 3.

R ¹ to R ⁴ independently of one another 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'-N (R ') (R "). In particular, R ¹ to R ⁴ independently of each other may be hydrogen or phenyl.

Further, adjacent groups of R ¹ to R ⁴ may combine with each other to form at least one ring. Here, R ¹ to R ⁴ which do not form a ring are the same as defined above, respectively.

For example, when a and b are both 2, adjacent R ^{1 s} may combine with each other to form a ring, and R ² may be an aryl group or a heterocyclic group independently of each other even when adjacent to each other.

Of course, when a is an integer of 2 or more, a plurality of R ^{1 s} may be the same or different from each other, and a group in which some of the neighboring groups are bonded to each other to form a ring and not form a remaining ring is selected from the above-defined substituent group . The same applies when b, c, and d are two or more integers.

The ring formed by the adjacent groups may be a C ₃ to C ₆₀ aliphatic ring or a C ₆ to C ₆₀ aromatic ring, a C ₂ to C ₆₀ hetero ring, a C ₃ to C ₆₀ alicyclic ring, And may be a single ring or multiple rings as well as a saturated or unsaturated ring.

L ¹ , L ² and L 'are independently a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; Specifically, L ¹ , L ² and L 'may independently be a single bond, phenyl, biphenyl, fluorene, pyrimidine or dibenzothiophene.

Wherein R 'and R "are independently selected from C ₆ ~ aryl group of C ₆₀ to each other; fluorene group; C ₃ ~ fused ring group of an aromatic ring of C ₆₀ of aliphatic rings and C ₆ ~ C _60; and O, N, A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from S, Si and P;

The aryl group, the fluorenyl group, the heterocyclic group, the fused ring group, the alkyl group, the alkenyl group, the alkynyl group, the alkoxyl group, the aryloxyl group, the arylene group and the fluorenylene group may be respectively substituted with deuterium; halogen; A silane group; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ to C ₂₀ ; A C ₁ to C ₂₀ alkoxyl group; An alkyl group having ₁ to ₂₀ carbon atoms; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; C ₆ -C ₂₀ An aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A heterocyclic group of C ₂ ~ C _20; A C ₃ to C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ to C ₂₀ ; And an arylalkenyl group having from ₈ to ₂₀ carbon atoms.

Here, the aryl group may be an aryl group having 6 to 60 carbon atoms, preferably 6 to 30 carbon atoms, and more preferably 6 to 20 carbon atoms,

The heterocyclic group may be a heterocycle having 2 to 60 carbon atoms, preferably 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms,

The arylene group may be an arylene group having 6 to 60 carbon atoms, preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms,

In the case of the alkyl group, the alkyl group may have 1 to 50 carbon atoms, preferably 1 to 30 carbon atoms, more preferably 1 to 20 carbon atoms, and particularly preferably 1 to 10 carbon atoms.

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

      &Lt; Formula 2 > < EMI ID =

       &Lt; Formula 4 > < EMI ID =

In the above Chemical Formulas 2 to 5, Ar ¹ to Ar ³ , R ¹ to R ⁴ , L ¹ , L ² , a, b, c and d may be defined as defined in Chemical Formula 1.

More specifically, the compounds represented by Chemical Formulas 1 to 5 may be any one of the following compounds.

In another embodiment, the present invention provides a compound for an organic electroluminescent device represented by the general formula (1).

In another embodiment, the present invention provides an organic electronic device containing the compound represented by the above formula (1).

The organic electroluminescent device includes a first electrode; A second electrode; And an organic material layer disposed between the first electrode and the second electrode. The organic material layer may include a compound represented by Formula 1, wherein Formula 1 is a hole injecting layer, a hole transporting layer, Or the light-emitting layer. That is, the compound represented by the formula (1) can be used as a material for the hole injection layer, the hole transport layer, the light emission assisting layer or the light emitting layer. Specifically, the present invention provides an organic electronic device including one of the compounds represented by Chemical Formulas (2) to (5) in an organic material layer. More specifically, the present invention provides an organic electronic device comprising an organic electronic device Lt; / RTI &gt;

In another embodiment of the present invention, the light efficiency improving layer is formed on at least one side of the one side of the first electrode opposite to the organic layer, or one side of the one side of the second electrode opposite to the organic layer, And an organic electroluminescent device.

Hereinafter, the synthesis examples of the compound represented by the formula according to the present invention and the production example of the organic electric device will be concretely described by way of examples, but the present invention is not limited to the following examples.

Synthetic example

Illustratively, the compounds according to the invention (Final Products) are prepared by reacting Sub 1 and Sub 2 as shown in Scheme 1 below, but are not limited thereto.

<Reaction Scheme 1>

Ⅰ. Sub  1

Sub 1 of Reaction Scheme 1 can be synthesized by the reaction path of Reaction Scheme 2 or Reaction Scheme 3, but is not limited thereto.

&Lt; Reaction Formula 2 > When L ² is not a single bond

<Reaction Formula 3> When L ² is a single bond

One. Sub  Synthesis Example of 1-1

Sub 1-1 of Scheme 2 or Scheme 3 may be synthesized by the reaction path of Scheme 4 or Scheme 6, but it is not limited thereto.

<Reaction Scheme 4> When L ¹ is not a single bond

Sub 1-1-1 (1 eq.), Sub 1-1-2 (1 eq.), Pd (PPh ₃ ) ₄ (0.03 eq.), NaOH (3 eq.), THF 1-1-1 mmol) and water (1.5 mL / Sub 1-1-1 mmol). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain Sub 1-1 (1).

Sub  Synthesis Example of 1-1-2

Sub 1-1-2 of Reaction Scheme 4 can be synthesized by the reaction path of Reaction Scheme 5 below, but it is not limited thereto.

<Reaction Scheme 5>

Sub 1-1-2-1 (1 equivalent), Sub 1-1-2-2 (1 equivalent), Pd ₂ (dba) ₃ (0.05 equivalent), PPh ₃ (0.1 equivalent), NaO t -Bu (3 eq.) And toluene (10.5 mL / Sub 1-1-2-1 1 mmol), and the reaction proceeds 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 1-1-2.

(One) Sub  Synthesis of 1-1 (1) -1

Put Sub 1-1-1 (6.3g, 20mmol) in a round bottom flask, Sub 1-1-2-1 (5.7g, 20mmol) , Pd (PPh 3) 4 (0.7g, 0.6mmol), NaOH ( 2.4 g, 60 mmol), THF (60 mL) and water (30 mL). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 7.5 g (yield: 79%) of Sub 1-1 (1) -1.

<Reaction Scheme 6> When L ¹ is a single bond

Sub 1-1-1 (1 equivalent), Sub 1-1-3 (1 equivalent), Pd ₂ (dba) ₃ (0.05 equivalent), PPh ₃ (0.1 equivalent), NaO t- Bu Equivalent) and toluene (10.5 mL / sub1-1-1 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. Subsequently, the resulting organic material was subjected to silicagel column and recrystallization to obtain Sub 1-1 (2).

(2) Sub  Synthesis of 1-1 (2) -1

Sub 1-1-1 (6.3 g, 20 mmol), Sub 1-1-3-1 (3.3 g, 20 mmol), pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ (0.5 g , NaO t- Bu (5.8 g, 60 mmol), and toluene (210 mL) were added, 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 6.7 g (yield: 84%) of Sub 1-1 (2) -1.

2. Sub  Synthesis example 1-2

Sub 1-2 of Reaction Scheme 2 may be synthesized by the reaction path of the following Reaction Scheme 7 but is not limited thereto.

<Reaction Scheme 7>

Sub  Synthesis example of 1-2-3

To a round bottom flask Sub 1-2-1 (1 eq.), Sub 1-2-2 (1 _{eq), Pd 2 (dba) 3} (0.05 eq.), PPh ₃ (0.1 equiv), NaO t -Bu (3 Equivalent), and toluene (10.5 mL / sub 1-2-1 mmol), followed by reaction at 100 &lt; 0 &gt; 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 1-2-3.

Sub  Synthesis example 1-2

Sub 1-2-3 (1 equivalent) was dissolved in anhydrous ether, the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.5M in hexane) (1.1 eq.) Was slowly added dropwise, &Lt; / RTI &gt; The temperature of the reaction was then lowered to -78 ° C and triisopropylborate (1.5 eq.) Was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and water. The organic layer was dried over MgSO ₄ and concentrated. Subsequently, the resulting organic material was subjected to silicagel column and recrystallization to obtain Sub 1-2.

(One) Sub  Synthesis of 1-2 (1)

Sub  Synthesis of 1-2-3-1

Sub-1-2-1-1 (5.7 g, 20 mmol), Sub 1-2-2-1 (3.4 g, 20 mmol), pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ 0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol), and toluene (210 mL). 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 4.9 g (yield: 76%) of Sub 1-2-3-1.

Sub  Synthesis of 1-2 (1)

Sub 1-2-3-1 (6.5 g, 20 mmol) was dissolved in anhydrous ether, the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.5 M in hexane) (1.4 g, 22 mmol) The reaction was then stirred for 30 minutes. The temperature of the reaction was then lowered to -78 ° C and triisopropyl borate (5.6 g, 30 mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After the reaction was completed, the reaction mixture was extracted with ethyl acetate and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 4.6 g (yield: 80%) of Sub 1-2 (1).

Examples of Sub 1-2 are shown below, but the present invention is not limited thereto, and their FD-MSs are shown in Table 1 below.

[Table 1]

3. Sub  Synthesis Example 1-3

Sub 1-3 of Scheme 3 is synthesized by the reaction path of Scheme 8 but is not limited thereto.

<Reaction Scheme 8>

Sub-1-3-1 (1 equivalent), Sub 1-3-2 (1 equivalent), Pd ₂ (dba) ₃ (0.05 equivalent), PPh ₃ (0.1 equivalent), NaO t- Bu , And toluene (10.5 mL / Sub 1-3-1 1 mmol) were 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. Subsequently, the resulting organic material was subjected to silicagel column and recrystallization to obtain Sub 1-3.

(One) Sub  Synthesis of 1-3 (9)

Sub 1-3-1-1 (1.9 g, 20 mmol), Sub 1-3-2-1 (5.5 g, 20 mmol), Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ 0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added to the mixture, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 5.2 g (64%) of Sub 1-3 (9).

(2) Sub  Synthesis of 1-3 (14)

Sub 1-3-1-2 (1.9 g, 20 mmol), Sub 1-3-2-2 (4.1 g, 20 mmol), Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ 0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added to the mixture, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 2.6 g (yield: 60%) of Sub 1-3 (14).

(3) Sub  Synthesis of 1-3 (28)

Sub-1-3-1-3 (3.4 g, 20 mmol), Sub 1-3-2-3 (4.7 g, 20 mmol), Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ 0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added to the mixture, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 4.2 g (yield: 65%) of Sub 1-3 (28).

Examples of Sub 1-3 are shown below, but the present invention is not limited thereto, and their FD-MS is shown in Table 2 below.

[Table 2]

4. Sub  Synthesis Example of 1 (1)

Sub 1-1 (1 eq.), Pd (PPh ₃ ) ₄ (0.03 eq.), NaOH (3 eq.), THF (3 mL / Sub 1-1 1 mmol) were added to a round bottom flask. ) And water (1.5 mL / Sub 1-1 1 mmol). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain Sub 1 (1).

(One) Sub  Synthesis of 1 (1) -1

Sub 1-2 (1) (5.8 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol) was added to a round bottom flask, Add NaOH (2.4 g, 60 mmol), THF (60 mL) and water (30 mL). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 8.3 g (yield: 73%) of Sub 1 (1) -1.

(2) Sub  Synthesis of 1 (1) -40

Sub 1-2 (1) (5.8 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol) was added to a round bottom flask, Add NaOH (2.4 g, 60 mmol), THF (60 mL) and water (30 mL). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 9.6 g (yield: 75%) of Sub 1 (1) -40.

5. Sub  Synthesis Example of 1 (2)

Sub-1-1 (1 equivalent), Sub 1-3 (1 equivalent), Pd ₂ (dba) ₃ (0.05 eq), PPh ₃ (0.1 eq.), NaO t- Bu (3 eq.), Toluene (10.5 mL / Sub 1-1 1 mmol), and the reaction proceeds 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 (2).

(One) Sub  Synthesis of 1 (2) -37

Sub 1-1 (2) -1 (8.0 g, 20 mmol), Sub 1-3 (30) (7.0 g, 20 mmol), Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ 0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added to the mixture, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was purified by silicagel column and recrystallized to obtain 9.9 g (yield: 74%) of Sub 1 (2) -37.

(2) Sub  Synthesis of 1 (2) -52

Sub 1-1 (1) -1 (9.5 g, 20 mmol), Sub 1-3 (8) (5.7 g, 20 mmol), Pd ₂ (dba) ₃ (0.9 g, 1 mmol), PPh ₃ 0.5 g, 2 mmol), NaO t- Bu (5.8 g, 60 mmol) and toluene (210 mL) were added to the mixture, and the mixture was refluxed at 100 ° C for 24 hours. ether and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was subjected to silicagel column and recrystallization to obtain 10.4 g (yield: 76%) of Sub 1 (2) -52.

Examples of Sub 1 include, but are not limited to, the FD-MS shown in Table 3 below.

[Table 3]

Ⅱ. Sub  2

Sub 2 of Reaction Scheme 1 can be synthesized by the reaction path of Reaction Scheme 9 below, but is not limited thereto.

<Reaction Scheme 9>

One. Sub  Synthesis Example of 2-2

Sub 2-2 of the above Reaction Scheme 9 may be synthesized by the reaction path of the following Reaction Scheme 10, but is not limited thereto.

<Reaction formula 10>

Sub  Synthesis Example of 2-2-3

Sub 2-2-2 (1 eq.), Pd (PPh ₃ ) ₄ (0.03 eq.), NaOH (3 eq.), THF (3 mL / 2-2-1 1 mmol) and water (1.5 mL / Sub 2-2-1 1 mmol). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain Sub 2-2-3.

Sub  Synthesis Example of 2-2

Sub 2-2-3 (1 eq.) And triphenylphosphine (3 eq.) Were dissolved in o-dichlorobenzene in a round bottom flask and refluxed for 24 hours. When the reaction was completed, the solvent was removed by distillation under reduced pressure, and the concentrated product was separated by column chromatography to obtain the desired Sub 2-2.

Examples of Sub 2-2 are as follows, but are not limited thereto, and their FD-MSs are shown in Table 4 below.

[Table 4]

2. Sub  Synthesis Example of 2-4

Sub 2-2 (1 eq.), Sub 2-3 (1 eq.), Pd ₂ (dba) ₃ (0.05 eq.), PPh ₃ (0.1 eq.), NaO t- Bu (3 eq.), Toluene (10.5 mL / Sub 2-2 mmol), and the reaction proceeds 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 2-4.

3. Sub  2

Sub 2-4 (1 eq.) Was dissolved in anhydrous ether, the temperature of the reaction was lowered to -78 ° C and n-BuLi (2.5 M in hexane) (1.1 eq.) Was slowly added dropwise and the reaction was stirred for 30 minutes . The temperature of the reaction was then lowered to -78 ° C and triisopropylborate (1.5 eq.) Was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. After completion of the reaction, the reaction mixture was extracted with ethyl acetate and water. The organic layer was dried over MgSO ₄ and concentrated. Subsequently, the resulting organic material was subjected to silicagel column and recrystallization to obtain Sub 2.

Meanwhile, examples of Sub 2 are as follows, but the present invention is not limited thereto, and the FD-MS values thereof are shown in Table 5 below.

[Table 5]

Ⅲ. The final product ( Final Products ) Synthesis of

Sub 1 (1 eq.), Pd (PPh ₃ ) ₄ (0.03 eq.), NaOH (3 eq.), THF (3 mL / / Sub 1 1 mmol). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain the final product.

1. Synthesis of 1-1

Sub 2 (1) (5.7 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol) and NaOH (2.4 g, 20 mmol) were placed in a round bottom flask. , 60 mmol), THF (60 mL) and water (30 mL). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 8.3 g (yield: 64%) of Compound 1-1.

2. Synthesis of 2-6

Sub 2 (9) (5.7 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol) and NaOH (2.4 g, 20 mmol) were placed in a round bottom flask. , 60 mmol), THF (60 mL) and water (30 mL). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 8.6 g (yield: 66%) of compound 2-6.

3. Synthesis of 3-11

Sub 2 (10) (5.7 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol) and NaOH (2.4 g, 20 mmol) were placed in a round bottom flask. , 60 mmol), THF (60 mL) and water (30 mL). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 12.7 g (yield: 71%) of Compound 3-11.

4. Synthesis of 4-76

Sub 2 (11) (5.7 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol) and NaOH (2.4 g, 20 mmol) were placed in a round bottom flask. , 60 mmol), THF (60 mL) and water (30 mL). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 11.4 g (yield: 65%) of 4-76.

5. Synthesis of 5-3

Sub 2 (10) (5.7 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol) and NaOH (2.4 g, 20 mmol) were placed in a round bottom flask. , 60 mmol), THF (60 mL) and water (30 mL). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 10.0 g (yield: 69%) of 5-3.

6. Synthesis of 5-43

Sub 2 (10) (5.7 g, 20 mmol), Pd (PPh ₃ ) ₄ (0.7 g, 0.6 mmol) and NaOH (2.4 g, 20 mmol) were placed in a round bottom flask. , 60 mmol), THF (60 mL) and water (30 mL). Then, the mixture is heated to reflux at 80 ° C to 90 ° C. When the reaction is complete, dilute with distilled water at room temperature and extract with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 11.3 g (yield: 70%) of compound 5-43.

Meanwhile, the FD-MS of the compounds 1-1 to 5-48 of the present invention prepared according to the above Synthesis Examples are shown in Table 6 below.

[Table 6]

Evaluation of manufacturing of organic electric device

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

An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention 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" hereinafter) was vacuum-deposited to a thickness of 60 nm to form a hole injection layer, and Compound 1-34 of the present invention was coated on the hole injection layer to a thickness of 60 nm To form a hole transporting layer. Subsequently, tris (2-phenylpyridine) -iridium (hereinafter referred to as "Ir (ppy) ₃ ") was added to the hole transport layer as a host material, and 4,4'-N, N'-dicarbazole- Quot;) as a dopant material was doped at a weight ratio of 90:10 by vacuum deposition to a thickness of 30 nm to form a light emitting layer. 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 (8-quinolinol) aluminum (hereinafter abbreviated as "Alq ₃ &quot;) was vacuum deposited on the hole blocking layer to a thickness of 40 nm to form an electron transport layer. Thereafter, LiF, which is 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. Thus, an organic electroluminescent device was manufactured.

[ Example  2] to [ Example  20] green organic light emitting device ( Hole transport layer )

1-40, 1-76, 1-79, 2-34, 2-40, 2-76, 2-79, and 3-7 of the present invention described in the following Table 7 were used instead of the compound 1-34 of the present invention as the hole transport layer material -34, 3-40, 3-76, 3-79, 4-34, 4-40, 4-76, 4-79 and 5-1 to 5-4. An organic electroluminescent device was prepared in the same manner.

[ Comparative Example  One]

An organic EL device was prepared in the same manner as in Example 1, except that the following compound A was used instead of the compound 1-34 of the present invention as a hole transport layer material.

    &Lt; Comparative Compound A >

[ Comparative Example  2]

An organic electroluminescent device was prepared in the same manner as in Example 1, except that the following compound B was used in place of the compound 1-34 of the present invention as the hole transport layer material.

    &Lt; Comparative Compound B >

[ Comparative Example  3]

An organic electroluminescent device was prepared in the same manner as in Example 1, except that the following compound C was used in place of the compound 1-34 of the present invention as a hole transport layer material.

    <Comparative compound C>

Electruminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples 1 to 20 and Comparative Examples 1 to 3 of the present invention And T95 lifetime was measured by a life measuring device manufactured by Mac Science Inc. at a luminance of 5000 cd / m 2. The measurement results are shown in Table 7 below.

[Table 7]

As can be seen from the results of Table 7, the organic electroluminescent device using the compound of the present invention as the material of the hole transport layer has a higher driving voltage, luminescent efficiency, and a lower luminance compared to the organic electroluminescent device using Comparative Compounds A to C as the material of the hole transport layer. The life can be remarkably improved.

In other words, a device using Comparative Compound C in which Carbazole was substituted with 2 and a compound of the present invention as a material of the hole transport layer, compared with the device using Comparative Compound A, which is NPB, and Comparative Compound B, And excellent device results in terms of driving voltage, luminous efficiency, and lifetime. Further, a device using the compound of the present invention in which one carbazole was substituted at the 9-position was used as the material of the hole transport layer, rather than the device using the comparative compound C in which all of the two carbazoles were substituted at the 3-position The best device results were obtained in terms of driving voltage, luminous efficiency and lifetime. This suggests that the properties of the compounds may vary significantly depending on the number of carbazole substituents, the position, or the type of other substituent group.

[ Example  21] red organic light emitting device The light- )

An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, 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, and 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 transport layer. Subsequently, Compound 1-1 of the present invention was vacuum-deposited on the hole transport layer to a thickness of 20 nm to form a light-emission-assisting layer, and bis- (1-phenylisoquinolyl) iridium (III) acetylacetonate (hereinafter abbreviated as "(piq) ₂ Ir (acac)") as a dopant in a weight ratio of 95: 5 was vacuum deposited at a thickness of 30 nm to form a light emitting layer. Subsequently, BAlq was vacuum deposited on the light emitting layer to form a hole blocking layer to form a hole blocking layer, and Alq ₃ was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transporting layer. Thereafter, LiF, which is 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. Thus, an organic electroluminescent device was manufactured.

[ Example  22] to [ Example  84] red organic light emitting device The light- )

The compounds 1-2 to 1-14, 1-24, 2-1 to 2-14, 2-24, 3-1 to 2-4 of the present invention described in the following Table 8 were used instead of the compound 1-1 of the present invention as the light- 3-14, 3-24, 4-1 to 4-14, 4-24, and 5-1 to 5-4 were used in place of the organic electroluminescent device of Example 21.

[ Comparative Example  4]

An organic EL device was prepared in the same manner as in Example 21 except that no light-emitting auxiliary layer was formed.

[ Comparative Example  5]

An organic EL device was prepared in the same manner as in Example 21, except that the compound A was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.

[ Comparative Example  6]

An organic electroluminescent device was prepared in the same manner as in Example 21 except that the compound B was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.

[ Comparative Example  7]

An organic EL device was prepared in the same manner as in Example 21, except that the compound C was used in place of the compound 1-1 of the present invention as the luminescent auxiliary layer material.

Electruminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples 21 to 84 and Comparative Examples 4 to 7 of the present invention And the T95 lifetime was measured using a life measuring device manufactured by Mac Science Inc. at a luminance of 2500 cd / m 2. The measurement results are shown in Table 8 below.

[Table 8]

[ Example  85] 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 as a light emitting auxiliary layer material. First, 2-TNATA was vacuum deposited on the ITO layer (anode) formed on the organic substrate to form a hole injection layer, and then a hole transport layer was formed by vacuum depositing NPD on the hole injection layer to a thickness of 60 nm . Subsequently, Compound 1-1 of the present invention was vacuum deposited on the hole transport layer to form a light emission-assisting layer, and CBP as a host material and Ir (ppy) ₃ as a dopant material To a weight ratio of 95: 5 by vacuum deposition to form a light emitting layer. Subsequently, BAlq was vacuum deposited on the light emitting layer to form a hole blocking layer to form a hole blocking layer, and Alq ₃ was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transporting layer. Thereafter, LiF, which is 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. Thus, an organic electroluminescent device was manufactured.

[ Example  86] to [ Example  148] green organic light emitting device The light- )

The compounds 1-2 to 1-14, 1-24, 2-1 to 2-14, 2-24, 3-1 to 4-12 of the present invention described in Table 9 below were used instead of the compound 1-1 of the present invention as the light- 3-14, 3-24, 4-1 to 4-14, 4-24, and 5-1 to 5-4 were used as the organic electroluminescent devices.

[ Comparative Example  8]

An organic EL device was prepared in the same manner as in Example 85, except that no light-emitting auxiliary layer was formed.

[ Comparative Example  9]

An organic electroluminescent device was prepared in the same manner as in Example 85, except that the compound A was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.

[ Comparative Example  10]

An organic electroluminescent device was prepared in the same manner as in Example 85, except that the compound B was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.

[ Comparative Example  11]

An organic electroluminescent device was prepared in the same manner as in Example 85, except that the compound C was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.

Electruminescence (EL) characteristics were measured with photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples 85 to 148 and Comparative Examples 8 to 11 of the present invention And T95 lifetime was measured by a life measuring device manufactured by Mac Science Inc. at a luminance of 5000 cd / m 2. The measurement results are shown in Table 9 below.

[Table 9]

[ Example  149] Blue organic light emitting device The light- )

An organic electroluminescent device was fabricated according to a conventional method using the compound of the present invention as a light emitting auxiliary layer material. First, 2-TNATA was vacuum deposited on the ITO layer (anode) formed on the organic substrate to form a hole injection layer, and then a hole transport layer was formed by vacuum depositing NPD on the hole injection layer to a thickness of 60 nm . Subsequently, Compound 1-1 of the present invention was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form a light emission-assisting layer. Then, 9,10-di (naphthalen-2-yl) anthracene As a material, BD-052X (manufactured by Idemitsu Kosan) was doped at a weight ratio of 93: 7 using a dopant material to form a light emitting layer by vacuum evaporation to a thickness of 30 nm. Subsequently, BAlq was vacuum deposited on the light emitting layer to form a hole blocking layer to form a hole blocking layer, and Alq ₃ was vacuum deposited to a thickness of 40 nm on the hole blocking layer to form an electron transporting layer. Thereafter, LiF, which is 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. Thus, an organic electroluminescent device was manufactured.

[ Example  150] to [ Example  212] blue organic light emitting device The light- )

The compounds 1-2 to 1-14, 1-24, 2-1 to 2-14, 2-24, 3-1 to 4-11 of the present invention described in Table 10 below were used instead of the compound 1-1 of the present invention as the light- 3-14, 3-24, 4-1 to 4-14, 4-24, and 5-1 to 5-4 were used as the organic electroluminescent devices.

[ Comparative Example  12]

An organic EL device was fabricated in the same manner as in Example 149 except that no light-emitting auxiliary layer was formed.

[ Comparative Example  13]

An organic electroluminescent device was prepared in the same manner as in Example 149 except that the compound A was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.

[ Comparative Example  14]

An organic EL device was prepared in the same manner as in Example 149, except that the compound B was used instead of the compound 1-1 of the present invention as a light-emitting auxiliary layer material.

[ Comparative Example  15]

An organic EL device was prepared in the same manner as in Example 149, except that the compound C was used instead of the compound 1-1 of the present invention as the luminescent auxiliary layer material.

Electruminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples 149 to 212 and Comparative Examples 12 to 15 of the present invention And the T95 lifetime was measured using a life measuring device manufactured by Mac Science Inc. at a luminance of 500 cd / m 2. The measurement results are shown in Table 10 below.

[Table 10]

As can be seen from the results of Tables 8, 9 and 10, the organic electroluminescence device using the compound of the present invention as the material of the light-emission-assisting layer can be manufactured by mixing the organic electroluminescence device without the light- Luminescent efficiency and lifetime were remarkably improved as compared with the organic electroluminescence device using the material as the material of the light emitting auxiliary layer.

That is, it can be confirmed that the devices using Comparative Compounds A to C and the compound of the present invention as a material for the light-emission assisting layer have improved luminous efficiency and lifetime, A device using a comparative compound C substituted with two carbazoles as a light emitting auxiliary layer material tends to exhibit higher efficiency and a longer lifetime than an element used as a layer material. It was also confirmed that the device using the compound of the present invention in which the number of the comparative compound C and the carbazole was the same but different types of bonding, was used as the material of the light-emitting auxiliary layer exhibited remarkably high efficiency and long lifetime.

This is because the compound of the present invention in which two carbazoles are bonded in an NC type has a higher T1 and a deeper HOMO level than the comparative compound C in which two carbazoles are bonded in CC type, The conjugation length of the compound of the present invention, which is one type of the NC type compound, is shorter than that of the compound of the present invention, thereby having a wider bandgap. This results in an electron blocking ability and a charge balance in the light emitting layer of holes and electrons charge balance) is increased, so that it is considered that the efficiency and the lifetime are maximized because the light emission is well performed inside the light emitting layer rather than at the interface of the hole transporting layer.

In general, when the light-emission-assisting layer is used as in Comparative Examples 5 to 7, 9 to 11, and 13 to 15 using the comparative compounds A to C, the efficiency and lifetime are increased but the driving voltage is increased The phenomenon can be confirmed. However, the results of the device using the compound of the present invention as a light-emitting auxiliary layer show that the driving voltage is not increased while improving the efficiency and lifetime. That is, the device using the compound of the present invention as a light emitting auxiliary layer improves the efficiency and lifetime, and at the same time, the driving voltage is not increased, and the power efficiency is improved by reducing the power consumption. This suggests that the characteristics of the compound may vary significantly depending on the number of carbazole substitution, bonding position, or other substituent group, as described in Table 7. [

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):
&Lt; Formula 1 >

In Formula 1,
Ar ¹ to Ar ³ independently of one another are i) a C ₆ to C ₆₀ aryl group; A fluorenyl 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 ii) Ar ¹ and Ar ² are selected from the group consisting of To form a ring (provided that Ar &lt; ³ &gt; is as defined in (i)
a, c and d are each an integer of 0 to 4, b is an integer of 0 to 3,
R ¹ to R ⁴ independently of one another are i) hydrogen; A C ₆ to C ₆₀ aryl group; And O, N, S, Si, and a heterocyclic group of C ₂ ~ C ₆₀ comprising at least one heteroatom selected from the group consisting of P; selected from the group consisting of or, or ⅱ) between groups neighboring bonded to each other (Provided that R ¹ to R ⁴ which do not form a ring are respectively the same as those defined in (i) above),
L ¹ and L ² independently of one another are a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; And a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P;
Each of the aryl group, the fluorenyl group, the heterocyclic group, the arylene group and the fluorenylene group is a C ₁ to C ₂₀ alkyl group; Or C ₆ -C ₂₀ An aryl group; The method according to claim 1,
Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;
&Lt; Formula 2 &gt;&lt; EMI ID =

&Lt; Formula 4 >&lt; EMI ID =

[In the above Chemical Formulas 2 to 5,
Ar ¹ to Ar ³ , R ¹ to R ⁴ , L ¹ , L ² , a, b, c and d are as defined in claim 1. The method according to claim 1,
Lt; / RTI &gt; is one of the following compounds.

An organic electric device comprising a compound according to any one of claims 1 to 3. 5. The method of claim 4,
A first electrode; A second electrode; And an organic material layer disposed between the first electrode and the second electrode, wherein the compound is contained in the organic material layer. 6. The method of claim 5,
Wherein the compound is contained in at least one of the hole injecting layer, the hole transporting layer, the luminescent auxiliary layer or the luminescent layer of the organic material layer. 6. The method of claim 5,
Further comprising a light-efficiency-improvement layer formed on at least one side of the one surface of the first electrode and the second electrode opposite to the organic material layer. 6. The method of claim 5,
Wherein the organic material layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process. A display device 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 electroluminescent device is at least one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, and a monochromatic or white illumination device.

Images