KR20170112913A - Compound for organic electronic element, organic electronic element comprising the same, and electronic device thereof - Google Patents

Abstract

Disclosed is an organic electronic device comprising a compound represented by Chemical Formula (1) and a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode, and an electronic device including the organic compound. The driving voltage of the organic electroluminescent device can be lowered, and the luminous efficiency and lifetime can be improved.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound for an organic electronic device, an organic electronic device using the compound, and an electronic device using the compound.

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 multi-layered structure made of different materials, and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

A material used as an organic material layer in an organic 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 is an important factor for portable displays, which have a limited power source, such as a battery, and efficiency and longevity are also important factors to be solved.

The efficiency, lifetime, and driving voltage are related to each other. As the efficiency increases, the driving voltage drops and the driving voltage drops. As a result, crystallization of the organic material due to Joule heating, which occurs during driving, And the lifetime tends to increase. However, simply improving the organic material layer can not maximize the efficiency. This is because, when the optimal combination of the energy level and T1 value between each organic material layer and the intrinsic properties (mobility, interface characteristics, etc.) of the material are achieved, long life and high efficiency can be achieved at the same time.

Recently, in order to solve the light emission problem in the hole transporting layer in organic electroluminescent devices, a method of using a light emission assisting layer between the hole transporting layer and the light emitting layer has been studied. According to each of the light emitting layers (R, G, B) The material properties are different, and it is necessary to develop the light-emission assisting layer for each light-emitting 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 produced in the light emitting layer is transferred to the interface of the hole transport layer or the hole transport layer, Resulting in charge unbalance in the light emitting layer and light emission 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 should be a material having a HOMO level between the HOMO energy level of the hole transporting layer and the HOMO energy level of the light emitting layer, and has a high T1 value and a hole mobility (within a driving voltage range of a full device blue device) mobility of the light-emitting layer.

However, this can not be achieved simply by the structural characteristics of the core of the light-emitting auxiliary layer material, and the proper combination of the characteristics of the core and the sub-substituent of the light-emitting auxiliary layer material and between the light emitting auxiliary layer, the hole transport layer, A high efficiency and a high number of devices can be realized.

On the other hand, it is also necessary to develop a hole injection / transport layer and a light-emitting auxiliary layer material having stable characteristics, that is, a high glass transition temperature, against joule heating generated when the device is driven. The low glass transition temperature of the hole transporting layer and the light emitting auxiliary layer material can be deformed due to the heat generated when the device is driven and the uniformity of the thin film surface is lowered when the device is driven, . 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, it is required that a material constituting the organic material layer in the device, for example, a hole injecting material, a hole transporting material, a light emitting material, an electron transporting 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.

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above-mentioned problems occurring in the prior art, and it is an object of the present invention to provide a compound having efficient electron blocking ability and hole transporting ability, , Color purity and lifetime, and an organic electronic 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.

According to the present invention, hole transport ability and thermal stability can be improved by using a specific compound which defines the type, position and number of amine groups connected to the dibenzothiophene core, And has a high HOMO energy level, a high T 1 value, and a high refractive index, which are easy to balance charges in the light emitting layer, thereby improving the luminous efficiency, heat resistance, lifetime and the like of the organic electronic device and lowering the driving voltage.

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

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

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

In describing the components of the present invention, the terms first, second, A, B, (a), (b), and the like can 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."

In addition, when an element such as a layer, film, region, plate, or the like is referred to as being "on" or "on" another element, And the like. On the contrary, when an element is referred to as being "directly on " another element, it should be understood that it does not have another element in the middle.

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 "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.

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 term "fluorenyl group" or "fluorenylene group" used in the present invention means a monovalent or divalent functional group in which R, R 'and R & Substituted fluorenyl group "or" substituted fluorenylene group "means that at least one of the substituents R, R 'and R" is a substituent other than hydrogen, and R and R' Together with a spy compound.

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, the aryl group or the arylene group includes a single ring, a ring group, a plurality of ring systems bonded together, a spiro compound and the like.

The term "heterocyclic group" as used herein includes not only aromatic rings such as "heteroaryl group" or "heteroarylene group ", but also nonaromatic rings, Means a ring of 2 to 60 rings, but is not limited thereto. The term "heteroatom ", as used herein, unless otherwise indicated, refers to N, O, S, P, or Si, wherein the heterocyclic group includes single ring, ring, And the like.

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.

As used herein, the term "ring" includes monocyclic and polycyclic rings, including hydrocarbon rings as well as heterocycles containing at least one heteroatom and including aromatic and non-aromatic rings.

As used herein, the term "polycyclic" includes ring assemblies such as biphenyl, terphenyl, and the like, as well as various fused ring systems and spiro compounds, including aromatic as well as non- The ring includes, of course, a heterocycle containing at least one heteroatom.

As used herein, the term "ring assemblies" means that two or more ring systems (a single ring or a fused ring system) are directly connected to each other through a single bond or a double bond, Means that the number of linkages is one less than the total number of rings in the compound. The ring assemblies may be directly connected to each other through a single bond or a double bond.

As used herein, the term " conjugated ring system "refers to a fused ring form shared by at least two atoms, in which the ring system of two or more hydrocarbons is conjugated and contains at least one heteroatom And at least one hetero ring system bonded thereto. Such conjugated ring systems may be aromatic rings, heteroaromatic rings, aliphatic rings or a combination of these rings.

The term "spiro compound" used in the present invention has a 'spiro union', and a spiro connection means a connection in which two rings share only one atom. In this case, the atoms shared in the two rings are called 'spyro atoms', and depending on the number of spyro atoms contained in one compound, they are referred to as' monospyros,' 'diospyros,' ' 'Compounds.

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

Moreover, no explicit description is one, the terms used in this invention in the "unsubstituted or substituted", "substituted" is an alkyl group of deuterium, a halogen, an amino group, a nitrile group, a nitro _{group, C 1 -C 20, C 1} - C ₂₀ alkoxy group, alkyl group of the alkyl amine group of _{C 1 -C 20, C 1 -C} 20 thiophene group, a C ₆ -C ₂₀ aryl thiophene group, alkenyl group, C ₂ of the C ₂ -C ₂₀ - alkynyl, C ₃ -C ₂₀ cycloalkyl, C ₆ of the C ₆ -C ₂₀ aryl group, a C ₈ -C ₂₀ substituted with an aryl group, a heavy hydrogen of the aryl -C ₂₀ alkenyl group, a silane group of C _20, And a C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si, and P, and at least one group selected from the group consisting of a hydrogen atom, Quot; means that the substituent is not limited to these substituents.

In the present specification, the 'group name' corresponding to the aryl group, the arylene group, the heterocyclic group and the like exemplified as the examples of the respective symbols and substituents thereof may be described as 'the name of the group reflecting the singer' You may. For example, in the case of phenanthrene, which is a kind of aryl group, monovalent 'group' refers to 'phenanthryl (group)' and divalent group refers to phenanthrylene (group) , But it may be described as "phenanthrene", which is the parent compound name, regardless of the singer. Similarly, in the case of the pyrimidine, the pyrimidine may be referred to as 'pyrimidine' irrespective of the valence, or the pyrimidinyl group may be used when it is monovalent, Name '.

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, the substituent R ¹ is absent. That is, when a is 0, it means that all of the carbons forming the benzene ring are bonded to hydrogen. In this case, And the chemical formula or compound may be described. 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, for example, , R < ¹ > may be the same or different from each other when a is an integer of 2 or more.

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

1, an organic electroluminescent device 100 according to an embodiment of the present invention includes a first electrode 120, a second electrode 180 and a first electrode 120 formed on a substrate 110, And an organic material layer containing a compound according to the present invention is provided between the two electrodes 180. 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, at least one of these layers may be omitted or may further include a hole blocking layer, an electron blocking layer, a light emitting auxiliary layer 151, an electron transporting auxiliary layer, a buffer layer 141, The hole transporting layer 140 and the electron transporting layer 160 may be formed of one or more layers.

Also, although not shown, the organic electroluminescent device according to an embodiment of the present invention further includes 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 can do.

The compound according to one embodiment of the present invention applied to the organic layer includes a hole injecting layer 130, a hole transporting layer 140, a light emitting auxiliary layer 151, an electron transporting auxiliary layer, an electron transporting layer 160, 170, a host of the light emitting layer 150, or a material of a dopant or a light efficiency improving layer. For example, the compound of the present invention may be used as a light emitting layer 150, a hole transporting layer 140, and / or a light emitting auxiliary layer 151 material.

On the other hand, even if the core is the same core, since the band gap, the electrical characteristics, the interface characteristics, and the like can be changed depending on which substituent is bonded at which position, the selection of the core and the combination of the sub- In particular, when the optimal combination of the energy level and T ₁ value between the organic layers, 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.

As described above, generally, in order to solve the light emission problem in the hole transporting layer in the organic electroluminescent device, it is preferable to form a light emission assisting layer between the hole transporting layer and the light emitting layer. It is necessary to develop different luminescence-assisting layers according to the above. 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)

Therefore, in the present invention, by forming the hole transporting layer and / or the light-emitting auxiliary layer by using the compound represented by the general formula (1), the energy level and T ₁ value between each organic material layer, the intrinsic properties (mobility, The lifetime and the efficiency of the organic electronic device can be improved at the same time.

An organic electroluminescent device according to an embodiment of the present invention may be manufactured using various deposition methods. For example, a metal or a metal oxide having conductivity or an alloy thereof may be deposited on a substrate to form a cathode 120, and a hole injection layer 130 may be formed thereon. A hole transport layer 140, a light emitting layer 150, an electron transport layer 160, and an electron injection layer 170, and then depositing a material that can be used as a cathode 180 on the organic layer. have. An emission auxiliary layer 151 may be further formed between the hole transport layer 140 and the emission layer 150 and an electron transport auxiliary layer may be further formed between the emission layer 150 and the electron transport layer 160.

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 an embodiment of the present invention may be a front 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 an embodiment of the present invention may be one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, or a device for monochromatic or white illumination.

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 the above formula (1), each symbol is defined as follows.

L ¹ is a C ₆ -C ₆₀ arylene group, preferably a C ₆ -C ₃₀ arylene group, more preferably a C ₆ -C ₁₈ arylene group, and examples thereof include phenyl, naphthalene, biphenyl, Phenyl, phenanthrene, triphenylene, and the like.

L ² and L ³ independently of one another are a single bond; C ₆ -C ₆₀ arylene groups; A fluorenylene group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; And a fused ring group of an aromatic ring of C ₆ -C ₆₀ and an aliphatic ring of C ₃ -C ₆₀ .

When L ² and L ³ are arylene groups, it is preferably a C ₆ -C ₃₀ arylene group, more preferably a C ₆ -C ₁₈ arylene group, and may be illustratively phenyl, naphthalene, biphenyl, and the like. When L ² and L ³ are a heterocyclic group, it is preferably a C ₂ -C ₃₀ heterocyclic group, a C ₂ -C ₁₀ heterocyclic group, and may be illustratively pyridine, dibenzothiophene, and the like.

Ar ¹ to Ar ⁵ independently represent a C _{6 to} C ₆₀ aryl group; Heterocyclic group of O, N, S, Se, C 2 -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fluorenyl group; A fused ring group of a C ₆ -C ₆₀ aromatic ring and a C ₃ -C ₆₀ aliphatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And a C ₆ -C ₃₀ aryloxy group. However, carbazole is excluded from Ar ² and Ar ³ .

When Ar ¹ to Ar ⁵ are aryl groups, it is preferably a C _{6 to} C ₆₀ aryl group, more preferably a C _{6 to} C ₁₈ aryl group, and is exemplified by phenyl, naphthyl, biphenyl, terphenyl, Phenanthrene, fluoranthene, and the like. When Ar ¹ to Ar ⁵ are heterocyclic groups, it is preferably a C ₂ -C ₆₀ heterocyclic group, more preferably a C ₂ -C ₁₈ heterocyclic group, and exemplarily thiophene, pyridine, indole, iso Quinoline, carbazole, indolocarbazole, dibenzofuran, dibenzothiophene, dibenzoselenophene, and the like. When Ar ¹ to Ar ⁵ are fluorenyl groups, examples thereof include 9,9-dimethyl-9H-fluorene, 9,9-diphenyl-9H-fluorene, 9,9'-spirobifluorene, . When Ar ¹ to Ar ⁵ are fused rings, it may be, for example, 1,2-dihydrocyclobutabenzene.

m and n are each an integer of 0 to 3;

R ¹ and R ² independently of one another are deuterium; Tritium; halogen; Cyano; A nitro group; An aryl group of C ₆ -C ₆₀ ; A fluorenyl group; Heterocyclic group of O, N, S, Se, C 2 -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₆ -C ₆₀ aromatic ring and a C ₃ -C ₆₀ aliphatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And C ₆ -C ₃₀ aryloxy groups. When m is an integer of 2 or more, neighboring R ^{1 s} may combine with each other to form a ring, and even when n is an integer of 2 or more, adjacent R ² groups may be bonded to each other Can be combined to form a ring. When m is an integer of 2 or more, a plurality of R ^{1 s} may be the same as or different from each other, and when n is an integer of 2 or more, a plurality of R ^{2 s} may be the same or different from each other.

When R ¹ and R ² are aryl groups, it may preferably be a C ₆ -C ₆₀ aryl group, more preferably a C ₆ -C ₁₀ aryl group, and may be illustratively a phenyl, naphthyl group and the like.

The ring formed by bonding adjacent R ^{1 s} and / or adjacent R ^{2 s to} each other is at least one selected from the group consisting of C ₆ -C ₆₀ aromatic rings, fluorene, O, N, S, Se, Si and P and the like fused ring group of C ₂ -C ₆₀ hetero ring, or C ₆ -C ₆₀ aliphatic ring of the aromatic ring and the C ₃ -C ₆₀ containing a hetero atom, and may ringil benzene illustratively. When neighboring R ^{1 s} and / or neighboring R ^{2 s} are bonded to each other to form a benzene ring, naphthalene, phenanthrene or the like may be formed together with the benzene ring to which they are bonded.

로 이루어진 군에서 선택된 하나 이상의 치환기로 더 치환될 수 있다.Ar ¹ to Ar ⁵ , R ¹ , R ² , L ¹ to L ³ , a ring formed by bonding adjacent R ¹ groups to each other, and a ring formed by bonding adjacent R ² groups to each other include deuterium; halogen; A silane group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; A phosphine oxide group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ -C ₂₀ ; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₆ -C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Se, Si and P; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ -C ₂₀ ; -N (R ^a ) (R ^b ); Aryl alkenyl group of C ₈ -C _20; And

≪ RTI ID = 0.0 > and / or < / RTI >

-N (R ^a ) (R ^b ), R ^a and R ^b are independently of each other a C ₆ -C ₆₀ aryl group; A fluorenyl group; And a C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Se, Si and P, and R ^a and R ^b are selected from the group consisting of deuterium; halogen; A silane group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ -C ₂₀ ; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₆ -C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Se, Si and P; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ -C ₂₀ ; And an arylalkenyl group having from _{8 to 20} carbon atoms.

Preferably, the formula (1) may be represented by one of the following formulas (2) to (5), and more preferably by one of the following formulas (6) to (10).

&Lt; Formula 2 > < EMI ID =

<Formula 4><Formula5>

&Lt; Formula 6 > < EMI ID =

<화학식 9> <화학식 10>

&Lt; Formula 9 >< EMI ID =

In the above Chemical Formulas 2 to 10, symbols such as Ar ¹ to Ar ⁵ , R ¹ , R ² , L ¹ to L ³ , m and n and the like are the same as defined in Chemical Formula 1.

In the above Chemical Formulas 1 to 10, L ¹ may be represented by one of the following Chemical Formulas L1-1 to L1-7.

&Lt; General Formula (L1-1) > < General Formula (L1-2) >

&Lt; Formula L1-4 > < Formula L1-5 > < Formula L1-6 &

A to c each represent an integer of 0 to 4, d represents an integer of 0 to 6, e represents an integer of 0 to 5, f and g each represent an integer of 0 to 3, , R ³ to R ⁵ independently represent an aryl group; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And a C ₆ -C ₃₀ aryloxy group, and when a to g are each an integer of 2 or more, each of R ³ to R ⁵ may be the same or different.

When L &lt; ^{1 &gt;} is L1-1, preferably L &lt; ¹ &gt; may be one of the following structures, and R &lt; ³ &gt;

,

,

,

,

Preferably, in the general formulas (1) to (10), at least one of Ar ¹ to Ar ⁵ may be represented by the following general formula (11).

  &Lt; Formula 11 >

In the formula (11), each symbol can be defined as follows.

When Ar ^1, Ar ^4, and at least one of Ar ⁵ is of the formula 11 X is S, Se, O, C ( R c) (R d) or N (R ^e) and, Ar ^2, and at least one of Ar ³ is X is S, Se, O, or C ( ^Rc ) ( ^Rd ).

C (R ^c ) (R ^d ) and N (R ^e ), R ^c to R ^e are independently of each other a C ₆ -C ₆₀ aryl group; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And aryloxy groups of C ₆ -C ₃₀ , and R ^c and R ^d may combine with each other to form a spiro compound together with the carbon to which they are bonded.

L ⁴ is a single bond; A C ₆ -C ₂₀ arylene group; A fluorenylene group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; And a fused ring group of a C ₃ -C ₂₀ aliphatic ring and a C ₆ -C ₂₀ aromatic ring.

o is an integer from 0 to 3, p is an integer from 0 to 4, R ⁶ and R ⁷ are independently from each other deuterium; Tritium; halogen; Cyano; A nitro group; An aryl group of C ₆ -C ₆₀ ; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And C ₆ -C ₃₀ aryloxy groups, and when o and p are each an integer of 2 or more, plural R ⁶ and R ⁷ may be the same or different, and when o and p are each 2 or more In case of an integer, neighboring R ^{6 s} and adjacent R s ⁷ may be bonded to each other to form a ring.

More preferably, at least one of Ar ¹ , Ar ² and Ar ⁵ is the above-described Formula 11, wherein X in Formula 11 may be S.

When at least one of Ar ¹ to Ar ⁵ is the formula (11), preferably, the formula (1) may be represented by one of the following formulas (1-1) to (1-3).

X is S, Se, O, C (R ^c ) (R ^d ) or N (R ^e ) is O or ^{c (R c) (R d} ), Ar 1 to Ar ^5, L ¹ to ^{L 3, R 1, R 2} , symbols such as m and n are the same as those defined in formula 1, L ⁴ , R ^c to R ^e , R ⁶ , R ⁷ , o, and p are the same as defined in Formula 11 above.

Specifically, Formula 1 may be one of the following compounds.

Another aspect of the present invention provides an organic electronic device comprising a first electrode, a second electrode, and an organic layer formed between the first electrode and the second electrode. At this time, the organic material layer contains the compounds represented by Chemical Formulas 1 to 10.

Preferably, the organic material layer includes at least one of a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer, a light emitting layer, an electron transporting auxiliary layer, an electron transporting layer and an electron injecting layer, and the hole injecting layer, At least one of the light emitting layer, the electron transporting auxiliary layer, the electron transporting layer and the electron injecting layer contains the above compound in the form of a single compound or a mixture of two or more kinds. More preferably, the organic material layer includes a light emitting layer and a light emitting auxiliary layer, and the light emitting layer includes a phosphorescent red light emitting material, and the compound is contained in the light emitting auxiliary layer.

According to still another aspect of the present invention, there is provided an electronic device including a display device including the organic electroluminescent device of claim 8 and a control unit for driving the display device, wherein the organic electroluminescent device is an organic electroluminescent device, A photovoltaic cell, an organophotoreceptor, an organic transistor, and a monochromatic or white illumination device.

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

Synthetic example

The compounds represented by formula (1) according to the present invention are synthesized by reacting Sub 1 and Sub 2 as shown in Reaction Scheme 1 below, but are not limited thereto.

Ar ¹ to Ar ⁵ , L ¹ to L ³ , R ¹ , R ² , m, and n are the same as those defined in formula (1).

<Reaction Scheme 1>

I. Synthesis of Sub 1

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

<Reaction Scheme 2>

In the case of the amine (HN-Ar ² Ar ³ ) reactant, the synthesis method disclosed in Korean Patent No. 10-1251451 (registered on March 31, 2013) of the present applicant was used in Reaction Formula 2.

Examples of the synthesis of specific compounds belonging to Sub 1 are as follows.

1. Sub 1-1, Sub 1-83 Synthetic example

<Reaction Scheme 3>

(1) Sub 1-III-1 Synthesis

Dibromodibenzo [ b , d ] thiophene (CAS Registry Number: 122-39-4) (17.24 g, 101.87 mmol) was dissolved in toluene (850 ml) in a round bottom flask, (52.27 g, 152.81 mmol), Pd ₂ (dba) ₃ (2.80 g, 3.06 mmol), 50% P ( t- Bu) ₃ (4.0 mL, 8.15 mmol), NaO t- Bu (29.37 g, 305.62 mmol) was added and stirred at 70 &lt; 0 &gt; 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 28.06 g (yield: 64%) of the product.

(2) Sub 1-1 Synthesis

Sub1-III-1 (12.22 g, 28.39 mmol), toluene (200 ml), aniline (CAS Registry Number: 62-53-3) (2.91 g, 31.23 mmol) and Pd ₂ dba) ₃ (0.78 g, 0.85 mmol), 50% P ( t- Bu) ₃ (1.1 ml, 2.27 mmol) and NaO t- Bu (8.19 g, 85.18 mmol). 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 chromatography and then recrystallized to obtain 10.43 g (yield: 83%) of the product.

(3) Sub 1-IV-83 Synthesis

Sub-1-III-1 (14.59 g, 33.90 mmol) obtained in the above synthesis was dissolved in THF (120 ml) in a round bottom flask, and then 4-chlorophenyl boronic acid (CAS Registry Number: 1679-18-1) g, 37.29 mmol), Pd ( PPh 3) 4 (1.57 g, 1.36 mmol), NaOH (4.07 g, 101.71 mmol), was added water (60ml) 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 10.34 g (yield: 66%) of the product.

(4) Sub 1-83 synthesis

Aniline (CAS Registry Number: 62-53-3) (2.29 g, 24.62 mmol) and Pd ₂ (dba) ₃ (0.61 g, 0.67 mmol) were added to Sub 1-IV-83 (10.34 g, 22.38 mmol) ), 50% P ( t- Bu) ₃ (0.9 ml, 1.79 mmol), NaO t- Bu (6.45 g, 67.14 mmol) and toluene (160 ml) (Yield: 81%).

2. Sub 1-20 Synthetic example

<Reaction Scheme 4>

(1) Sub 1-I-20 synthesis

The starting material, 4-bromophenyl boronic acid (CAS Registry Number: 5467-74-3) (15.17 g, 75.54 mmol) was dissolved in toluene (755 ml) in a round bottom flask and then N- phenyldibenzo [ b , d ] thiophen -2-amine (CAS Registry Number: 1300028-91-4) (20.80 g, 75.54 mmol), Pd 2 (dba) 3 (2.08 g, 2.27 mmol), 50% P (t -Bu) 3 (2.2ml, 4.53 mmol), NaO t- Bu (21.78 g, 226.61 mmol) was added and stirred at 100 ° 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 25.68 g (yield: 86%) of the product.

(2) Sub 1-II-20 Synthesis

Sub-1-I-20 (25.68 g, 64.97 mmol) obtained in the above synthesis was dissolved in THF (230 ml) in a round bottom flask and 2,4-dibromo-1- (methylsulfinyl) benzene (CAS Registry Number: 1820757-87 6) a (21.30 g, 71.46 mmol), Pd (PPh 3) 4 (3.00 g, 2.60 mmol), NaOH (7.80 g, 194.90 mmol), water (115ml) was added and the mixture was 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 25.12 g (yield: 68%) of the product.

(3) Sub 1-III-20 Synthesis

Sub-1-II-20 (25.12 g, 44.18 mmol) obtained in the above synthesis was added to a round bottom flask with triflic acid (58.6 ml, 662.74 mmol) and stirred at room temperature for 24 hours. A pyridine aqueous solution (775 ml, H ₂ O = 1: 5) was slowly added dropwise and the mixture was refluxed with stirring for 30 minutes. 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 11.62 g (yield: 49%) of the product.

(4) Sub 1-20 synthesis

(CAS Registry Number: 92-67-1) (4.03 g, 23.82 mmol) and Pd (1,1'-biphenyl-4-amine) were added to Sub 1-III- ₂ (dba) ₃ (0.59 g, 0.65 mmol), 50% P ( t- Bu) ₃ (0.8 ml, 1.73 mmol), NaO t- Bu (6.24 g, 64.98 mmol) Sub-1-1 synthesis was used to obtain 10.83 g (yield: 80%) of the product.

3. Sub 1-28 Synthetic example

<Reaction Scheme 5>

(1) Sub 1-I-28 synthesis

Diphenylamine (CAS Registry Number: 122-39-4) (19.78 g, 116.90 mmol) was added to the starting material, 3-bromonaphthalen-2-yl boronic acid (CAS Registry Number: 1301205-62-8) _{mmol), Pd 2 (dba)} 3 (3.21 g, 3.51 mmol), 50% P (t -Bu) 3 (3.4ml, 7.01 mmol), NaO t -Bu (33.71 g, 350.71 mmol), toluene (1170ml) And 29.34 g (yield: 74%) of the product was obtained using the Sub 1-I-20 synthesis method.

(2) Sub 1-II-28 Synthesis

2,4-dibromo-1- (methylsulfinyl) benzene (CAS Registry Number: 1820757-87-6) (28.35 g, 95.15 mmol) was added to Sub 1-I-28 (29.34 g, 86.50 mmol) _{(PPh 3) 4 (4.00 g} , 3.46 mmol), NaOH (10.38 g, 259.49 mmol), THF (300ml), was added to water (150ml) and use the Sub 1-II-20 synthesis product was 24.82 g (yield: : 56%).

(3) Sub 1-III-28 Synthesis

Triflic acid (64.3 ml, 726.48 mmol) and pyridine aqueous solution (850 ml, pyridine: H ₂ O = 1: 5) were added to Sub 1-II-28 (24.82 g, 48.43 mmol) 11.63 g (Yield: 50%) of the product was obtained using the III-20 synthesis method.

(4) Sub 1-28 Synthesis

5-phenylthiophen-2-amine (CAS Registry Number: 14770-85-5) (4.67 g, 26.63 mmol) and Pd ₂ (dba) _{3 were added to} Sub 1-III-28 (11.63 g, 24.21 mmol) (0.67 g, 0.73 mmol), 50% P ( t- Bu) ₃ (0.9 ml, 1.94 mmol), NaO t- Bu (6.98 g, 72.62 mmol) and toluene (170 ml) 8.77 g (yield: 63%) of the product was obtained.

4. Sub 1-44, Sub 1-96 Synthetic example

<Reaction Scheme 6>

(1) Sub 1-III-44 Synthesis

The starting material, N - (p -tolyl) dibenzo [ b, d] furan-4-amine (CAS Registry Number: 1609080-05-8) 3,7-dibromodibenzo [b, d] a (33.00 g, 120.73 mmol) Pd ₂ (dba) ₃ (3.32 g, 3.62 mmol), 50% P ( t- Bu) ₃ (4.7 ml, 9.66 mmol), thiophene (CAS Registry Number: 83834-10-0) (61.94 g, 181.09 mmol) , NaO t- Bu (34.81 g, 362.19 mmol) and toluene (1000 ml) were added, and 38.07 g (Yield: 59%) of the product was obtained using the Sub 1-III-1 synthesis method.

(2) Sub 1-44 Synthesis

Indolo [3,2,1- jk ] carbazol-5-amine (CAS Registry Number: 1191512-09-0) (5.50 g, 21.45 mmol) was added to Sub 1-III-44 (10.42 g, 19.50 mmol) ), Pd ₂ (dba) ₃ (0.54 g, 0.58 mmol), 50% P ( t- Bu) ₃ (0.8 ml, 1.56 mmol), NaO t- Bu (5.62 g, 58.49 mmol) And 9.96 g (Yield: 72%) of the product was obtained using the Sub 1-1 synthesis method described above.

(3) Sub 1-IV-96 Synthesis

(5-chloropyridin-3-yl) boronic acid (CAS Registry Number: 872041-85-5) (8.91 g, 56.60 mmol) and Pd (Yield: 14.88 g) was obtained using Sub 1-IV-83 synthesis method by adding PPh ₃ ( ₄ ) (2.38 g, 2.06 mmol), NaOH (6.17 g, 154.36 mmol), THF (180 ml) 51%).

(4) Sub 1-96 Synthesis

3- (pyridin-3-yl) aniline (CAS Registry Number: 57976-57-5) (4.91 g, 28.86 mmol) and Pd ₂ (0.25 mmol) were added to Sub 1-IV-96 (14.88 g, 26.24 mmol) _{dba) 3 (0.72 g, 0.79} mmol), 50% P (t -Bu) 3 (1.0ml, 2.10 mmol), NaO t -Bu (7.57 g, 78.72 mmol), was added to toluene (185ml), and wherein Sub 1 -1 &lt; / RTI &gt; synthesis method was used to obtain 9.93 g (yield: 54%) of the product.

5. Sub 1-46 and Sub 1-73 Synthetic example

<Reaction Scheme 7>

(1) Sub 1-I-46 synthesis

Diphenylamine (CAS Registry Number: 122-39-4) (32.29 g, 190.81 mmol) was added to the starting material (3-bromophenyl) boronic acid (CAS Registry Number: 89598-96-9) (38.32 g, 190.81 mmol) To the mixture was added dropwise a solution of ₂ (dba) ₃ (5.24 g, 5.72 mmol), 50% P ( t- Bu) ₃ (5.6 ml, 11.45 mmol), NaO t- Bu (55.02 g, 572.42 mmol) Sub-1-I-20 Synthesis method was used to obtain 50.20 g (yield: 91%) of the product.

(2) Sub 1-II-46 Synthesis

4-bromo-1-iodo-2- (methylsulfinyl) benzene (CAS Registry Number: 1638151-06-0) (65.89 g, 190.98 mmol) was added to Sub 1-I-46 (50.20 g, 173.62 mmol) _{, Pd (PPh 3) 4 (} 8.03 g, 6.94 mmol), NaOH (20.83 g, 520.85 mmol), THF (610ml), was added to water (305ml) and use the Sub 1-II-20 synthesis product 60.21 g (Yield: 75%).

(3) Synthesis of Sub 1-III-46 and Sub 1-III-73

Triflic acid (115.2 ml, 1302.09 mmol) and pyridine aqueous solution (1520 ml, pyridine: H ₂ O = 1: 5) were added to Sub 1-II-46 (60.21 g, 130.21 mmol) 23.54 g (Yield: 42%) of Sub 1-III-46 and 20.73 g (Yield: 37%) of Sub 1-III-71 were obtained using the III-20 synthesis method.

(4) Sub 1-46 Synthesis

Aniline (CAS Registry Number: 62-53-3) (2.74 g, 29.47 mmol) and Pd ₂ (dba) ₃ (0.74 g, 0.80 mmol) were added to Sub 1-III-46 (11.53 g, 26.79 mmol) ), 50% P ( t- Bu) ₃ (1.0 ml, 2.14 mmol), NaO t- Bu (7.72 g, 80.37 mmol) and toluene (190 ml) (Yield: 85%).

(5) Sub 1-73 Synthesis

(CAS Registry Number: 2243-47-2) (4.39 g, 25.97 mmol) and Pd (1,1'-biphenyl) -3 -amine (10.16 g, 23.61 mmol) _{To this solution was added a solution of 2} (dba) ₃ (0.65 g, 0.71 mmol), 50% P ( t- Bu) ₃ (0.9 ml, 1.89 mmol), NaO t- Bu (6.81 g, 70.82 mmol) Sub-1-1 synthesis method was used to obtain 9.80 g (yield: 80%) of the product.

6. Sub 1-60 Synthetic example

<Reaction Scheme 8>

Dibenzo [ b , d ] thiophen-2-amine (CAS Registry Number: 7428-91-3) (5.98 g, 30.01 mmol) and Pd ₂ (dba) ₃ (0.75 g, 0.82 mmol), 50% P ( t- Bu) ₃ (1.1 ml, 2.18 mmol), NaO t- Bu (7.87 g, 81.84 mmol) (Yield: 71%) of the product.

7. Sub 1-79 Synthetic example

<Reaction Scheme 9>

(1) Sub 1-I-79 Synthesis

N- phenylnaphthalen-1-amine (CAS Registry Number: 90-30-2) (24.57 g, 112.04 mmol) was added to (4-bromophenyl) boronic acid (CAS Registry Number: 5467-74-3) _{, 112.04 mmol), Pd 2 (} dba) 3 (3.08 g, 3.36 mmol), 50% P (t -Bu) 3 (3.3ml, 6.72 mmol), NaO t -Bu (32.30 g, 336.11 mmol), toluene ( 1120 ml) was added, and 35.34 g (yield: 93%) of the product was obtained using the Sub 1-I-20 synthesis method.

(2) Sub 1-II-79 Synthesis

1,3-dichloro-2- (methylsulfinyl) benzene (CAS Registry Number: 122199-98-8) (23.96 g, 114.60 mmol) was added to Sub 1-I-79 (35.34 g, 104.19 mmol) _{(PPh 3) 4 (4.82 g} , 4.17 mmol), NaOH (12.50 g, 312.56 mmol), THF (360ml), was added to water (180ml) and use the Sub 1-II-20 synthesis product was 25.36 g (yield: : 52%).

(3) Sub 1-III-79 Synthesis

Triflic acid (71.9 ml, 812.80 mmol) and pyridine aqueous solution (950 ml, pyridine: H ₂ O = 1: 5) were added to the Sub 1-II-79 obtained in the above synthesis (25.36 g, 54.19 mmol) 11.10 g (yield: 47%) of the product was obtained using the III-20 synthesis method.

(4) Sub 1-79 Synthesis

Dibenzo [ b , d ] thiophen-4-amine (CAS Registry Number: 72433-66-0) (5.58 g, 28.01 mmol) and Pd ₂ (dba) ₃ (0.70 g, 0.76 mmol), 50% P ( t- Bu) ₃ (1.0 ml, 2.04 mmol), NaO t- Bu (7.34 g, 76.38 mmol) 10.37 g (Yield: 68%) of the product was obtained by the synthesis of 1-1.

8. Sub 1-109, Sub 1-114, Sub 1-119 Synthetic example

<Reaction formula 10>

(1) Sub 1-I-109 synthesis

(CAS Registry Number: 122) was added to the starting material (3'-bromo- [1,1'-biphenyl] -3-yl) boronic acid (CAS Registry Number: 1048990-21-1) (73.05 g, 263.79 mmol) (44.64 g, 263.79 mmol), Pd ₂ (dba) ₃ (7.25 g, 7.91 mmol), 50% P ( t- Bu) ₃ (7.7 ml, 15.83 mmol), NaO t- g, 791.38 mmol) and toluene (1760 ml) were added, and 86.71 g (yield: 90%) of the product was obtained using the Sub 1-I-20 synthesis method.

(2) Sub 1-II-109 Synthesis

4-bromo-1-iodo-2- (methylsulfinyl) benzene (CAS Registry Number: 1638151-06-0) (90.09 g, 261.15 mmol) was added to Sub 1-I-109 (86.71 g, 237.41 mmol) _{, Pd (PPh 3) 4 (} 10.97 g, 9.50 mmol), NaOH (28.49 g, 712.22 mmol), THF (830ml), was added to water (415ml) and use the Sub 1-II-20 synthesis product 95.88 g (Yield: 75%).

(3) Sub 1-III-109 Synthesis

Triflic acid (157.6 ml, 1780.50 mmol) and pyridine aqueous solution (2080 ml, pyridine: H ₂ O = 1: 5) were added to Sub 1-II-109 obtained in the above synthesis (95.88 g, 178.05 mmol) III-20 Synthesis was carried out to obtain 36.97 g (yield: 41%) of the product.

(4) Sub 1-109 Synthesis

(CAS Registry Number: 92-67-1) (3.75 g, 22.18 mmol) and Pd (3 g) were added to Sub 1-III-109 (10.21 g, 20.16 mmol) ₂ was added to _{(dba) 3 (0.55 g,} 0.60 mmol), 50% P (t -Bu) 3 (0.8ml, 1.61 mmol), NaO t -Bu (5.81 g, 60.48 mmol), toluene (140ml) and the Sub-1-1 synthesis was used to obtain 9.47 g (yield: 79%) of the product.

(5) Sub 1-114 Synthesis

Dibenzo [ b , d ] thiophen-2-amine (CAS Registry Number: 7428-91-3) (4.58 g, 23.00 mmol) and Pd ₂ (dba) ₃ (0.57 g, 0.63 mmol), 50% P ( t- Bu) ₃ (0.8 ml, 1.67 mmol), NaO t- Bu (6.03 g, 62.73 mmol) Using the synthesis of 1-1, 9.80 g of the product (yield: 75%) was obtained.

9. Sub 1-119 Synthetic example

<Reaction Scheme 11>

(1) Sub 1-IV-119 Synthesis

(3-chlorophenyl) boronic acid (CAS Registry Number: 63503-60-6) (5.37 g, 34.34 mmol) and Pd (PPh ₃ ) ₄ (15.81 g, 31.22 mmol) (Yield: 63%) was obtained by the method of Sub 1-IV-83 using the above compound (1.44 g, 1.25 mmol), NaOH (3.75 g, 93.65 mmol), THF (110 ml) .

(2) Sub 1-119 Synthesis

Dibenzo [b, d] furan-4-amine (CAS Registry Number: 50548-43-1) (3.96 g, 21.63 mmol) and Pd ₂ (dba) ₃ (0.54 g, 0.59 mmol), 50% P ( t- Bu) ₃ (0.8 ml, 1.57 mmol), NaO t- Bu (5.67 g, 58.98 mmol) 9.29 g (Yield: 69%) of the product was obtained by the synthesis of 1-1.

The compound belonging to Sub 1 may be, but not limited to, the following compounds, and Table 1 shows FD-MS (Field Desorption-Mass Spectrometry) values of some compounds belonging to Sub 1.

[Table 1]

II. Synthesis of Sub 2

Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 11, but is not limited thereto. Hal ³ is I or Br.

<Reaction Scheme 12>

In the case of the amine (HN-Ar ⁴ Ar ⁵ ) reactant, the synthesis method disclosed in Korean Patent No. 10-1251451 (registered on March 31, 2013) of the present applicant was used.

Examples of the synthesis of specific compounds belonging to Sub 2 are as follows.

1. Sub 2-1 Synthetic example

<Reaction Scheme 13>

Diphenylamine (CAS Registry Number: 122-39-4) (7.93 g, 43.86 mmol), the starting material, was dissolved in toluene (390 ml) in a round bottom flask and then 1-bromo-3-iodobenzene (19.89 g, 70.29 mmol), Pd ₂ (dba) ₃ (1.29 g, 1.41 mmol), 50% P ( t- Bu) ₃ (1.8 ml, 3.75 mmol), NaO t- 140.58 mmol) and stir at 70 [deg.] 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 10.48 g of the product (yield: 69%).

2. Sub 2-3 Synthetic example

<Reaction Scheme 14>

1-bromo-3-iodobenzene (CAS Registry Number: 591-18-4) (18.84 g, 66.61 mmol) was added to di- p- toluylamine (CAS Registry Number: 620-93-9) _{mmol), Pd 2 (dba)} 3 (1.22 g, 1.33 mmol), 50% P (t -Bu) 3 (1.7ml, 3.55 mmol), NaO t -Bu (12.80 g, 133.21 mmol), toluene (370ml) And 10.17 g (yield: 65%) of the product was obtained using the Sub 2-1 synthesis method described above.

3. Sub 2-4 Synthetic example

<Reaction Scheme 15>

3-bromo-5-iodo-1,1'-biphenyl (CAS Registry Number: 136649-44-0) (20.08) was added to diphenylamine (CAS Registry Number: 122-39-4) (6.31 g, 37.29 mmol) _{g, 55.93 mmol), Pd 2} (dba) 3 (1.02 g, 1.12 mmol), 50% P (t -Bu) 3 (1.5ml, 2.98 mmol), NaO t -Bu (10.75 g, 111.86 mmol), toluene (310 ml) was added and 10.90 g of the product (yield: 73%) was obtained using the Sub 2-1 synthesis method.

4. Sub 2-13 Synthetic example

<Reaction Scheme 16>

1-bromo-3-iodobenzene (CAS Registry Number: 591-18) was added to N- phenyldibenzo [ b , d ] thiophen-2-amine (CAS Registry Number: 1300028-91-4) (9.42 g, 34.21 mmol) -4) (14.52 g, 51.31 mmol ), Pd 2 (dba) 3 (0.94 g, 1.03 mmol), 50% P (t -Bu) 3 (1.3ml, 2.74 mmol), NaO t -Bu (9.86 g, 102.63 mmol) and toluene (285 ml) were added, and 10.31 g (yield: 70%) of the product was obtained using the Sub 2-1 synthesis method.

5. Sub 2-29 Synthetic example

<Reaction Scheme 17>

The starting material of diphenylamine (CAS Registry Number: 122-39-4) (4.29 g, 25.35 mmol) in 2,11-dibromotriphenylene (CAS Registry Number: 24253-51-8) (14.68 g, 38.03 mmol), Pd 2 ( _{dba) 3 (0.70 g, 0.76} mmol), 50% P (t -Bu) 3 (1.0ml, 2.03 mmol), NaO t -Bu (7.31 g, 76.05 mmol), was added to toluene (210ml) and the Sub 2 -1 &lt; / RTI &gt; synthesis method was used to obtain 9.02 g (yield: 75%) of the product.

6. Sub 2-30 Synthetic example

<Reaction Scheme 18>

1-bromo-4-iodobenzene (CAS Registry Number: 589-87-7) (19.26 g, 68.07 mmol) was added to the starting material diphenylamine (CAS Registry Number: 122-39-4) (7.68 g, 45.38 mmol) ₂ (dba) ₃ (1.25 g, 1.36 mmol), 50% P ( t- Bu) ₃ (1.8 ml, 3.63 mmol), NaO t- Bu (13.08 g, 136.15 mmol) 10.59 g (Yield: 72%) of the product was obtained using Sub 2-1 synthesis method.

7. Sub 2-43 Synthetic example

<Reaction Scheme 19>

4-bromo-4'-iodo-1,1'-biphenyl (CAS Registry Number: 105946-82-5) was added to diphenylamine (CAS Registry Number: 122-39-4) (6.57 g, 38.82 mmol) 20.91 g, 58.23 mmol), Pd 2 (dba) 3 (1.07 g, 1.16 mmol), 50% P (t -Bu) 3 (1.5ml, 3.11 mmol), NaO t -Bu (11.19 g, 116.47 mmol), toluene (325 ml) was added, and 10.10 g (Yield: 65%) of the product was obtained using the Sub 2-1 synthesis method described above.

8. Sub 2-52 Synthetic example

<Reaction Scheme 20>

Bromo-2-iodobenzene (CAS) was added to the starting material, 4- (dibenzo [ b , d ] furan-2-yl) - N -phenylaniline (CAS Registry Number: 1381976-37-9) (12.46 g, 37.15 mmol) Registry Number: 583-55-1) (15.76 g , 55.72 mmol), Pd 2 (dba) 3 (1.02 g, 1.11 mmol), 50% P (t -Bu) 3 (1.4ml, 2.97 mmol), NaO t -Bu (10.71 g, 111.45 mmol) and toluene (310 ml) were added, and 9.66 g of the product (yield: 53%) was obtained using the Sub 2-1 synthesis method.

The compound belonging to Sub 2 may be, but not limited to, the following compounds, and Table 2 shows FD-MS (Field Desorption-Mass Spectrometry) values of some compounds belonging to Sub 2.

[Table 2]

III. Product synthesis

Sub 1 (1 eq.) Was dissolved in toluene in a round bottom flask and then Sub 2 (1 eq.), Pd ₂ (dba) ₃ (0.03 eq.), (T- Bu ₃ P 3 eq.) Was added and stirred at 100 [deg.] 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 subjected to silicagel column and recrystallization to obtain final product.

1. P-1 Synthetic example

<Reaction Scheme 21>

Sub 1-1 (3.96 g, 8.95 mmol) obtained in the above synthesis was dissolved in toluene (90 ml) in a round bottom flask and Sub 2-1 (2.90 g, 8.95 mmol) and Pd ₂ (dba) ₃ (0.25 g, 0.27 mmol), 50% P ( t- Bu) ₃ (0.3 ml, 0.54 mmol) and NaO t- Bu (2.58 g, 26.84 mmol) were added and stirred at 100 ° 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 5.65 g (yield: 92%) of the product.

2. P-20 Synthetic example

<Reaction Formula 22>

Sub 2-13 (2.62 g, 6.10 mmol), Pd ₂ (dba) ₃ (0.17 g, 0.18 mmol) and 50% P ( t- Bu) were added to Sub 1-20 (3.81 g, 6.10 mmol) ₃ (0.2 ml, 0.37 mmol), NaO t- Bu (1.76 g, 18.29 mmol) and toluene (60 ml) were added and 5.11 g of the product (yield: 86%) was obtained using the P-1 synthesis method.

3. P-35 Synthetic example

<Reaction Scheme 23>

Sub 2-29 (3.33 g, 7.01 mmol), Pd ₂ (dba) ₃ (0.19 g, 0.21 mmol) and 50% P ( t- Bu) were added to Sub 1-28 (4.03 g, 7.01 mmol) _{3 (0.2ml, 0.42 mmol),} NaO t -Bu (2.02 g, 21.03 mmol), was added toluene (70ml), and using the P-1 synthesis product was 4.89 g (yield: 72%) was obtained.

4. P-40 Synthetic example

<Reaction Scheme 24>

Sub-2-3 (2.32 g, 6.58 mmol), Pd ₂ (dba) ₃ (0.18 g, 0.20 mmol) and 50% P ( t- Bu) were added to Sub 1-44 (4.67 g, 6.58 mmol) _{3 (0.2ml, 0.39 mmol),} NaO t -Bu (1.90 g, 19.74 mmol), was added toluene (65ml), and using the P-1 synthesis product was 4.97 g (yield: 77%) was obtained.

5. P-52 Synthetic example

<Reaction Scheme 25>

(3.20 g, 8.00 mmol), Pd ₂ (dba) ₃ (0.22 g, 0.24 mmol) and 50% P ( t- Bu) were added to Sub 1-46 (3.54 g, 8.00 mmol) ₃ (0.2 ml, 0.48 mmol), NaO t- Bu (2.31 g, 24.00 mmol) and toluene (80 ml) were added and the product P-1 was used to obtain 5.42 g of the product (yield: 89%).

6. P-71 Synthetic example

<Reaction Scheme 26>

(2.42 g, 7.47 mmol), Pd ₂ (dba) ₃ (0.21 g, 0.22 mmol) and 50% P ( t- Bu) were added to Sub 1-60 (4.10 g, 7.47 mmol) ₃ (0.2 ml, 0.45 mmol), NaO t- Bu (2.15 g, 22.42 mmol) and toluene (75 ml) were added and the product P-1 was used to obtain 5.33 g (yield: 90%) of the product.

7. P-79 Synthetic example

<Reaction Scheme 27>

Sub 2.43 (2.91 g, 7.28 mmol), Pd ₂ (dba) ₃ (0.20 g, 0.22 mmol) and 50% P ( t- Bu) were added to Sub 1-46 (3.22 g, 7.28 mmol) ₃ (0.2 ml, 0.44 mmol), NaO t- Bu (2.10 g, 21.83 mmol) and toluene (75 ml) were added and the product P-1 was used to obtain 4.71 g (yield: 85%) of the product.

8. P-85 Synthetic example

<Reaction Scheme 28>

52 (3.84 g, 7.83 mmol), Pd ₂ (dba) ₃ (0.22 g, 0.23 mmol) and 50% P ( t- Bu) were added to Sub 1-73 (4.06 g, 7.83 mmol) ₃ (0.2 ml, 0.47 mmol), NaO t- Bu (2.26 g, 23.48 mmol) and toluene (80 ml) were added and the product P-1 was used to obtain 5.30 g of the product (yield: 73%).

9. P-89 Synthetic example

<Reaction Scheme 29>

Sub-30 (2.29 g, 7.06 mmol), Pd ₂ (dba) ₃ (0.19 g, 0.21 mmol) and 50% P ( t- Bu) were added to Sub 1-79 (4.23 g, 7.06 mmol) ₃ (0.2 ml, 0.42 mmol), NaO t- Bu (2.04 g, 21.19 mmol) and toluene (70 ml) were added and the product P-1 was used to obtain 5.29 g of the product (yield: 89%).

10. P-96 Synthetic example

<Reaction Scheme 30>

Sub 2-1 (2.91 g, 8.97 mmol), Pd ₂ (dba) ₃ (0.25 g, 0.27 mmol) and 50% P ( t- Bu) were added to Sub 1-83 (4.65 g, 8.97 mmol) ₃ (0.3 ml, 0.54 mmol), NaO t- Bu (2.58 g, 26.90 mmol) and toluene (90 ml) were added and the product P-1 was used to obtain 5.87 g of the product (yield: 86%).

11. P-101 Synthetic example

<Reaction Scheme 31>

Sub 2-3 (2.77 g, 7.88 mmol), Pd ₂ (dba) ₃ (0.22 g, 0.24 mmol) and 50% P ( t- Bu) were added to Sub 1-96 (5.52 g, 7.88 mmol) ₃ (0.2 ml, 0.47 mmol), NaO t- Bu (2.27 g, 23.63 mmol) and toluene (80 ml) were added and the product P-1 was used to obtain 4.90 g of the product (yield: 64%).

12. P-119 Synthetic example

<Reaction equation 32>

Sub 2-1 (2.79 g, 8.61 mmol), Pd ₂ (dba) ₃ (0.24 g, 0.26 mmol) and 50% P ( t- Bu) were added to Sub 1-109 (5.12 g, ₃ (0.3 ml, 0.52 mmol), NaO t- Bu (2.48 g, 25.82 mmol) and toluene (85 ml) were added and the product P-1 was used to obtain 5.56 g of the product (yield: 77%).

13. P-125 Synthetic example

<Reaction Scheme 33>

Sub 2-1 (2.78 g, 8.58 mmol), Pd ₂ (dba) ₃ (0.24 g, 0.26 mmol) and 50% P ( t- Bu) were added to Sub 1-114 (5.36 g, 8.58 mmol) ₃ (0.3 ml, 0.51 mmol), NaO t- Bu (2.47 g, 25.74 mmol) and toluene (85 ml) were added and the product P-1 was used to obtain 5.29 g of the product (yield: 71%).

14. P-135 Synthetic example

<Reaction formula 34>

Sub 2-1 (2.66 g, 8.19 mmol), Pd ₂ (dba) ₃ (0.23 g, 0.25 mmol) and 50% P ( t- Bu) were added to Sub 1-119 (5.61 g, 8.19 mmol) ₃ (0.2 ml, 0.49 mmol), NaO t- Bu (2.36 g, 24.57 mmol) and toluene (80 ml) were added and 5.17 g (yield: 68%) of the product was obtained using the P-1 synthesis method.

The FD-MS values of some compounds of the present invention prepared according to the above synthesis examples are shown in Table 3 below.

[Table 3]

In the above has been described for an exemplary composite of the present invention represented by the general formula (1), all of Buchwald-Hartwig cross coupling reaction, Suzuki cross-coupling reaction, Intramolecular acid-induced cyclization reaction (J. mater. Chem. 1999, 9, 2095.), the reaction proceeds even if other substituents (Ar ¹ to Ar ⁵ , L ¹ to L ³ , R ¹ , R ² , m and n) defined in Chemical Formula 1 are bonded in addition to the substituents specified in the specific synthesis examples It will be readily understood by those skilled in the art. Sub 1 - III -> Sub 1 reaction, Sub 1 - III reaction, Sub 1 - III reaction, Sub 1 - I reaction, 1 - IV -> Sub 1 reaction In Scheme 12, the starting materials -> Sub 2 reactions are all based on the Buchwald-Hartwig cross coupling reaction and in Scheme 2, Sub 1 -I -> Sub 1-II reactions, Sub 1-III -> Sub 1-IV reaction is based on the Suzuki cross-coupling reaction, in the reaction scheme 2 Sub 1-II -> Sub 1-III reactions Intramolecular acid-induced cyclization reaction (J. mater Chem 1999, 9, 2095.. .). The above reactions will proceed even if a substituent not specifically mentioned is attached.

Evaluation of manufacturing of organic electric device

[ Example  One] 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, 4,4 ', 4 "-tris [2-naphthyl (phenyl) amino] triphenylamine (hereinafter abbreviated as" 2-TNATA ") was deposited on the ITO layer (anode) To form a hole injection layer. Then, the compound P-1 of the present invention was vacuum deposited on the hole injection layer to a thickness of 60 nm to form a hole transport layer. Subsequently, tris (2-phenylpyridine) -iridium (hereinafter referred to as "Ir (ppy) 2") was used as a host material on the hole transport layer, and 4,4'-N, N'-dicarbazole- ) ₃ &quot;) as a dopant material was doped in a ratio of 90:10 by weight and vacuum deposited 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 &quot; Alq ₃ &quot;) was vacuum deposited on the hole blocking layer 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 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  33] Green organic electroluminescent device  ( Hole transport layer )

An organic electroluminescent device was fabricated in the same manner as in Example 1, except that the compounds P-6 to P-134 of the present invention described in the following Table 4 were used in place of the compound P-1 of the present invention as the hole transport layer material .

[ Comparative Example  1] to [ Comparative Example  6] Green organic electroluminescent device  ( Hole transport layer )

An organic electroluminescent device was fabricated in the same manner as in Example 1 except that the following Comparative Compounds 1 to 6 described in Table 4 were used in place of the compound P-1 of the present invention as a hole transport layer material.

&Lt; Comparative Compound 1 > < Comparative Compound 2 > < Comparative Compound 3 &

&Lt; Comparative Compound 4 > < Comparative Compound 5 > < Comparative Compound 6 &

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 33 and Comparative Examples 1 to 6 of the present invention And the T95 lifetime was measured by a lifetime measuring apparatus manufactured by Mac Science Inc. at a reference luminance of 5000 cd / m ^2. The measurement results are shown in Table 4 below.

[Table 4]

As can be seen from the results of Table 4, the organic electroluminescent device using the compound of the present invention as the hole transport layer material has a relatively low driving voltage as compared with the organic electroluminescent device using Comparative Compounds 1 to 6 as the hole transport layer material, It can be confirmed that not only the luminous efficiency is improved but also the lifetime and the like are improved.

Compared with the compound P-6 of the present invention and Comparative Compounds 3 to 5, they all have the same skeleton but differ in the kind of atoms (S, C, N, O) introduced into the core. It can be seen that the characteristics of the device are different when a compound in which the kinds of atoms to be atomized are different from each other is used as the hole transporting layer material. It can be seen that when the dibenzothiophene in which S is introduced into the core as the hole transport layer material as in the present invention, the efficiency and lifetime of the organic electric device are the most excellent.

This is because when a dibenzothiophene is introduced into a heterocyclic core instead of carbazole (Example 4) or dibenzofuran (Example 5), it has a deep HOMO energy level and a high refractive index and is used as a hole transport layer material Since the device has a high light transmittance, the luminous efficiency is increased, and the hole movement through the deep HOMO energy level is facilitated, so that the charge balance in the light emitting layer of holes and electrons is increased, thereby maximizing the luminous efficiency and lifetime Seems to be.

Comparing the comparative example 3, the comparative example 4, the comparative example 5, and the embodiment of the present invention, it can be seen that the lifetime and the efficiency are remarkably improved when the atoms are heteroatoms introduced onto the same skeleton. Particularly, when the core contains Sp3 carbon as in Comparative Compound 3, it exhibits lower thermal stability than the compound of the present invention, so that the Joule heat generated between the organic layer and the organic layer or between the organic layer and the metal electrode during electroluminescence It was confirmed that the heat resistance and the resistance under high temperature environment were reduced.

Comparing the examples using the compound of Comparative Example 2 with the compounds of the present invention (particularly P-1 and P-6), it can be seen that the driving voltage is lowered and the efficiency and lifetime are remarkably improved in the embodiment of the present invention. Compounds P-1 and P-6 of the present invention and Comparative Compound 2 are the same in that diphenylamine (-N (C ₆ H ₆ ) ₂ ) is bonded to both benzene rings of the dibenzothiophene skeleton by a substituent , In the case of the compounds of the present invention, one of the diphenylamine substituents phenyl is further substituted with diphenylamine. That is, when a diamine type in which an amine (-L ¹ -NAr ⁴ Ar ⁵ ) is directly or indirectly substituted with an amine substituent directly or indirectly bonded to a dibenzothiophene is used as a hole transport layer material , The life and efficiency are remarkably improved as compared with Comparative Example 2. [ This is because the HOMO energy level of the hole transport layer is lowered by introducing the compound of the present invention within an appropriate range without excessively increasing the number of aryl (-L ¹ -NAr ⁴ Ar ⁵ ) substituted with an amine as an amine substituent, And the hole transport layer has the most appropriate HOMO energy level difference with the light emitting layer, so that the charge balance is increased and the light emission in the light emitting layer is better performed.

Comparing Comparative Example 6 with the Examples of the present invention, it can be seen that the luminous efficiency and lifetime of Examples of the present invention are remarkably improved as compared with Comparative Example 6. Comparing the compound used in Comparative Example 6 with the compound used in Examples of the present invention, the comparative Compound 6 and the compounds P-51 and P-58 of the present invention have an amine group (-L ³ -N (Ar ² ) (Ar ³ )), Ar ² is the same but Ar ³ is different from each other. That is, in Comparative Compound 6 and the compounds P-51 and P-58 of the present invention, L ³ is a single bond and Ar ² is the same as phenyl, while Ar ³ is a carbazole derivative, -51 is different from phenyl, and P-58 is different from dibenzothiophene. Therefore, even in the structure having the same skeleton, the characteristics of the device are different depending on the kind of the amine group substituted in the dibenzothiophene core, and when Ar ² and / or Ar ³ is a carbazole (carbazole derivative) Is used as a hole transporting layer material, the use of the compound of the present invention as a hole transporting layer material can remarkably improve the light emitting efficiency and lifetime. Particularly, when Compound P-58 in which dibenzothiophene is introduced as a substituent substituting for an amine group is used as a hole transport layer material, Comparative Compound 6 in which carbazole is introduced as a substituent substituting for an amine is used as a hole transport layer material, It is confirmed that the refractive index is higher and the luminous efficiency is remarkably improved.

On the other hand, in the compound of the present invention, when the linking group L ¹ connecting the amine and the amine is phenylene, the characteristics of the device are different depending on the bonding position. Compounds P-1 and P-11 of the present invention can be synthesized by reacting an amine group with meta or ortho of the phenylene of the linking group, P-6 is an example in which the amine group is bonded to the para position of the phenylene at the linkage and that these compounds are used as the hole transport layer material in Example 1 (using the compound P-1), Example 2 (Using the compound P-6) and Example 6 (using the compound P-11), the luminous efficiency and lifetime of Example 2 are better. Therefore, when the linking group L &lt; ¹ &gt; is phenylene, it can be seen that the compound in which the amine is bonded to the linking group in the para position is more suitable as the hole transporting layer material. On the other hand, when the linking group L &lt; ¹ &gt; is phenylene, the compound in which the amine is bound to the linking group in the meta or ortho position has a deeper HOMO energy level than the compound in the para position and consequently the amine is bonded to the linking group in the meta or ortho position It can be confirmed that the compound is more suitable as the light emitting auxiliary layer material.

Taking all of the above-mentioned characteristics (high refractive index, high thermal stability and deep HOMO energy level) into consideration, it is considered that two amines are substituted for the kind of atoms (S, C, N, O) and core (dibenzothiophene) (-L ¹ -NAr ⁴ Ar ⁵ ) substituted with an amine as an amine substituent is further introduced and the type of the amine substituent, the band gap, the electrical characteristics, the interface characteristics, and the like are largely changed , Which can be seen as a major factor in improving the performance of the device.

In the case of the hole transporting layer, it is necessary to grasp the relationship with the light emitting layer (host), and it is an object of the present invention to infer the advantageous effect (characteristic) shown by using the compound according to the present invention as a hole transporting layer material, Even ordinary technicians who belong to it will be very difficult.

[ Example  34] Red organic electroluminescent 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. 2-TNATA was vacuum-deposited on the ITO layer (anode) formed on the glass substrate to a thickness of 60 nm to form a hole injection layer. Then, NPB was vacuum deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer Respectively. Subsequently, Compound P-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. Then, CBP (bis- (1-phenylisoquinolyl) Iridium (III) acetylacetonate (hereinafter abbreviated as "(piq) ₂ Ir (acac)") as a dopant was doped at a weight ratio of 95: 5 and vacuum deposited to 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 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. Thus, an organic electroluminescent device was manufactured.

[ Example  35] to [ Example  104] Red organic electroluminescent device  ( The light- )

Except that the compounds P-2 to P-134 of the present invention were used instead of the compound P-1 of the present invention as the luminescent auxiliary layer material as shown in the following Table 5, Respectively.

[ Comparative Example  7]

An organic electroluminescent device was fabricated in the same manner as in Example 34 except that no luminescent auxiliary layer was formed.

[ Comparative Example  8] to [ Comparative Example  14]

An organic electroluminescent device was produced in the same manner as in Example 34 except that the following Compounds 2 to 8 were used instead of the compound P-1 of the present invention as the luminescent auxiliary layer material, Respectively.

     &Lt; Comparative Compound 7 > < Comparative Compound 8 >

Electruminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured by Examples 34 to 104 and Comparative Examples 7 to 14 of the present invention And the T95 lifetime was measured through a life measuring apparatus manufactured by Mac Science Inc. at a reference luminance of 2500 cd / m ^2. The measurement results are shown in Table 5 below.

[Table 5]

As can be seen from the results of Table 5, the organic electroluminescent device using the compound of the present invention as the light emitting auxiliary layer material has improved luminous efficiency and significantly improved lifetime compared to the organic electroluminescent devices of Comparative Examples 7 to 14 .

Compared to Comparative Example 7 in which the light-emission-assisting layer was not formed, Comparative Examples 8 to 14 in which a light-emission-assisting layer was formed using Comparative Compounds 2 to 8 and Comparative Examples 8 to 14 in which the light- The luminous efficiency and lifetime of the organic electroluminescent device of the embodiment of the present invention are improved. Particularly, according to the embodiment of the present invention, the luminous efficiency and lifetime are remarkably improved.

In the same manner as mentioned in Table 4 above, it is considered that the type of the atoms (S, C, N, O) introduced into the core and the amine substituent in the structure in which two amines are substituted in the core (dibenzothiophene) Whether or not the substituted aryl (-L ¹ -NAr ⁴ Ar ⁵ ) is further introduced and the type of the amine substituent act as a main factor for improving the performance of the device not only in the hole transporting layer but also in the light emission-assisting layer (red phosphorescence) , A high T1 value, and a deep HOMO energy level capable of efficiently transporting holes in the hole transport layer, thereby facilitating charge balance within the light emitting layer.

Particularly, when at least one heterocyclic substituent such as dibenzothiophene is introduced in the substituent substituted with an amine among the compounds of the present invention, the refractive index is higher than that in the case where at least one substituent substituted with an amine has at least one aryl or carbazole , Indicating a high Tg value, it was confirmed that the light emitting efficiency and the thermal stability were improved.

On the other hand, in the evaluation results of the above-described device fabrication, the device characteristics in which the compound of the present invention is applied to only one of the hole transporting layer and the light emitting auxiliary layer has been described. However, the compound of the present invention may be applied to both the hole transporting layer and the light emitting supporting layer.

The foregoing description is merely illustrative of the present invention, and various modifications may be made without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are intended to be illustrative, not limiting, and are not intended to limit the scope and spirit of the present invention. The scope of protection of the present invention should be construed according to the 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 (13)

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

In Formula 1,
L ¹ is a C ₆ -C ₆₀ arylene group,
L ² and L ³ independently of one another are a single bond; C ₆ -C ₆₀ arylene groups; A fluorenylene group; A C ₂ -C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; And a fused ring group of an aromatic ring of C ₆ -C ₆₀ and an aliphatic ring of C ₃ -C ₆₀ ,
Ar ¹ to Ar ⁵ independently represent a C _{6 to} C ₆₀ aryl group; Heterocyclic group of O, N, S, Se, C 2 -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fluorenyl group; A fused ring group of a C ₆ -C ₆₀ aromatic ring and a C ₃ -C ₆₀ aliphatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And an aryloxy group of C ₆ -C ₃₀ , with the proviso that the carbazole is excluded from Ar ² and Ar ³ ,
m and n are each an integer of 0 to 3,
R ¹ and R ² independently of one another are deuterium; Tritium; halogen; Cyano; A nitro group; An aryl group of C ₆ -C ₆₀ ; A fluorenyl group; Heterocyclic group of O, N, S, Se, C 2 -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₆ -C ₆₀ aromatic ring and a C ₃ -C ₆₀ aliphatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And a C ₆ -C ₃₀ aryloxy group, and when m and n are each an integer of 2 or more, a plurality of R ^{1 s} and R ^{2 s} are the same or different, and adjacent R ^{1 s} or adjacent R ^{2 s} They may be bonded to each other to form a ring,
Ar ¹ to Ar ⁵ , R ¹ , R ² , L ¹ to L ³ , a ring formed by bonding adjacent R ¹ groups to each other, and a ring formed by bonding adjacent R ² groups to each other include deuterium; halogen; A silane group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; A phosphine oxide group substituted or unsubstituted with an alkyl group having _{1 to 20} carbon atoms or an aryl group having _{6 to 20} carbon atoms; Siloxyl group; Boron group; Germanium group; Cyano; A nitro group; An alkyl thio group of C ₁ -C ₂₀ ; A C ₁ -C ₂₀ alkoxyl group; A C ₁ -C ₂₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₆ -C ₂₀ aryl group; A C ₆ -C ₂₀ aryl group substituted by deuterium; A fluorenyl group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Se, Si and P; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ -C ₂₀ ; -N (R ^a ) (R ^b ); Aryl alkenyl group of C ₈ -C _20; And

&Lt; RTI ID = 0.0 &gt; and / or &lt; / RTI &gt; The method according to claim 1,
(1) is represented by one of the following Chemical Formulas (2) to (5):
&Lt; Formula 2 >< EMI ID =

<Formula 4><Formula5>

In the above Chemical Formulas 2 to 5, Ar ¹ to Ar ⁵ , R ¹ , R ² , L ¹ to L ³ , m and n are the same as defined in claim 1. The method according to claim 1,
The compound of formula (I) is represented by one of the following formulas (6) to (10):
&Lt; Formula 6 >< EMI ID =

&Lt; Formula 9 &gt;&lt; EMI ID =

In the above Chemical Formulas 6 to 10, Ar ¹ to Ar ⁵ , R ¹ , R ² , L ¹ to L ³ , m and n are the same as defined in claim 1. The method according to claim 1,
Wherein L < ¹ > is represented by one of the following formulas L1-1 to L1-7:
&Lt; General Formula (L1-1) >< General Formula (L1-2) >

&Lt; Formula L1-4 >< Formula L1-5 >< Formula L1-6 &

In the above formulas L1-1 to L1-7,
a to c each represent an integer of 0 to 4, d represents an integer of 0 to 6, e represents an integer of 0 to 5, f and g each represent an integer of 0 to 3,
R ³ to R ⁵ independently represent an aryl group; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And a C ₆ -C ₃₀ aryloxy group, and when a to g are each an integer of 2 or more, each of R ³ to R ⁵ may be the same or different. The method according to claim 1,
Wherein at least one of Ar &^lt; ¹ > to Ar &^lt; ⁵ &gt;
&Lt; Formula 11 &gt;

In Formula 11,
When Ar ^1, Ar ^4, and at least one of Ar ⁵ is of the formula 11 X is S, Se, O, C ( R c) (R d) or N (R ^e) and, Ar ^2, and at least one of Ar ³ is when the formula 11 X is S, Se, and O, or ^{C (R c) (R d} ), C (R c) (R d) and in N (R ^e), R ^c to R ^e are independently C together An aryl group of _{6 to 60} carbon atoms; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And an aryloxy group of C ₆ -C ₃₀ , R ^c and R ^d may combine with each other to form a spiro compound together with the carbon to which they are bonded,
L ⁴ is a single bond; A C ₆ -C ₂₀ arylene group; A fluorenylene group; A C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; And a fused ring group of a C ₃ -C ₂₀ aliphatic ring and a C ₆ -C ₂₀ aromatic ring,
o is an integer from 0 to 3, p is an integer from 0 to 4, R ⁶ and R ⁷ are independently from each other deuterium; Tritium; halogen; Cyano; A nitro group; An aryl group of C ₆ -C ₆₀ ; A fluorenyl group; Heterocyclic group of _{O, N, S, C 2} -C 60 containing at least one heteroatom selected from the group consisting of Si and P; A fused ring group of a C ₃ -C ₆₀ aliphatic ring and a C ₆ -C ₆₀ aromatic ring; A C ₁ -C ₅₀ alkyl group; An alkenyl group of C ₂ -C ₂₀ ; A C ₂ -C ₂₀ alkynyl group; A C ₁ -C ₃₀ alkoxyl group; And C ₆ -C ₃₀ aryloxy groups, and when o and p are each an integer of 2 or more, each of a plurality of R ⁶ and R ⁷ is the same or different,
When o and p are each an integer of 2 or more, adjacent R ⁶ and adjacent R ⁷ may be bonded to each other to form a ring. 6. The method of claim 5,
At least one of Ar ¹ , Ar ² and Ar ⁵ is the formula (11), wherein X is S in the formula (11). The method according to claim 1,
Wherein the compound of formula (I) is one of the following compounds:

An organic electroluminescent device comprising a first electrode, a second electrode, and an organic layer formed between the first electrode and the second electrode,
Wherein the organic material layer contains the compound of any one of claims 1 to 7. 9. The method of claim 8,
Wherein the organic material layer includes at least one of a hole injecting layer, a hole transporting layer, a light emitting auxiliary layer, a light emitting layer, an electron transporting auxiliary layer, an electron transporting layer and an electron injecting layer,
Wherein at least one of the hole injecting layer, the hole transporting layer, the luminescent auxiliary layer, the light emitting layer, the electron transporting auxiliary layer, the electron transporting layer and the electron injecting layer contains the compound as a single species compound or a mixture of two or more species. Electric device. The method of claim 9, wherein
Wherein the organic layer includes a light emitting layer and a light emitting auxiliary layer,
Wherein the light emitting layer comprises a phosphorescent red light emitting material, and the compound is contained in the light emitting auxiliary layer. 9. The method of claim 8,
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 8; And
And a control unit for driving the display device. 13. The method of claim 12,
Wherein the organic electroluminescent device is one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, and a monochromatic or white illumination device.

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