KR20170037135A - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

Provided are a compound capable of improving light emitting efficiency, driving voltage and lifespan, an organic electronic element using the same and an electronic device thereof. The organic electronic element (100) comprises: a first electrode (120) formed on a substrate (110); a second electrode (180); and an organic layer interposed between the first electrode (110) and the second electrode (180) and containing the compound of the present invention.

Description

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

The present invention relates to a novel retarding fluorescent material, an organic electroluminescent device using the retarding fluorescent material, and an electronic device therefor.

Research on increasing the luminous efficiency of organic electroluminescent devices (organic electroluminescent devices) has been actively conducted until recently, and this has been a big issue in the development of organic electroluminescent devices.

In recent years, an organic electroluminescent device using a retardation fluorescent material, which is evaluated as a material for a third generation organic electroluminescent device following fluorescent and phosphorescent materials, is attracting attention.

This material is a material that converts triplet exciton into singlet and converts it into light, unlike a phosphorescent material that converts singlet excitons into triplets and converts them into light. Since the retarded fluorescent material can theoretically change both singlet and triplet excitons to light, it is expected to be a material capable of overcoming the lifetime and efficiency limitations of the blue phosphorescent material by enabling 100% internal quantum efficiency .

Organic electroluminescent devices using a delayed fluorescent compound containing metals such as Cu, Pt, In, Pd, Sn, and Zn have been reported in Patent Documents 1 to 4, and a combination of an acceptor compound and a donor compound Recently, there has been a growing trend in the use of exciplex-based retarded fluorescent materials.

As delayed fluorescent materials using exciplex, five-ring cyclic compound derivatives including a heterocyclic ring, anthracene derivatives, biscarbazole derivatives, and fluorene derivatives have been reported in Patent Documents 5 to 8.

[Patent Document 1] JP2011-213643 (published)

[Patent Document 2] JP2013-095688 (published)

[Patent Document 3] JP2013-112608 (published)

[Patent Document 4] JP2013-120770 (published)

[Patent Document 5] JP2014-009352 (published)

[Patent Document 6] JP5565743 (registered)

[Patent Document 7] JP2013-265214 (published)

[Patent Document 8] JP2014-141571 (published)

A new retardation fluorescent material using an exciplex has been developed and applied to an organic electroluminescent device to improve luminous efficiency.

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

(Wherein A comprises a carbocyclic or heterocyclic aromatic ring, and plural A's are the same or different from each other)

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, a high luminous efficiency and a low driving voltage of the device can be achieved, and the lifetime of the device can be greatly improved.

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).

The term "alkyl" or "alkyl group ", as used herein, unless otherwise indicated, has a single bond of from 1 to 60 carbon atoms and includes straight chain alkyl groups, branched chain alkyl groups, cycloalkyl (alicyclic) Quot; means a radical of a saturated aliphatic functional 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 terphenyl group, a naphthyl group, an anthracenyl group, a fluorene group, a spirobifluorene 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, a heterocycle of 2 to 60 carbon atoms, or a combination thereof, Saturated or unsaturated ring.

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

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

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

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

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

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

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

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

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

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

The compound according to the present invention applied to the organic material layer may be a host or 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.

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- In particular, when the optimal combination of the energy level and T1 value and the intrinsic properties (mobility, interfacial characteristics, etc.) between the organic layers is achieved, it is possible to achieve long life and high efficiency at the same time.

Accordingly, in the present invention, by forming the light emitting layer using the compound represented by the general formula (1), it is possible to optimize the energy level and the Tl value between the respective organic layers, the mobility of the material, And efficiency can be improved at the same time.

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

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

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

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

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

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

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

A compound according to one aspect of the present invention is represented by the following formula (1). The present compound may be a retarded fluorescent compound.

≪ Formula 1 >

In Formula 1,

R 'is independently from each other deuterium; halogen; An alkyl group having _{1 to 60} carbon atoms; An aryl group of C ₆ -C ₆₀ ; A fluorenyl group; Cyano; 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 ; 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 ; A C ₂ -C ₆₀ carbocyclic aromatic ring; Heterocyclic C ₂ -C ₆₀ aromatic ring; if may be selected from the group consisting of, it is possible to exclude the carbazole or condensed (fused) carbazole, n = 0 is a hydrogen, a plurality of R ' May be the same or different.

A may comprise a C ₂ -C ₆₀ carbocyclic or heterocyclic aromatic ring and may exclude a carbazole or fused carbazole and the plurality of A may be the same or different from each other .

l is an integer of 0 to 4, m is an integer of 1 to 5, and n is an integer of 0 to 4.

Each of the aryl group, the alkyl group, the fluorenyl group, the cyano group, the heterocyclic group, the fused ring group, the alkenyl group, the alkynyl group, the alkoxyl group, the aryloxy group, the carbocyclic aromatic ring and the heterocyclic aromatic ring, , a silane group, a siloxane group, a boron group, a germanium group, a cyano group, a nitro _{group, -L'-N (R c)} (R d) ( wherein L 'is a single bond; an aryl group of C ₆ ~ C _60; A fused ring group of a C ₃ to C ₆₀ aliphatic ring and a C ₆ to C ₆₀ aromatic ring, and a C ₂ to C ₆₀ heterocyclic group; and R _c and R _d is independently 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, S, Si and P And a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of C ₁ ~ C ₂₀ coming of the alkylthio, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkene group, C ₂ ~ C ₂₀ alkynyl, C ₆ ~ C ₂₀ of the a substituted aryl group, a deuterium, C ₆ ~ C ₂₀ aryl group, fluorenyl group, C ₂ ~ C heterocyclic group of _20, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C aryl group of _20, C ₈ ~ C ₂₀ aryl alkenyl group, a carbonyl group, an ether group, C ₂ ~ C ₂₀ of the alkoxyl group, C ₆ ~ aryloxy _{C 30, -O-Si (R} x) 3, and R ^x O-Si (R ^x ) ₂ - wherein R ^x is hydrogen, a C ₆ to C ₂₀ aryl group, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₈ to C ₂₀ arylalkenyl group, An arylalkoxyl group having ₇ to ₂₀ carbon atoms, or an alkoxycarbonyl group having ₂ to ₂₀ carbon atoms).

Here, the aryl group may be an aryl group having 6 to 60 carbon atoms, preferably 6 to 40 carbon atoms, and more preferably 6 to 30 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,

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, A in the formula (1) may be represented by one of the following formulas. When m is 2 and A is 2, two or more A's may be different from each other, but the present invention is not limited thereto.

 &Lt; Formula 2 > < EMI ID =

 &Lt; Formula 5 > < EMI ID =

In the above Chemical Formulas 2 to 6,

X is O, S or CR &lt; ⁶ &gt; R &lt; ^{7 &} gt ;.

Y ¹ to Y ⁴ are independently of each other CR "or N, and at least one is N, and when a plurality of R" s exist, the plurality of R "s may be the same or different from each other.

R ⁶ and R ⁷ are independently of each other hydrogen; heavy hydrogen; An alkyl group having _{1 to 60} carbon atoms; A C ₆ -C ₆₀ aryl group;

Further, R ⁶ and R ⁷ may combine with each other to form at least one ring. Here, R ⁶ and R ⁷ which do not form a ring may be defined as defined above.

R ⁸ - R ⁴⁵ and R "are independently of each other hydrogen, deuterium, halogen, nitro, C ₁ -C ₆₀ alkyl (straight chain, branched chain), C ₁ -C ₆₀ alkoxy, C ₆ -C ₆₀ aryloxy; An amino group, a silyl group, a C ₂ -C ₆₀ alkenyl group, a C ₆ -C ₆₀ aryl group, a C ₂ -C ₆₀ heteroaryl group, a carbonyl group, an ester group, a nitrile group, a sulfanyl group, ; A phosphino group; and a fluorenyl group.

In addition, two arbitrary two adjacent groups of R ⁸ to R ¹⁵ , two adjacent arbitrary groups of R ¹⁶ to R ¹⁹ , two adjacent arbitrary groups of R ²⁰ to R ²⁷ , and R ³⁰ to R ³³ Two arbitrary adjacent two groups, any two adjacent groups of R ⁴² to R ⁴⁵ , and any two adjacent groups of the plurality of R "s may be bonded to each other to form at least one ring. R &lt; ⁸ &gt; to R &lt; ^{8 &} R ⁴⁵ and R "may be defined as defined above.

L is a single bond, a C ₆ -C ₆₀ arylene group, a C ₂ -C ₆₀ heterocyclic group, or a fluorenylene group. Here, the term "single bond" means that L does not exist and bonds directly, and compounds 1'-1, 2'-1, 3'-1, 4'-1, 5 ' -1, 6'-1 and the like, L is a single bond.

When R ⁶ to R ⁴⁵ , R ', R "and L are an aryl group or an arylene group, R ⁶ to R ⁴⁵ , R', R" and L each independently represent a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, A phenanthryl group or a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group or a phenanthrylene group.

Specifically, when two adjacent groups of R ⁸ to R ¹⁵ in the formula (2) are bonded to each other to form a ring, the formula (2) may be represented by one of the following formulas, but is not limited thereto.

&Lt; Formula 2-1 > < Formula 2-2 > < Formula 2-3 &

&Lt; Formula 2-5 > < Formula 2-6 > < Formula 2-7 &

&Lt; Formula 2-9 > < Formula 2-10 > < Formula 2-11 &

<Formula 2-13> Formula 2-14> Formula 2-15> Formula 2-16>

&Lt; Formula 2-17 > < Formula 2-18 >

In the above formulas (2-1) to (2-18)

The above X, R ⁸ to R ¹⁵ and L is X, R ⁸ to R ¹⁵ and L.

Z ¹ to Z ²⁶ are independently of each other CR "or N, R" is the same as R "defined in the above Chemical Formulas 2 to 6, and when there are plural R" s, plural R "s are the same or different from each other .

Specifically, two adjacent groups among R ¹⁶ to R ¹⁹ in Formula 3 are bonded to each other When the ring is formed, the formula (3) may be represented by one of the following formulas, but is not limited thereto.

&Lt; Formula 3-1 > < Formula 3-2 > < Formula 3-3 &

In the above Formulas 3-1 to 3-4,

R ¹⁶ to R ¹⁹ and L represents R ¹⁶ to R ¹⁹ defined in the above Chemical Formulas 2 to 6 and L, and Y ⁵ to Y ²⁰ are the same as Y ¹ to Y ⁴ defined in the above Chemical Formulas 2 to 6.

Specifically, when two adjacent groups of R ²⁸ to R ³³ in the formula (4) are bonded to each other to form a ring, the formula (4) may be represented by one of the following formulas, but is not limited thereto.

&Lt; Formula 4-1 > < Formula 4-2 > < Formula 4-3 &

In the above Chemical Formulas 4-1 to 4-4,

R ²⁸ to R ³³ and L are the same as R ²⁸ to R ³³ and L defined in the above Chemical Formulas 2 to 6.

Specifically, when two adjacent groups of R ³⁴ to R ⁴⁵ in Formula 5 are bonded to each other to form a ring, Formula 5 may be represented by one of the following formulas, but is not limited thereto.

&Lt; Formula 5-1 > < Formula 5-2 > < Formula 5-3 &

In the above Formulas 5-1 to 5-4,

R ³⁴ to R ⁴⁵ and L are the same as R ³⁴ to R ⁴⁵ and L defined in the above Chemical Formulas 2 to 6.

More specifically, the compound represented by Formula 1 may be any one of the following compounds, but is not limited to 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, and the compound represented by Formula 1 may include a hole injecting layer, a hole transporting layer, , The light emitting auxiliary layer, the light emitting layer, the electron transporting layer, and the electron injecting layer. Particularly, the compound represented by the formula (1) can be included in the light emitting layer.

That is, the compound represented by the formula (1) can be used as a material for the hole injecting layer, the hole transporting layer, the light emitting auxiliary layer, the light emitting layer, the electron transporting layer or the electron injecting layer. In particular, the compound represented by the formula (1) can be used as a material for the light emitting layer. Specifically, the organic electroluminescent device includes one of the compounds represented by the formula (1), and more specifically, (1'-1 to 1'-16, 2'-1 to 2'-27, 3'-1 to 3'-30, 4'-1 to 4'-30, To 5'-23 and 6'-1 to 6'-4).

In still another embodiment, the compound is contained singly in at least one layer of the hole injection layer, the hole transport layer, the light emission assisting layer, the light emitting layer, the electron transport layer, and the electron injection layer of the organic material layer, Wherein the compound is contained in combination of two or more different compounds, or the compound is contained in combination with two or more kinds of other compounds. In other words, each of the layers may contain a compound corresponding to the formula (I) alone, and may include a mixture of two or more compounds of the formula (I). The compound of any one of claims 1 to 7 and the compound And mixtures thereof. Herein, the compound not corresponding to the present invention may be a single compound or may be two or more compounds. When the compound is contained in combination with two or more kinds of other compounds, the other compound may be a known compound of each organic layer or a compound to be developed in the future. At this time, the compound contained in the organic material layer may be composed of the same kind of compound, but it may be a mixture of two or more different kinds of compounds represented by the general formula (1).

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 (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 or Sub 3 as shown in Reaction Schemes 1 to 3 below, but are not limited thereto.

When L in A 'is a single bond (Hal ¹ = F, Cl, Br or I)

(A, A 'is a carbocyclic or heterocyclic aromatic ring and is characterized by the formulas (2) to (6), p is an integer from 0 to 4, and 1 and n are as defined in formula (1)

When L in A 'is a single bond (Hal ¹ = F, Cl, Br or I)

(A, A ', p, l and n are the same as defined in Reaction Scheme 1)

When L in A 'is not a single bond (Hal ¹ = F, Cl, Br or I)

(A, A ', p, l and n are the same as defined in Reaction Scheme 1)

Ⅰ. Synthetic example of Sub 1

Sub 1 of the above Reaction Schemes 1 to 3 can be synthesized by the reaction path of the following Reaction Schemes 4 to 6, but is not limited thereto. Table 1 also shows FD-MS values of compounds belonging to Sub 1.

When L of A is a single bond (Hal ¹ = F, Cl, Br or I)

(A, p, l and n are the same as defined in Reaction Scheme 1)

When L in A is a single bond (Hal ¹ = F, Cl, Br or I)

(A, p, l and n are the same as defined in Reaction Scheme 1)

When L in A is not a single bond (Hal ¹ = F, Cl, Br or I)

(A, p, l and n are the same as defined in Reaction Scheme 1)

1. Synthesis of Sub 1-1

<Reaction Scheme 7>

A mixture of 10H-phenothiazine (5.95 g, 29.86 mmol) and K ₂ CO ₃ (5.36 g, 29.86 mmol) in DMSO (49 mL) was stirred at room temperature for 1 hour. 4,5-Difluorophthalonitrile (4.9 g, 29.86 mmol) was added to the reaction mixture, stirred for 2 hours, and then stirred at 50 degrees for 15 hours. It was cooled to room temperature, poured into H ₂ O and filtered. Washed with H ₂ O and the resulting solid was dissolved in dichloromethane and the organic layer was separated. Dried over MgSO ₄ and concentrated after filtration with a silica gel. Recrystallization from dichloromethane and methanol gave 6.25 g of product. (Yield: 61%).

2. Synthesis of Sub 1-3

<Reaction Scheme 8>

9,9-dimethyl-9,10-dihydroacridine ( 6.25g, 29.86mmol), K 2 CO 3 (5.36g, 38.82mmol), DMSO (49mL), wherein the 4,5-difluorophthalonitrile (4.9g, 29.86mmol) Sub-1-1 synthesis method was used to obtain 6.12 g of the product. (Yield: 58%).

3. Synthesis of Sub 1-4

<Reaction Scheme 9>

To a round bottom flask was added 4,5-dibromophthalonitrile (6.2g, 21.68mmol) , 9,9-diphenyl-9,10-dihydroacridine (7.23g, 21.68mmol), Pd 2 (dba) 3 (0.14 g, 1.08 mmol), P (t-Bu) ₃ (0.44 g, 2.17 mmol), NaOt-Bu (3.13 g, 32.53 mmol) and toluene (228 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 7.59 g of the product. (Yield: 65%).

4. Synthesis of Sub 1-27

<Reaction formula 10>

A solution of 4,5-dibromophthalonitrile (6.2 g, 21.68 mmol), 6- (quinazolin-2-yl) -9H-pyrido [2,3- b] indole (6.43 g, 21.68 mmol), Pd _{2 ) 3 (0.99g, 1.08mmol),} P (t-Bu) 3 (0.44g, 2.17mmol), NaO t -Bu (3.13g, 32.53mmol), a toluene (228ml) to the Sub 1-4 synthesis To give 6.52 g of the product. (Yield: 60%).

5. Synthesis of Sub 1-36

<Reaction Scheme 11>

9H-dibenzo [e, g] pyrido [2,3-b] indole (8.01g, 29.86mmol), K 2 CO 3 (5.36g, 38.82mmol), DMSO (49mL), 3,5-difluorophthalonitrile (4.9g , 29.86 mmol) was obtained 7.02 g of the product using the Sub 1-1 synthesis method described above. (Yield: 57%).

6. Synthesis of Sub 1-41

<Reaction Scheme 12>

A round bottomed flask was charged with 4,5-dibromophthalonitrile (5.2 g, 18.19 mmol), 9,9-dimethyl-N, N-diphenyl-7- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan- 2-yl) -9H-fluoren- 2-amine (8.87g, 18.19mmol), Pd 2 (dba) 3 (0.83g, 0.91mmol), P (t-Bu) 3 (0.37g, 1.82mmol), NaOt -Bu (2.62 g, 27.28 mmol) and toluene (191 ml) were obtained 6.49 g of the product using the Sub 1-4 synthesis method. (Yield: 63%).

7. Synthesis of Sub 1-102

<Reaction Scheme 13>

1,1,2,2,3,3,4,4-octamethyl-6- (pyridin-3-yl) -2,3,4,9-tetrahydro-1H-carbazole (8.79 g, 24.37 mmol), K ₂ CO ₃ (4.38 g, 31.69 mmol), DMSO (40 mL) and 4,5-difluorophthalonitrile (4.0 g, 24.37 mmol) were used to obtain 6.52 g of the product. (Yield: 53%).

8. Synthesis of Sub 1-106

<Reaction Scheme 14>

4,5-dibromophthalonitrile (6.3 g, 22.03 mmol) was added to a round bottom flask and 9- (4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- 2,3,4,9-tetrahydro-1H-carbazole ( 8.23g, 22.03mmol), Pd (PPh 3) 4 (0.38g, 0.33mmol), NaOH (1.32g, 33.05mmol), THF (97mL), water (48 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 6.18 g of the product. (Yield: 63%).

Example of Sub 1

[Table 1]

Ⅱ. Synthetic example of Sub 2

The above-mentioned Reaction Scheme 1 and Sub 2 of Reaction Scheme 2 can be synthesized by the reaction path of the following Reaction Scheme 15 and Reaction Scheme 16, but the present invention is not limited thereto. In addition, Table 2 shows the FD-MS values of the compounds belonging to Sub 2.

&Lt; Reaction Formula 15 >

(Where, Hal ² is Br or Cl, Ar ^1, Ar ² are independently an aryl group of C ₆ -C ₆₀ with each other; fluorene group; of O, N, S, at least one selected from the group consisting of Si and P a C ₂ -C ₆₀ hetero atom containing heterocyclic group or a C ₃ -C ₆₀ alicyclic and C ₆ group is a fused ring of an aromatic ring of -C _60.)

(Reaction Scheme 16) When R ^a and R ^{b, which} are secondary substituents of Ar ¹ and Ar ² , combine to form a ring

(Wherein Ar ¹ and Ar ² are the same as defined in Reaction Formula 15, and Ra and Rb have the same definitions as the secondary substituent in Claim 1, and q and r are integers of 0 to 8.)

1. Synthesis of Sub 2-23

<Reaction Scheme 17>

To a round bottom flask was added 4-Aminobiphenyl (5.23g, 30.9mmol) , 4-Bromobiphenyl (7.2g, 30.9mmol), Pd 2 (dba) 3 (1.41g, 1.54mmol), P (t -Bu) 3 (0.62g , NaO t- Bu (8.91 g, 92.7 mmol) and toluene (324 mL) were added, 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 6.75 g of the product. (Yield: 68%).

2. Synthesis of Sub 2-29

<Reaction Scheme 18>

Pd ₂ (dba) ₃ (1.34 g, 1.46 mmol), P ( t -Bu), 2-bromo-9,9-dimethyl-9H-fluorene (8g, 29.29mmol), 4-Aminobiphenyl (4.96g, 29.29mmol) ) ₃ (0.59 g, 2.93 mmol), NaO t- Bu (4.22 g, 43.93 mmol) and toluene (307 mL). (Yield: 64%).

3. Synthesis of Sub 2-30

<Reaction Scheme 19>

Aniline (2.25 g, 24.17 mmol), Pd ₂ (dba) ₃ (1.11 g, 1.21 mmol), P ( t- Bu) dibenzo [b, d] thiophene (8.2 g, 24.17 mmol) ) ₃ (0.49 g, 2.42 mmol), NaO t- Bu (3.48 g, 36.26 mmol) and toluene (254 mL). (Yield: 77%)

4. Sub 2-8 synthesis

<Reaction Scheme 20>

Dibenzo [b, d] thiophen-2-yl] pyridine was prepared by dissolving 6-bromo-1-methyl-9H-pyrido [2,3- b] indole (7.21 g, 29.18 mmol) It was added ylboronic acid (6.66g, 29.18mmol), Pd (PPh 3) 4 (1.01g, 0.88mmol), K 2 CO 3 (8.07g, 58.36mmol), water (64ml) 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 9.00 g (yield: 88%) of the product.

5. Sub 2-50 synthesis

<Reaction Scheme 21>

THF (88 ml), 6-bromo-2,3,4,9-tetrahydro-2-pyrrolidinone were added to the starting material [1,1 ': 3', 1 "-terphenyl] -1H-carbazole (5g, 19.99mmol) , Pd (PPh 3) 4 (0.69g, 0.6mmol), K 2 CO 3 (5.53g, 39.98mmol), the Sub 2-8 synthesis of water (44ml) To obtain 7.27 g (yield: 91%) of the product.

Example of Sub 2

[Table 2]

Ⅲ. Example of synthesis of Sub 3

Sub 3 of Scheme 3 may be synthesized by the reaction path of Scheme 22, but is not limited thereto. In addition, Table 3 shows FD-MS values of compounds belonging to Sub 3.

&Lt; Reaction Formula 22 > When L is not a single bond

(Wherein Ar ¹ , Ar ² , Ra, Rb, q and r are the same as defined in the above Reaction Scheme 15 and Reaction Scheme 16)

1. Synthesis of Sub 3-7

<Reaction Scheme 23>

(1) Intermediate Sub 3-I-7 Synthesis

Sub-2-3 (4.7 g, 27.95 mmol) obtained in the above synthesis was dissolved in nitrobenzene (140 ml) in a round bottom flask, and 7-bromo-2-iododibenzo [b, d] furan (11.47 g, 30.74 mmol) ₂ SO ₄ (3.97 g, 27.95 mmol), K ₂ CO ₃ (3.86 g, 27.95 mmol) and Cu (0.53 g, 8.38 mmol) were added and stirred at 200 ° C. When the reaction was complete, nitrobenzene was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 7.28 g (yield: 63%) of the product.

(2) Sub 3-7 Synthesis

Obtained in the above Synthesis Sub 3-I-7 (7.1g , 17.18mmol) was dissolved in DMF (108ml) in a round bottom flask, Bis (pinacolato) diboron (4.8g , 18.9mmol), Pd (dppf) Cl 2 ( 0.25 g, 0.35 mmol) and KOAc (3.39 g, 34.53 mmol) were added and stirred at 90 ° C. When the reaction was complete, DMF was removed by distillation and extracted with CH ₂ Cl ₂ and water. The organic layer was dried over MgSO ₄ and concentrated. The resulting compound was purified by silicagel column and recrystallized to obtain 6.72 g (yield: 85%) of the product.

2. Synthesis of Sub 3-14

<Reaction Scheme 24>

(1) Intermediate Sub 3-I-14 Synthesis

Sub 2-44 obtained in the above Synthesis (5.29g, 30.87mmol), nitrobenzene ( 140ml), 2-bromo-7-iodo-9,9-dimethyl-9H-fluorene (11.2g, 28.07mmol), Na 2 SO 4 7.39 g (Yield: 59%) of the product was obtained by using the Sub 3-I-7 synthesis method described above (3.99 g, 28.07 mmol), K ₂ CO ₃ (3.88 g, 28.07 mmol) .

(2) Sub 3 to 14 synthesis

(7.3 g, 16.5 mmol), DMF (104 ml), Bis (pinacolato) diboron (4.61 g, 18.15 mmol) and Pd (dppf) Cl ₂ (0.36 g, 0.5 mmol) KOAc (4.86 g, 49.5 mmol) was obtained 6.54 g (Yield: 81%) of the product using the Sub 3-9 synthesis method described above.

3. Synthesis of Sub 3-28

<Reaction Scheme 25>

(1) Intermediate Sub 3-I-28 Synthesis

The starting material 2,3-di (pyridin-4-yl) -1H-indole (7.23 g, 26.66 mmol), nitrobenzene (121 ml), 3-bromo-3'-iodo-1,1'- _{, 24.23mmol), Na 2 SO 4} (3.44g, 24.23mmol), K 2 CO 3 (3.35g, 24.23mmol), and the Cu (0.46g, 7.27mmol) using the Sub 3-I-7 synthesis 7.31 g (yield: 60%) of the product was obtained.

(2) Sub 3-28 Synthesis

(7.3 g, 14.53 mmol), DMF (92 ml), Bis (pinacolato) diboron (4.06 g, 15.98 mmol) and Pd (dppf) Cl ₂ (0.32 g, 0.44 mmol) KOAc (4.28 g, 43.59 mmol) was obtained 6.63 g (Yield: 83%) of the product using the above Sub 3-7 synthesis method.

4. Synthesis of Sub 3-4

<Reaction Scheme 26>

(1) Intermediate Sub 3-I-4 Synthesis

(5.87 g, 34.91 mmol), nitrobenzene (159 ml), 2-bromo-6-iodonaphthalene (10.6 g, 31.74 mmol), Na ₂ SO ₄ (4.51 g, 7.35 g (Yield: 62%) of the product was obtained by using Sub 3-I-7 synthesis method using K ₂ CO ₃ (4.39 g, 31.74 mmol) and Cu (0.61 g, 9.52 mmol).

(2) Sub 3-4 synthesis

(7.3 g, 19.56 mmol), DMF (123 ml), Bis (pinacolato) diboron (5.46 g, 21.51 mmol) and Pd (dppf) Cl ₂ (0.43 g, 0.59 mmol) KOAc (5.76 g, 58.67 mmol) was obtained 6.58 g (Yield: 80%) of the product using the Sub 3-7 synthesis method described above.

5. Synthesis of Sub 3-32

<Reaction Scheme 27>

(1) Intermediate Sub 3-I-32 Synthesis

The starting material, 4-methoxy-N-phenylaniline ( 7.6g, 38.14mmol), nitrobenzene (190ml), 1-bromo-3-iodobenzene (11.87g, 41.96mmol), Na 2 SO 4 (5.42g, 38.14mmol), 7.57 g (Yield: 56%) of the product was obtained using K ₂ CO ₃ (5.27 g, 38.14 mmol) and Cu (0.73 g, 11.44 mmol) using the above Sub 3-I-7 synthesis method.

(2) Sub 3-32 synthesis

(7.5 g, 21.17 mmol), DMF (133 ml), Bis (pinacolato) diboron (5.91 g, 23.29 mmol), Pd (dppf) Cl ₂ (0.25 g, 0.35 mmol) KOAc (3.39 g, 34.53 mmol) was obtained 6.71 g (Yield: 79%) of the product using the above Sub 3-7 synthesis method.

Example of Sub 3

[Table 3]

IV. Example of Final Product Synthesis

1. Synthesis of 1'-9

<Reaction Scheme 28>

A mixture of Sub 2-1 (3.02 g, 17.93 mmol) and K ₂ CO ₃ (3.22 g, 23.31 mmol) in DMSO (29 mL) was stirred at room temperature for 1 hour. Sub-1-8 (5.87 g, 17.93 mmol) was added to the reaction mixture, and the mixture was stirred for 2 hours and then at 50 ° C for 15 hours. It was cooled to room temperature, poured into H ₂ O and filtered. Washed with H ₂ O and the resulting solid was dissolved in dichloromethane and the organic layer was separated. Dried over MgSO ₄ and concentrated after filtration with a silica gel. Recrystallization from dichloromethane and methanol gave 6.14 g of product. (Yield: 72%).

2. 1'-1 Synthesis

<Reaction Scheme 29>

Sub 2-57 (2.96 g, 17.47 mmol), K ₂ CO ₃ (3.14 g, 22.72 mmol), DMSO (29 mL) and Sub 1-1 (6.00, 17.47 mmol) 6.02 g of the product was obtained. (Yield: 70%).

3. Synthesis of 1'-4

<Reaction Scheme 30>

(3.77 g, 11.81 mmol), Pd (PPh ₃ ) ₄ (0.41 g, 0.35 mmol), NaOH (1.42 g, 35.43 mmol) mmol), THF (52 mL) and water (26 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 6.00 g of the product. (Yield: 78%).

4. Synthesis of 2'-15

<Reaction Scheme 31>

Sub 1-27 (5.58g, 11.13mmol), Sub 3-8 (5.55g, 11.13mmol), Pd (PPh 3) 4 (0.39g, 0.33mmol), NaOH (1.34g, 33.39mmol), THF (49 mL) and water (25 mL) were used to obtain 6.00 g of the product using the above 1'-4 synthesis method. (Yield: 68%).

5. Synthesis of 2'-22

<Reaction equation 32>

Sub-3-37 (5.46 g, 11.61 mmol), K ₂ CO ₃ (2.09 g, 15.10 mmol), DMSO (19 mL) and Sub 1-114 6.03 g of product was obtained. (Yield: 68%).

6. Synthesis of 3'-3

<Reaction Scheme 33>

Sub 1-41 (5.02g, 8.86mmol), Sub 3-34 (4.32g, 8.86mmol), Pd (PPh 3) 4 (0.31g, 0.27mmol), NaOH (1.06g, 26.59mmol), THF (39mL ) And water (20 ml), 6.01 g of the product was obtained using the 1'-4 synthesis method described above. (Yield: 80%).

7. Synthesis of 3'-16

<Reaction formula 34>

Sub 2-31 (3.51g, 13.52mmol), K 2 CO 3 (2.55g, 18.44mmol), DMSO (20mL), Sub 1-53 (4.96g, 12.30mmol) the use of the 1'-9 Synthesis To obtain 6.00 g of the product. (Yield: 69%).

8. Synthesis of 3'-24

<Reaction Scheme 35>

Sub 1-59 (4.25g, 9.44mmol), Sub 3-29 (5.39g, 9.43mmol), Pd (PPh 3) 4 (0.33g, 0.28mmol), NaOH (1.13g, 28.31mmol), THF (42mL ) And water (21 ml), 6.00 g of the product was obtained using the above 1'-4 synthetic method. (Yield: 78%).

9. Synthesis of 4'-21

<Reaction Formula 36>

Sub 1-84 (4.83g, 14.99mmol), Sub 3-25 (6.38g, 14.99mmol), Pd (PPh 3) 4 (0.52g, 0.45mmol), NaOH (1.8g, 44.98mmol), THF (66mL ) And water (33 ml), 6.00 g of the product was obtained using the 1'-4 synthesis method described above. (Yield: 74%).

10. Synthesis of 5'-14

(Reaction Scheme 37)

Sub-2-55 (4.86 g, 13.47 mmol), K ₂ CO ₃ (2.42 g, 17.52 mmol), DMSO (22 mL) and Sub 1-102 (6.8 g, 13.47 mmol) 6.04 g of product was obtained. (Yield: 53%).

11. Synthesis of 5'-23

<Reaction Formula 38>

To a round bottom flask Sub 1-106 (6.1g, 10.81mmol), Sub 2-50 (4.32g, 10.81mmol), Pd 2 (dba) 3 (0.49g, 0.54mmol), P (t-Bu) 3 ( 0.25 g, 1.08 mmol), NaO t- Bu (1.56 g, 16.21 mmol) and toluene (113 ml). After completion of reaction, drying the ether was extracted with water and the organic layer was concentrated after MgSo ₄ and the generated organic substances silicagel column and recrystallized to give the product 6.01g. (Yield: 63%).

12. Synthesis of 6'-1

<Reaction Scheme 39>

Sub-2-59 (2.77 g, 10.10 mmol), K ₂ CO ₃ (1.00 g, 7.22 mmol), DMSO (7.89 mL) and Sub 1-115 (2.1 g, 4.81 mmol) To give 6.40 g of product. (Yield: 67%).

Meanwhile, the FD-MS values of the compounds 1'-1 to 6'-4 of the present invention prepared according to the above Synthesis Examples are shown in Table 4 below.

[Table 4]

Evaluation of manufacturing of organic electric device

[ Example  1] Fabrication and Testing of Organic Electroluminescent Devices Delayed fluorescence )

An organic electroluminescent device was fabricated according to a conventional method using a compound obtained through synthesis as a dopant material of a light emitting layer. First, N ¹ - (naphthalen-2-yl) -N ⁴ and N ⁴ -bis (4- (naphthalen-2-yl (phenyl) amino) phenyl) -N1-phenylbenzene-1,4-diamine (abbreviated as 2-TNATA) was formed by vacuum deposition to a thickness of 60 nm. Subsequently, 4,4-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vapor-deposited as a hole transport compound on the film to a thickness of 20 nm to form a hole transport layer . On top of the hole transport layer, 6% by weight of the inventive compound 1'-1 and 4,4-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (mCP) Emitting layer was deposited. (2-methyl-8-quinolinolato) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm as a hole blocking layer to form an electron transport layer Tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq3) was deposited to a thickness of 40 nm. Thereafter, LiF as an alkali metal halide was deposited to a thickness of 0.2 nm, Al was subsequently deposited to a thickness of 150 nm, and this Al / LiF was used as a cathode to produce an organic electroluminescent device.

[mCP]

[ Comparative Example  One]

An organic electroluminescence device was fabricated in the same manner as in Example 1 except that Comparative Compounds 1 and 2 were used instead of Compound 1'-1 of the present invention.

<Comparative Compound 1>

&Lt; Comparative Compound 2 >

[ Example  2] to [ Example  22]

An organic electroluminescent device was fabricated in the same manner as in Example 1 except that the compounds 1'-9 to 5'-21 of the present invention were used instead of the compound 1'-1 of the present invention.

Electruminescence (EL) characteristics were measured with a photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices thus prepared and the comparative organic electroluminescence devices. The measurement result was 500 cd / m ² standard luminance Measured the T90 lifetime through a life-time instrument manufactured by McAfee. Table 5 shows the results of device fabrication and evaluation.

[Table 5]

As can be seen from the results of Table 5, the organic electroluminescence device using the organic electroluminescence device material of the present invention as a light emitting layer material can remarkably improve the luminous efficiency, the driving voltage and the lifetime.

 In other words, the compound of the present invention, which contains at least one cyano group and at least one donor unit in the benzene ring, has lower driving voltage, higher efficiency and longer life than the comparative compound 1, which is a general fluorescent dopant in which an anthracene core is substituted with two amine groups .

In particular, when the compound of the present invention has a single bond or an atom as a linking group in the formula (6) having an amine group (-NAr ¹ Ar ² ) in which an aryl group connected to N is opened, N and an aryl group (2) to (5) which planarly hold the structure of the organic EL device showed better device performance in terms of driving voltage, efficiency, and lifetime.

In formulas (2) to formula (5) were the compounds having the general formula (2) than the formula (4) with an indole core excellent in efficiency and life, were the compound is a linking group X of the general formula (2) having a CR ⁶ R ⁷ excellent in life side, the linking group X S, and O were superior in terms of efficiency. Also, Formula 5, which has a bulky core substituted by an alkyl group rather than a compound having Formula 2, is more excellent in efficiency. Formula 3, which is a carboline containing a heteroatom N in the backbone core than Formula 5, And showed excellent device performance results.

It has also been confirmed that the devices using the compounds of the present invention (fused) in which the aromatic rings are further condensed in the general formulas (2) to (5) (Examples 2 to 4, Examples 9 and 16 to 17) show improved lifetimes. This is because the packing density is higher than that of the compound having no additional ring formation during the deposition of the device, and thus the joule heating caused by the overvoltage is small and the thermal stability is obtained.

In the case of efficiency, substitution of a bulky substituent such as tert-buthyl with a secondary substituent of the compound of the present invention minimizes the steric hindrance of molecules to each other, thereby facilitating migration of the exciton between the host and the dopant to increase efficiency In a similar manner, the compound of formula (6) having many alkyl groups in the backbond core is also considered to have a similar effect.

The thermally activated delayed fluorescence (TADF) material of the present invention, which can solve the problem of external quantum efficiency of a conventional fluorescent material like Comparative Compound 1, can be obtained by appropriately combining electron electron donor unit and electron acceptor unit And it can be explained that it results in high efficiency, long life and low driving voltage because it forms an exciplex.

That is, even though it is the same core, the energy level changes depending on the substituent, and the characteristics of the device itself may be significantly different. Although the device characteristics have been described from the viewpoint of the light emitting layer in the evaluation results of the above-described device fabrication, the materials commonly used for the light emitting layer are organic electronic devices such as the electron transport layer, electron injection layer, hole injection layer, And may be used alone or in combination with other materials. Therefore, the compound of the present invention can be used in combination with a single or different materials in addition to the light emitting layer, for example, an electron transporting layer, an electron injecting layer, a hole injecting layer, a hole transporting layer and a light emitting auxiliary 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 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 present invention 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 (12)

A delayed fluorescent compound represented by the following formula:
&Lt; Formula 1 >

[In the above formula (1)
R 'is independently from each other deuterium; halogen; An alkyl group having _{1 to 60} carbon atoms; An aryl group of C ₆ -C ₆₀ ; A fluorenyl group; Cyano; 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 ; 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 ; A C ₂ -C ₆₀ carbocyclic aromatic ring; A heterocyclic aromatic ring of C ₂ -C ₆₀ , but is hydrogen when n = 0 except for carbazole or fused carbazole, and plural R 's are the same or different from each other and,
A comprises a C ₂ -C ₆₀ carbocyclic or heterocyclic aromatic ring but with the exception of carbazole or fused carbazole, the plurality of A's are the same or different from each other,
l is an integer of 0 to 4, m is an integer of 1 to 5, n is an integer of 0 to 4,
Wherein A is represented by one of the following formulas,
&Lt; Formula 2 &gt;&lt; EMI ID =

&Lt; Formula 5 >< EMI ID =

[In the above Chemical Formulas 2 to 6,
X is O, S or CR &lt; ⁶ &gt; R &lt; ⁷ &
Y ¹ to Y ⁴ independently of one another are CR "or N, at least one is N, plural R" s are present, plural R "s are the same as or different from each other,
R ⁶ and R ⁷ are independently selected from the group consisting of: i) independently of one another hydrogen; heavy hydrogen; An alkyl group having _{1 to 60} carbon atoms; C ₆ -C ₆₀ aryl group; or ii) R ⁶ and R ⁷ may combine with each other to form at least one ring (provided that R ⁶ and R ⁷ , which do not form a ring, Is the same as defined in (i) above),
R ⁸ - R ⁴⁵ and R "are ⅰ) each independently selected from hydrogen; nitro; heavy hydrogen; halogen alkyl C ₁ -C ₆₀ (straight-chain, branched-chain); C ₁ -C ₆₀ alkoxy group; a C ₆ -C ₆₀ aryl An amino group, a silyl group, a C ₂ -C ₆₀ alkenyl group, a C ₆ -C ₆₀ aryl group, a C ₂ -C ₆₀ heteroaryl group, a carbonyl group, an ester group, a nitrile group, a sulfanyl group, a sulfinyl group, A sulfonyl group, a phosphino group, and a fluorenyl group; or ii) two adjacent arbitrary two of R ⁸ to R ¹⁵ , two adjacent arbitrary two of R ¹⁶ to R ¹⁹ groups are selected from the group consisting of R between two groups ^{of 20} to R ²⁷ any adjacent one, R ³⁰ to R ³³ any two adjacent to each other two groups, of R ⁴² to R ⁴⁵ 2 any adjacent of any adjacent two groups with each other and a plurality of R "of And the groups may be bonded to each other to form at least one ring (provided that at least one of R &lt; ⁸ &gt; to R &lt; ⁸ &gt; R ⁴⁵ and R "are as defined in i) above,
L is a single bond, a C ₆ -C ₆₀ arylene group, a C ₂ -C ₆₀ heterocyclic group or a fluorenylene group.]
Each of the aryl group, the alkyl group, the fluorenyl group, the cyano group, the heterocyclic group, the fused ring group, the alkenyl group, the alkynyl group, the alkoxyl group, the aryloxy group, the carbocyclic aromatic ring and the heterocyclic aromatic ring, , a silane group, a siloxane group, a boron group, a germanium group, a cyano group, a nitro _{group, -L'-N (R c)} (R d) ( wherein L 'is a single bond; an aryl group of C ₆ ~ C _60; A fused ring group of a C ₃ to C ₆₀ aliphatic ring and a C ₆ to C ₆₀ aromatic ring, and a C ₂ to C ₆₀ heterocyclic group; and R _c and R _d is independently 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, S, Si and P And a C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from the group consisting of C ₁ ~ C ₂₀ coming of the alkylthio, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl, C ₆ ~ C ₂₀ of the a substituted aryl group, a deuterium, C ₆ ~ C ₂₀ aryl group, fluorenyl group, C ₂ ~ C heterocyclic group of _20, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C aryl group of _20, C ₈ ~ C ₂₀ aryl alkenyl group, a carbonyl group, an ether group, C ₂ ~ C ₂₀ of the alkoxyl group, C ₆ ~ aryloxy _{C 30, -O-Si (R} x) 3, and R ^x O-Si (R ^x ) ₂ - wherein R ^x is hydrogen, a C ₆ to C ₂₀ aryl group, a C ₁ to C ₂₀ alkyl group, a C ₂ to C ₂₀ alkenyl group, a C ₈ to C ₂₀ arylalkenyl group, An aryloxycarbonyl group having ₁ to ₂₀ carbon atoms, an arylalkoxyl group having ₇ to ₂₀ carbon atoms, or an alkoxycarbonyl group having ₂ to ₂₀ carbon atoms. The method according to claim 1,
Wherein two adjacent groups of R ⁸ to R ¹⁵ of Formula 2 are bonded to each other to form a ring, Formula 2 is represented by the following formula.
&Lt; Formula 2-1 >< Formula 2-2 >< Formula 2-3 &

&Lt; Formula 2-5 >< Formula 2-6 >< Formula 2-7 &

&Lt; Formula 2-9 >< Formula 2-10 >< Formula 2-11 &

<Formula 2-13> Formula 2-14> Formula 2-15> Formula 2-16>

&Lt; Formula 2-17 &gt;&lt; Formula 2-18 &gt;

[In the above Chemical Formulas 2-1 to 2-18,
The above X, R ⁸ to R ¹⁵ and L is the same as defined in the above Chemical Formulas 2 to 6,
Z ¹ to Z ²⁶ are independently of each other CR "or N, and R" is the same as defined in the above Chemical Formulas 2 to 6, and when a plurality of R "s exist, the plurality of R" s are the same or different from each other. The method according to claim 1,
The adjacent two groups of R ¹⁶ to R ¹⁹ in the above formula (3) Wherein when the ring is formed, the formula (3) is represented by the following formula.
&Lt; Formula 3-1 >< Formula 3-2 >< Formula 3-3 &

(In the above formulas 3-1 to 3-4,
R ¹⁶ to R ¹⁹ and L is the same as defined in the above Chemical Formulas 2 to 6 and Y ⁵ to Y ²⁰ are the same as Y ¹ to Y ⁴ defined in the above Chemical Formulas 2 to 6, The method according to claim 1,
When two adjacent groups of R ²⁸ to R ³³ in the formula (4) are bonded to each other to form a ring, the formula (4) is represented by the following formula:
&Lt; Formula 4-1 >< Formula 4-2 >< Formula 4-3 &

(In the formulas (4-1) to (4-4)
Wherein R ²⁸ to R ³³ and L are the same as defined in the above Chemical Formulas 2 to 6) The method according to claim 1,
Wherein the adjacent two of R ³⁴ to R ⁴⁵ in the formula (5) are bonded to each other to form a ring, the formula (5) is represented by the following formula:
&Lt; Formula 5-1 >< Formula 5-2 >< Formula 5-3 &

(In the formulas (5-1) to (5-4)
Wherein R ³⁴ to R ⁴⁵ and L are the same as defined in the above formulas (2) to (6) The method according to claim 1,
Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;

A first electrode;
A second electrode; And
And at least one organic material layer including a light emitting layer between the first electrode and the second electrode,
Wherein the light emitting layer contains the retarded fluorescent compound according to any one of claims 1 to 6. 8. The method of claim 7,
Wherein the light emitting layer is a mixture of the same or a different kind of compound of any one of claims 1 to 7. 8. The method of claim 7,
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. 8. The method of claim 7,
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 7; And
And a control unit for driving the display device. 12. The method of claim 11,
Wherein the organic electroluminescent device is one of an organic electroluminescent device, an organic solar cell, an organophotoreceptor, an organic transistor, and a device for monochromatic or white illumination.

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