KR20180136151A - Compound for organic electronic element, organic electronic element comprising the same, and electronic device thereof - Google Patents

Abstract

Disclosed are an organic electronic element including a compound represented by chemical formula 1, a first electrode, a second electrode, and an organic material layer between the first electrode and the second electrode, and an electronic device comprising the same. By comprising the compound represented by the chemical formula 1 in the organic material layer, the driving voltage of the organic electronic element can be lowered, and the luminous efficiency and lifetime of the organic electronic element 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 multilayer structure composed of different materials, and may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

A material used as an organic material layer in an organic electric device may be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions.

The light emitting material may be classified into a polymer type and a low molecular type depending on the molecular weight, and may be classified into a phosphorescent material derived from singlet excited state of electrons and a phosphorescent material derived from the triplet excited state of electrons . Further, the light emitting material can be classified into blue, green, and red light emitting materials and yellow and orange light emitting materials required to realize better natural color depending on the luminescent color.

On the other hand, when only one material is used as a light emitting material, there arises a problem that the maximum light emission wavelength shifts to a long wavelength due to intermolecular interaction, the color purity decreases, or the efficiency of the device decreases due to the light emission attenuating effect. A host / dopant system may be used as a light emitting material in order to increase the light emitting efficiency through the light emitting layer. When the dopant having a smaller energy band gap than the host forming the light emitting layer is mixed with a small amount of the light emitting layer, the excitons generated in the light emitting layer are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on the type of the dopant used.

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

The efficiency, lifetime, and driving voltage are related to each other. As the efficiency increases, the driving voltage decreases. As the driving voltage decreases, the crystallization of the organic material due to Joule heating, which occurs during driving, And the lifetime tends to increase. However, simply improving the organic material layer can not maximize the efficiency. This is because, when the optimum combination of the energy level and the T ₁ value between the respective 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. Therefore, it is necessary to develop a light emitting material having high thermal stability and achieving a charge balance in the light emitting layer efficiently.

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

An object of the present invention is to provide a compound capable of lowering the driving voltage of a device and improving the luminous efficiency, color purity and lifetime of the device, an organic electric device using the same, and an electronic device therefor.

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

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

By using the compound according to the embodiment of the present invention, not only the driving voltage of the device can be lowered, but also the luminous efficiency, color purity and 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 symbols as possible even if they are shown in different drawings. In the following description of the present invention, a detailed description of known functions and configurations incorporated herein will be omitted when it may make the subject matter of the present invention rather unclear.

In describing the components of the present invention, 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. At this time, atoms shared in two rings are called 'spyro atoms', and they are referred to as 'monospyros,' 'di spyroses,' and 'tri-spyros', depending on the number of spyro atoms contained in a compound. 'Compounds.

Also, if 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.

In addition, a no explicit description, 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, 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, C ₂ -C of ₂₀ alkynyl, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, of a C ₆ -C ₂₀ aryl group substituted with a heavy hydrogen, C ₈ -C ₂₀ aryl alkenyl group, a silane group, a boron 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, with the proviso that at least one substituent And 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, a monovalent 'group' may be named 'phenanthryl' and a bivalent group may be named 'phenanthrylene' It may be described as "phenanthrene" which is the name of the parent compound. Similarly, in the case of pyrimidine, it may also be described as 'pyrimidine' irrespective of the valence number, or may be described as the 'name of the group' of the corresponding singer, such as pyrimidine di have.

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, It may also serve as a hole blocking layer.

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 or a dopant material of the light emitting layer 150, or a material of the light efficiency improving layer. For example, the compound of the present invention can be used as a material for the light emitting layer 150, the hole transporting layer 140, and / or the light emitting auxiliary layer 151, and can be preferably used as a host material for the light emitting layer 150.

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.

Accordingly, in the present invention, by forming the light emitting layer 150 using the compound represented by Chemical Formula 1, the energy level and T ₁ value between each organic material layer, the intrinsic characteristics (mobility, interface characteristics, etc.) It is possible to simultaneously improve the life span and the efficiency.

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. A light emitting auxiliary layer 151 may be further formed between the hole transporting layer 140 and the light emitting layer 150 and an electron transporting auxiliary layer may be further formed between the light emitting layer 150 and the electron transporting 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 may be defined as follows.

Ar ¹ to Ar ⁴ are independently a C ₆ to C ₆₀ aryl group, Ar ¹ and Ar ² may be bonded to each other to form a ring, and Ar ³ and Ar ⁴ may be bonded to each other to form a ring .

Ar ¹ and Ar ² may be symmetrical to each other, and Ar ³ and Ar ⁴ may be symmetrical to each other. That is, Ar ¹ = Ar ² or Ar ³ = Ar ⁴ . Ar ¹ and Ar ² may be asymmetric with each other, and Ar ³ and Ar ^{4 may} also be asymmetric with respect to each other. That is, Ar ¹ ≠ Ar ² or Ar ³ ≠ Ar ⁴ .

When Ar ¹ to Ar ⁴ are aryl groups, they may preferably be C ₆ to C ₃₀ aryl groups, more preferably C ₆ to C ₁₂ aryl groups, specifically, phenyl, naphthyl, biphenyl, and the like.

R ¹ and R ² are independently of each other hydrogen; heavy hydrogen; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R _a ) (R _b ); n is an integer of 0 to 4; and m is an integer of 0 to 3. When n is an integer of 2 or more, a plurality of R ^{1 s} may be the same or different and adjacent R ^{1 s} may combine with each other to form a ring. When m is an integer of 2 or more, a plurality of R ^{2 s} may be the same or different from each other, and adjacent R ^{2 s} may combine with each other to form a ring. The ring formed by bonding adjacent R ¹ and / or adjacent R ^{2 to} each other is a C ₆ to C ₆₀ aromatic hydrocarbon, a C ₂ to C ₆₀ hetero ring, a fluorene or a derivative thereof, a C ₃ to C ₆₀ aliphatic A fused ring group of a ring and a C ₆ to C ₆₀ aromatic ring, or a combination thereof.

When R ¹ and R ² are aryl groups, they may preferably be C ₆ to C ₃₀ aryl groups, more preferably C ₆ to C ₁₂ aryl groups, specifically, phenyl, naphthyl, biphenyl, and the like. When R ¹ and R ² are a heterocyclic group, preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₁₂ heterocyclic group, specifically, pyridine, dibenzofuran, dibenzothiophene , Carbazole, and the like.

L ¹ is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from the group consisting of O, N, S, Si and P, o is an integer of 0 or 1,

When L ¹ is an arylene group, it may preferably be an arylene group having ₆ to ₃₀ carbon atoms, more preferably an arylene group having ₆ to ₁₂ carbon atoms, specifically, phenyl, naphthalene, biphenyl, and the like. When L ¹ is a heterocyclic group, preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₁₂ heterocyclic group, specifically, pyridine, dibenzofuran, dibenzothiophene, carbazole And so on.

X ¹ to X ⁴ are C (R ₀ ) or N, and at least two of X ¹ to X ⁴ are preferably N.

Wherein R < ₀ > is independently selected from the group consisting of hydrogen; heavy hydrogen; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R _a ) (R _b ); and adjacent R ₀ may be bonded to each other to form a ring.

When R ₀ is an aryl group, it may preferably be an aryl group of C ₆ to C ₃₀ , more preferably a C ₆ to C ₁₂ aryl group, specifically, phenyl, naphthyl, biphenyl, and the like. When R ₀ is a heterocyclic group, preferably a C ₂ to C ₃₀ heterocyclic group, more preferably a C ₂ to C ₁₂ heterocyclic group, specifically, pyridine, triazine, dibenzofuran, carbazole, etc. have. When R < ₀ > is a fluorenyl group, 9,9-diphenyl-9H-fluorene, 9,9-dimethyl-9H-fluorene, 9,9'-spirobifluorene, spirofluorene benzofluor Or the like.

The Z ring is a C ₆ to C ₆₀ aromatic hydrocarbon or a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si and P.

When the Z ring is an aromatic hydrocarbon, it is preferably a C ₆ to C ₃₀ aromatic hydrocarbon, more preferably a C ₆ to C ₁₄ aromatic hydrocarbon, specifically benzene, naphthalene, phenanthrene, and the like. When Z ring heterocyclic group, preferably C ₂ ~ heterocyclic group of the C ₃₀ heterocyclic group, more preferably a C ₂ ~ C ₂₃ of, in particular pyridine, quinazoline, quinoline, benzoquinoline, benzo quinazoline, Benzothiophene, benzofuran, indole, indene or a derivative thereof, dihydro-dimethyl-indene, dihydro-diphenyl-indene, spiroid fluorene indene, dihydronaphthofuran and the like.

L 'is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group; and R _a and R _b are independently of each other a C ₆ to C ₆₀ aryl group; A fluorenyl group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si, and P;

A ring formed by bonding Ar ¹ to Ar ⁴ , R ¹ , R ² , R ₀ , R _a , R _b , L ¹ and Z ring, Ar ¹ and Ar ^{2 to} each other, Ar ³ and Ar ⁴ are bonded to each other form a ring, formed by coupling together the adjacent rings together R ^1, R ² adjacent the ring formed by combining each other, and formed by adjacent R ₀ bonded to each other, each ring is 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, Si and P; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ -C ₂₀ ; Aryl alkenyl group of C ₈ -C _20; And a combination of these.

The formula (1) may be represented by one of the following formulas (2) to (5).

          &Lt; Formula 2 > < EMI ID =

<화학식 4> <화학식 5>

&Lt; Formula 4 >< EMI ID =

In the above formulas (2) to (5), each symbol can be defined as follows.

Ar ¹ to Ar ⁴ , R ¹ , R ² , n, m, L ¹ and X ¹ to X ⁴ are as defined in formula (1).

F ¹ and F ² are each independently selected from N (R '), S, O or C (R') (R " ), a and b is an integer of 0 or 1, a + b is an integer of 1 or more . If a or b is 0 and the other is 1, the F-containing ring can be a pentagonal ring, and if both are 1, the F-containing ring can be a hexagonal ring.

Wherein R 'and R " are independently selected from the group consisting of hydrogen, a C ₁ to C ₂₀ alkyl group, a C ₆ to C ₂₀ aryl group, and a C ₂ to C ₆ heteroatom containing at least one heteroatom selected from O, N, To C ₂₀ heterocyclic groups; and R 'and R " may be bonded to each other to form a ring.

Preferably, in the general formulas (1) to (5), X ¹ and X ³ are N, X ² and X ⁴ are N, or X ¹ and X ⁴ are N. Further, preferably, adjacent R ^{1 s} or adjacent R ^{2 s} may combine with each other to form a ring.

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

.

.

In another aspect of the present invention, there is provided an organic electroluminescent device comprising a first electrode, a second electrode, and an organic material layer disposed between the first electrode and the second electrode, And a compound to be displayed. The compound may be included in the organic material layer in the form of a single compound or two or more compounds.

The organic material layer is at least one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer and a light emitting layer, and the compound represented by the formula (1) can be used as a host material of a light emitting layer, particularly a green phosphorescent host material.

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

Illustratively, the compound represented by Formula 1 according to the present invention (Final Products) can be prepared by reacting Sub 1 and Sub 2 as shown in Reaction Scheme 1 below.

<Reaction Scheme 1>

1. Sub 1 synthesis  example

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

<Reaction Scheme 2>

(1) Sub 1 (1) Synthetic example

Sub 1-3-1 Synthetic Example

Sub 1-1-1 (184.6 g, 760.7 mmol) was dissolved in THF (2,500 mL), the temperature of the reaction was lowered to -78 ° C, n-BuLi (324.56 mL, 2.5 M in hexane) The reaction was stirred for 1 hour. Sub 1-2-1 (79.6 g, 507.1 mmol) was dissolved in THF, and the mixture was stirred at room temperature for 4 hours. After the completion of the reaction, water was added to the reaction mixture to quench the reaction mixture, and water in the reaction mixture was removed. After the filtration under reduced pressure, the organic layer was dried over MgSO ₄ and concentrated to obtain 136.6 g of the product (yield: 56%).

Sub 1-4-1 Synthetic Example

Sub 1-3-1 (136.3 g, 425 mmol) is dissolved in chloroform in a round bottom flask and acetyl bromide (203 ml, 2507 mmol) is slowly added dropwise at 0 ° 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 109.3 g (yield: 67%) of the product.

Sub 1-6-1 Synthetic Example

To a round bottom flask Sub 1-4-1 (85.2g, 222mmol) and Sub 1-5-1 (40.6g, 190mmol), K 2 CO 3 (46.03 g, 333 mmol), Pd (PPh 3) 4 (7.7 g, 6.66 mmol), THF (490 mL) and water (245 mL) were added and dissolved, followed by reflux at 80 ° C for 12 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was separated by silicagel column to obtain the desired Sub 1-6-1 (51.6 g, 61%).

Sub 1-7-1 Synthetic Example

Sub-1-6-1 (51.8 g, 130 mmol) and Sub 1-2-1 (11.0 g, 90 mmol) were subjected to the synthesis of Sub 1-3-1 to obtain 37.6 g (yield: 63%) of the final product .

Sub 1-8-1 Synthetic Example

Sub 1-7-1 (37.2 g, 81 mmol) was subjected to the synthesis of Sub 1-4-1 to obtain 29.2 g (yield: 69%) of the final product.

Sub 1 (1) Synthetic example

Sub-1-8-1 (20.9 g, 40 mmol) and Sub 1-9-1 (4.9 g, 40 mmol) were subjected to the synthesis of Sub 1-6-1 to obtain 13.3 g (yield: 64%) of the final product .

(2) Example of synthesis of Sub 1 (8)

Sub 1-3-2 Synthetic Example

Sub-1-1-2 (368.1 g, 760.7 mmol) and Sub 1-2-1 (79.6 g, 507.1 mmol) were reacted with 235.2 g (55% .

Sub 1-4-2 Synthetic Example

Sub-1-3-2 (234.9 g, 418 mmol) was subjected to the synthesis of Sub 1-4-1 to obtain 169.8 g (yield: 65%) of the product.

Sub 1-6-2 Synthetic Example

Sub-1-4-2 (138.7 g, 222 mmol) and Sub 1-5-1 (40.6 g, 190 mmol) were subjected to the synthesis of Sub 1-6-1 to obtain 87.0 g (yield: 63%) of the product.

Sub 1-7-2 Synthetic Example

Sub-1-6-2 (80.9 g, 130 mmol) and Sub 1-2-1 (11.0 g, 90 mmol) were subjected to synthesis of Sub 1-3-1 to obtain 54.6 g (yield: 60%) of the final product .

Sub 1-8-2 Synthetic Example

Sub 1-7-2 (53.2 g, 76 mmol) was subjected to synthesis of Sub 1-4-1 to obtain 38.3 g (yield: 66%) of the final product.

Sub 1 (8) Synthetic example

18.6 g (Yield: 61%) of Sub 1-8-2 (30.5 g, 40 mmol) and Sub 1-9-1 (4.9 g, 40 mmol) were obtained using the synthesis method of Sub 1-6-1 .

(3) Example of synthesis of Sub 1 (11)

Sub 1-3-3 Synthetic Example

169.3 g (Yield: 60%) of Sub 1-1-3 (222.7 g, 760.7 mmol) and Sub 1-2-1 (79.6 g, 507.1 mmol) .

Sub 1-4-3 Synthetic Example

Sub 1-3-3 (155.0 g, 418 mmol) was subjected to synthesis of Sub 1-4-1 to obtain 125.1 g (yield: 69%) of the product.

Sub 1-6-3 Synthetic Example

63.1 g (Yield: 66%) of Sub 1-4-3 (96.3 g, 222 mmol) and Sub 1-5-1 (40.6 g, 190 mmol) were obtained using the synthesis method of Sub 1-6-1.

Sub 1-7-3 Synthetic Example

Sub-1-6-3 (56.0 g, 130 mmol) and Sub 1-2-1 (11.0 g, 90 mmol) were subjected to synthesis of Sub 1-3-1 to obtain 44.3 g (yield: 67%) of the final product .

Sub 1-8-3 Synthetic Example

Sub-1-7-3 (38.7g, 76mmol) was obtained as a final product (30.9g, Yield: 71%) by the synthesis method of Sub 1-4-1.

Sub 1 (11) Synthetic example

Sub-1-8-3 (22.9 g, 40 mmol) and Sub 1-9-1 (4.9 g, 40 mmol) were subjected to the synthesis of Sub 1-6-1 to obtain 15.0 g (yield: 66%) of the final product .

Examples of Sub 1 are as follows, but are not limited thereto.

[Table 1]

Sub Two examples

Examples of Sub 2 include, but are not limited to, the following.

[Table 2]

2. Of the final compound Synthetic example

1-1 Synthetic Example

Pd (PPh ₃ ) ₄ (7.7 g, 0.67 mmol), Sub 2-1 (4.8 g, 19.0 mmol), K ₂ CO ₃ (46.03 g, 33.3 mmol) Was placed in a round bottom flask, and dissolved in THF (49 mL) and water (25 mL), and refluxed at 80 ° C for 12 hours. When the reaction was completed, the temperature of the reaction mixture was cooled to room temperature, extracted with CH ₂ Cl ₂ and wiped with water. The organic layer was dried over MgSO ₄ and concentrated. The resulting organic material was separated using a silicagel column to obtain final compound 1-1 (9.9 g, 65%).

1-14 Synthetic Examples

Sub-1 (1) (11.5 g, 22.2 mmol) and Sub 2-14 (6.4 g, 19.0 mmol) were used to synthesize the final compound 1-14 (10.5 g, 61%).

1-27 Synthetic Examples

Sub-1 (7) (13.7 g, 22.2 mmol) and Sub 2-27 (13.1 g, 19.0 mmol) were used to synthesize the final compound 1-27 (16.4 g, 60%).

2-6 Synthetic Examples

Sub-1 (1) (11.5 g, 22.2 mmol) and Sub 2-42 (7.2 g, 19.0 mmol) were used to synthesize the final compound 2-6 (11.5 g, 63%).

2-20 Synthetic Example

Sub-1 (1) (11.5 g, 22.2 mmol) and Sub 2-56 (8.1 g, 19.0 mmol) were used to synthesize the final compound 2-20 (12.7 g, 61%).

2-29 Synthetic Examples

Sub-1 (1) (11.5 g, 22.2 mmol) and Sub 2-65 (10.6 g, 19.0 mmol) were subjected to synthesis of 1-1 described above to give final compound 2-29 (13.7 g, 62%).

3-11 Synthetic Examples

Sub-3 (14.3 g, 22.2 mmol) and Sub 2-83 (8.4 g, 19.0 mmol) were subjected to synthesis of 1-1 described above to give final compound 3-11 (13.4 g, 60%).

3-21 Synthetic Example

Sub-1 (1) (11.5 g, 22.2 mmol) and Sub 2-93 (9.1 g, 19.0 mmol) were subjected to synthesis of 1-1 described above to give final compound 3-21 (12.4 g, 61%).

3-34 Synthetic examples

Sub-1 (10) (13.7 g, 22.2 mmol) and Sub 2-108 (6.7 g, 19.0 mmol) were used to synthesize final compound 3-34 (12.3 g, 62%).

4-5 Synthetic Examples

Sub-1 (1) (11.5 g, 22.2 mmol) and Sub 2-113 (7.0 g, 19.0 mmol) were used to synthesize final compound 4-5 (12.3 g, 69%).

4-16 Synthetic Example

The final compound 4-16 (13.8 g, 60%) was obtained by using Sub 1 (5) (14.5 g, 22.2 mmol) and Sub 2-124 (8.8 g, 19.0 mmol) using the synthesis method of 1-1 described above.

4-22 Synthetic Example

Sub-1 (6) (13.2 g, 22.2 mmol) and Sub 2-130 (10.8 g, 19.0 mmol) were used to synthesize final compound 4-22 (15.9 g, 66%).

4-25 Synthetic Example

The desired 4-25 (16.2 g, 65%) of Sub 1 (1) (11.5 g, 22.2 mmol) and Sub 2-133 (13.0 g, 19.0 mmol) was obtained using the synthesis method of 1-1 described above.

Evaluation of manufacturing of organic electric device

[ Example  One] Green organic electroluminescent device (Phosphorescent host)

A 4,4 ', 4 "-tris [2-naphthyl (phenyl) amino] triphenylamine (hereinafter abbreviated as" 2-TNATA ") film was vacuum deposited on the ITO layer (anode) After the formation of the injection layer, a 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as NPD) film was vacuum deposited to a thickness of 60 nm to form a hole transport layer. Then, the compound 1-1 of the present invention was used as a host material and tris (2-phenylpyridine) -iridium (hereinafter referred to as "Ir (ppy) ₃ ") was used as a dopant on the hole transport layer at a weight ratio of 95: (1, 1'-biphenyl-4-olato) bis (2-methyl-8-quinolinolato) aluminum (hereinafter referred to as "BAlq") as a hole blocking layer was formed on the light emitting layer. after the abbreviated) a 10 nm thickness by vacuum vapor deposition, and the hole-tris- the electron transport layer on the blocking layer (8-hydroxyquinoline) aluminum (hereinafter abbreviated as "Alq _3"), and vacuum deposited to a thickness of 40 nm., As the electron injection layer The halogenated alkali metal, an LiF deposited to 0.2 nm thickness, and then Al was prepared in the organic electroluminescent device by forming a negative electrode was deposited in a thickness of 150 nm.

[ Example  2] to [ Example  36]

An organic electroluminescent device was prepared in the same manner as in Example 1, except that the compound of the present invention described in Table 4 was used instead of the compound 1-1 of the present invention as a host material of the light emitting layer.

[ Comparative Example  1] to [ Comparative Example  3]

An organic electroluminescence device was prepared in the same manner as in Example 1, except that one of the following Comparative Compounds A to C was used in place of Compound 1-1 of the present invention as a host material in the light emitting layer.

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

Electruminescence (EL) characteristics were measured with photoresearch PR-650 by applying a forward bias DC voltage to the organic electroluminescent devices manufactured in Examples 1 to 36 and Comparative Examples 1 to 3 of the present invention And the T95 lifetime was measured using a life measuring instrument manufactured by Mac Science Inc. at a 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 organic electroluminescent device material of the present invention as a phosphorescent host significantly improved the driving voltage, lifetime and luminous efficiency as compared with the organic electroluminescent devices of the comparative examples.

Comparing Comparative Examples 1 to 3, it can be seen that the comparative compound B in which carbazole is substituted for the same core as the present invention and the comparative compound C are used rather than the comparative compound A, which is CBP mainly used as a host material, It can be seen that it is excellent. It is also seen that the driving voltage, lifetime and efficiency of the device are further improved by using the compound of the present invention in which quinazoline rather than carbazole is substituted for the same core as Comparative Examples 2 and 3 as a host material.

These results show that even though the same core is used, the characteristics of the device are changed according to the substituent substituted in the core. The energy level of the compound (HOMO level, LUMO level, T1 level) And that the difference in the physical properties of such compounds may act as a major factor (eg, energy balance) in improving the device performance during device deposition, which may result in different device characteristics.

While the present invention has been described with reference to exemplary embodiments, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. Accordingly, the embodiments disclosed herein are intended to be illustrative rather than limiting, and the spirit and scope of the present invention is not limited by these embodiments. The scope of protection of the present invention should be construed according to the following claims, and all the techniques within the scope of the same should be construed as being included in the scope of the present invention.

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

Claims (14)

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

Ar ¹ to Ar ⁴ are each independently a C ₆ to C ₆₀ aryl group, Ar ¹ and Ar ² may be bonded to each other to form a ring, Ar ³ and Ar ⁴ may be bonded to each other to form a ring ,
R ¹ and R ² are independently of each other hydrogen; heavy hydrogen; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R _a ) (R _b ); adjacent R ^{1 s} may be bonded to each other to form a ring, and neighboring R ^{2 s} may be bonded to each other to form a ring N is an integer of 0 to 4, m is an integer of 0 to 3,
L ¹ is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from the group consisting of O, N, S, Si and P, o is an integer of 0 or 1,
X ¹ to X ⁴ are C (R ₀ ) or N, at least two of X ¹ to X ⁴ are N,
The Z ring is a C ₆ to C ₆₀ aromatic hydrocarbon or a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si and P,
Wherein R &lt; ₀ &gt; is independently selected from the group consisting of hydrogen; heavy hydrogen; halogen; A C ₆ to C ₆₀ aryl group; A fluorenyl group; A C ₂ to C ₆₀ heterocyclic group containing at least one heteroatom selected from O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; A C ₁ to C ₅₀ alkyl group; An alkenyl group having ₂ to ₂₀ carbon atoms; An alkynyl group having ₂ to ₂₀ carbon atoms; A C ₁ to C ₃₀ alkoxyl group; An aryloxy group of C ₆ to C ₃₀ ; And -L'-N (R _a ) (R _b ); adjacent R ₀ may be bonded to each other to form a ring,
L 'is a single bond; An arylene group having ₆ to ₆₀ carbon atoms; A fluorenylene group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group,
R _a and R _b are each independently a C ₆ to C ₆₀ aryl group; A fluorenyl group; A fused ring group of an aliphatic ring of C ₃ to C ₆₀ and an aromatic ring of C ₆ to C ₆₀ ; And a C ₂ to C ₆₀ heterocyclic group containing at least one hetero atom selected from O, N, S, Si and P;
A ring formed by bonding Ar ¹ to Ar ⁴ , R ¹ , R ² , R ₀ , R _a , R _b , L ¹ and Z ring, Ar ¹ and Ar ^{2 to} each other, Ar ³ and Ar ⁴ are bonded to each other form a ring, formed by coupling together the adjacent rings together R ^1, R ² adjacent the ring formed by combining each other, and formed by adjacent R ₀ bonded to each other, each ring is 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, Si and P; A C ₃ -C ₂₀ cycloalkyl group; An arylalkyl group of C ₇ -C ₂₀ ; Aryl alkenyl group of C ₈ -C _20; And a combination of these. The method according to claim 1,
(1) is represented by one of the following Chemical Formulas (2) to (5): < EMI ID =
&Lt; Formula 2 &gt;&lt; EMI ID =

&Lt; Formula 4 >< EMI ID =

In the above Chemical Formulas 2 to 5,
Ar ¹ to Ar ⁴ , R ¹ , R ² , n, m, L ¹ , X ¹ to X ⁴ are the same as defined in claim 1,
F ¹ and F ² are independently of each other N (R '), S, O or C (R') (R "),
Wherein R 'and R &quot; are independently selected from the group consisting of hydrogen, a C ₁ to C ₂₀ alkyl group, a C ₆ to C ₂₀ aryl group, and a C ₂ to C ₆ heteroatom containing at least one heteroatom selected from O, N, To C ₂₀ heterocyclic groups, and R 'and R "may combine with each other to form a ring,
a and b are each an integer of 0 or 1, and a + b is an integer of 1 or more. The method according to claim 1,
Wherein X ¹ and X ³ are N, X ² and X ⁴ are N, and X ¹ and X ⁴ are N. The method according to claim 1,
Adjacent R &lt; ¹ &gt; s or adjacent R &lt; ^{2 &gt;} are bonded to each other to form a ring. The method according to claim 1,
Ar ¹ = Ar ² or compound, characterized in that Ar ³ = Ar ^4. The method according to claim 1,
Ar ¹ ≠ Ar ² or compound, characterized in that Ar ³ ≠ Ar ^4. The method according to claim 1,
Wherein the compound of formula (I) is one of the following compounds:

. A first electrode; A second electrode; And an organic material layer formed between the first electrode and the second electrode and containing a compound according to any one of claims 1 to 7. 9. The method of claim 8,
Wherein the compound is contained in the organic compound layer in the form of a single compound or a mixture of two or more compounds. 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 the compound is contained in the light emitting layer. 10. The method of claim 9,
Wherein the compound is used as a phosphorescent host material of the light emitting 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. 14. The method of claim 13,
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.

Images