KR102220954B1 - Compound for organic electronic element, organic electronic element using the same, and an electronic device thereof - Google Patents

Abstract

The present invention provides a novel compound capable of improving luminous efficiency, stability, and lifespan of a device, an organic electric device using the same, and an electronic device thereof.

Description

Compound for organic electric device, organic electric device using the same, and electronic device thereof {COMPOUND FOR ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF}

The present invention relates to a compound for an organic electric device, an organic electric device using the same, and an electronic device thereof.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic electric device using an organic light emission phenomenon has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

Materials used as an organic material layer in an organic electric device can be classified into light-emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, according to their functions.

Lifespan and efficiency are the most problematic in organic electroluminescent devices, and as displays become larger, these efficiency and lifetime issues must be resolved.

Efficiency, lifespan, and driving voltage are related to each other, and when the efficiency is increased, the driving voltage decreases relatively, and as the driving voltage decreases, crystallization of organic materials by Joule heating generated during driving decreases. It indicates a tendency to increase life expectancy.

However, simply improving the organic material layer cannot maximize efficiency. This is because the long life and high efficiency can be achieved at the same time when an optimum combination of the energy level and T1 value between each organic material layer and the intrinsic properties of the material (mobility, interfacial properties, etc.) is achieved.

In addition, in order to solve the problem of light emission in the hole transport layer in recent organic electroluminescent devices, a light emission auxiliary layer must exist between the hole transport layer and the light emitting layer, and different light emission assistance according to each light emitting layer (R, G, B) It is the time when layer development is necessary.

In general, electrons are transferred from the electron transport layer to the light emitting layer, and holes are transferred from the hole transport layer to the light emitting layer, thereby generating excitons through recombination.

However, in the case of a material used in the hole transport layer, since it must have a low HOMO value, most have a low T1 value, and this causes excitons generated in the emission layer to pass to the hole transport layer, resulting in charge unbalance in the emission layer. This results in light emission at the hole transport layer interface.

When light is emitted at the hole transport layer interface, the color purity and efficiency of the organic electronic device are deteriorated, and the lifespan is shortened. Therefore, development of a light emitting auxiliary layer having a high T1 value and having a HOMO level between the HOMO energy level of the hole transport layer and the HOMO energy level of the light emitting layer is urgently required.

On the other hand, while delaying the penetration and diffusion of metal oxides from the anode electrode (ITO) into the organic layer, which is one of the causes of shortening the lifespan of organic electronic devices, stable properties against Joule heating generated when the device is driven, that is, high glass transition It is necessary to develop a material for a hole injection layer having a temperature. The low glass transition temperature of the hole transport layer material has a property of lowering the uniformity of the thin film surface when the device is driven, and it is reported that it has a great effect on the life of the device. In addition, OLED devices are mainly formed by a vapor deposition method, and it is necessary to develop a material that can withstand a long time during deposition, that is, a material having strong heat resistance.

In other words, in order to fully exhibit the excellent characteristics of organic electronic devices, materials that make up the organic material layer in the device, such as hole injection materials, hole transport materials, light-emitting materials, electron transport materials, electron injection materials, and light-emitting auxiliary layer materials, are stable and efficient. Supported by the material must precede, but the development of a stable and efficient organic material layer material for organic electric devices has not been sufficiently achieved. Accordingly, development of new materials is continuously required, and in particular, development of a material combination of a light emitting auxiliary layer and a hole transport layer is urgently required.

The technology serving as the background of the present invention is disclosed in the publications described in the following patent documents.

Republic of Korea Patent Publication No. 10-2006-0059613 (2006.6.2.) US patent publication US6242115 (2001.6.5.)

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

In one aspect, the present invention provides a compound represented by the following formula.

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

By using the compound according to the present invention, the driving voltage of the device can be lowered, and color purity, luminous efficiency, and lifespan can be greatly improved.

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

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings.

In adding reference numerals to elements of each drawing, it should be noted that the same elements are assigned the same numerals as possible even if they are indicated on different drawings. In addition, in describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the subject matter of the present invention, a detailed description thereof will be omitted.

In addition, in describing the constituent elements of the present invention, terms such as first, second, A, B, (a), (b) may be used. These terms are only used to distinguish the component from other components, and the nature, order, or order of the component is not limited by the term. When a component is described as being "connected", "coupled" or "connected" to another component, the component may be directly connected or connected to that other component, but another component between each component It should be understood that elements may be “connected”, “coupled” or “connected”.

Meanwhile, the term "halo" or "halogen" used herein includes fluorine, chlorine, bromine, and iodine unless otherwise stated.

The term "alkyl" or "alkyl group" as used herein has a carbon number of 1 to 60 unless otherwise specified, and is not limited thereto.

The terms "alkenyl" or "alkynyl" used in the present invention each have a double bond or triple bond of 2 to 60 carbon atoms, unless otherwise specified, and are not limited thereto.

The term "cycloalkyl" as used in the present invention means an alkyl forming a ring having 3 to 60 carbon atoms, unless otherwise specified, and is not limited thereto.

The term "alkoxy group" used in the present invention has a carbon number of 1 to 60 unless otherwise specified, and is not limited thereto.

The terms "aryl group" and "arylene group" used in the present invention each have 6 to 60 carbon atoms, and are not limited thereto.

In the present invention, an aryl group or an arylene group refers to a single ring or multiple ring aromatics, and includes an aromatic ring formed by neighboring substituents participating in a bond or reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, or a spirofluorene group.

As used herein, the term “heteroalkyl” refers to an alkyl containing one or more heteroatoms unless otherwise specified. The term "heteroaryl group" or "heteroarylene group" as used herein refers to an aryl group or arylene group having 2 to 60 carbon atoms each including one or more heteroatoms, unless otherwise specified, and is limited thereto Not only a single ring but also multiple rings are included, and neighboring groups may be formed by bonding.

The terms "heterocycloalkyl" and "heterocyclic group" as used herein include one or more heteroatoms, have 2 to 60 carbon atoms, and include multiple rings as well as single rings, unless otherwise specified, , May be formed by combining adjacent groups. In addition, "heterocyclic group" may mean an alicyclic and/or aromatic containing a hetero atom.

The term "heteroatom" as used herein refers to N, O, S, P and Si unless otherwise specified.

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

Unless otherwise specified, the term "ring" used in the present invention refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms or an aromatic ring having 6 to 60 carbon atoms or a hetero ring having 2 to 60 carbon atoms or a combination thereof, It contains saturated or unsaturated rings.

Other hetero compounds or hetero radicals other than the aforementioned hetero compounds include one or more heteroatoms, but are not limited thereto.

In addition, unless explicitly stated, the term "substituted or unsubstituted" used in the present invention means "substituted" deuterium, halogen, amino group, nitrile group, nitro group, C ₁ to C ₂₀ alkyl group, C ₁ to C ₂₀ alkoxy group, C ₁ to C ₂₀ alkylamine group, C ₁ to C ₂₀ alkylthiophene group, C ₆ to C ₂₀ arylthiophene group, C ₂ to C ₂₀ alkenyl group, C ₂ to C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₆ ~ C ₂₀ aryl group _{substituted with deuterium, C 8} ~ C ₂₀ arylalkenyl group, silane group, boron It means substituted with one or more substituents selected from the group consisting of a group, a germanium group, and a C ₂ ~ C _{20 heterocyclic group, and is not limited to these substituents.}

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

Referring to FIG. 1, the organic electric device 100 according to the present invention includes a first electrode 120, a second electrode 180, and a first electrode 110 and a second electrode 180 formed on a substrate 110. ) Between the organic material layer containing the compound represented by the formula (1). In this case, the first electrode 120 may be an anode (anode), the second electrode 180 may be a cathode (cathode), and in the case of an inverted type, the first electrode may be a cathode and the second electrode may be an anode.

The organic material layer may include a hole injection layer 130, a hole transport layer 140, an emission layer 150, an electron transport layer 160, and an electron injection layer 170 sequentially on the first electrode 120. In this case, other layers other than the emission layer 150 may not be formed. A hole blocking layer, an electron blocking layer, a light emission auxiliary layer 151, a buffer layer 141, etc. may be further included, and the electron transport layer 160 may serve as a hole blocking layer.

Further, although not shown, the organic electric device according to the present invention may further include a protective layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer.

The compound according to the present invention applied to the organic material layer is a material of a hole injection layer 130, a hole transport layer 140, an electron transport layer 160, an electron injection layer 170, a host of the emission layer 150, a dopant, or a capping layer. Can be used as Preferably, the compound of the present invention may be used as at least one of a host material of a light emitting layer, a hole transport layer material, and a light emitting auxiliary layer material.

On the other hand, even with the same core, the band gap, electrical characteristics, and interfacial characteristics may vary depending on which substituent is bonded to any position, so the selection of the core and the combination of sub-substituents bonded thereto are also very It is important, and in particular, long life and high efficiency can be achieved at the same time when an optimum combination of the energy level and T1 value between each organic material layer and the intrinsic properties of the material (mobility, interfacial properties, etc.) is achieved.

As described above, in order to solve the problem of light emission in the hole transport layer in recent organic electroluminescent devices, it is preferable to form a light emitting auxiliary layer between the hole transport layer and the light emitting layer, and each light emitting layer (R, G, B) It is the time when it is necessary to develop another light emitting auxiliary layer. On the other hand, in the case of the light-emitting auxiliary layer, since the correlation between the hole transport layer and the light-emitting layer (host) must be grasped, even if a similar core is used, it will be very difficult to infer its characteristics if the used organic material layer is different.

Therefore, in the present invention, by using the compound represented by Formula 1 as a material for a hole transport layer and a material for a light emission auxiliary layer, the energy level and T1 value between each organic material layer, intrinsic properties of the material (mobility, interface characteristics, etc.) By optimizing, it is possible to improve the life and efficiency of the organic electronic device at the same time.

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

In addition, the organic material layer is a solution process or a solvent process other than a deposition method using various polymer materials, such as a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, a roll-to-roll process, and a doctor blaze. It can be manufactured with fewer layers by a method such as a printing process, a screen printing process, or a thermal transfer method. 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 electric device according to the present invention may be a top emission type, a bottom emission type, or a double side emission type depending on the material used.

In addition, the organic electric device according to the present invention may be one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a single color or white lighting device.

Another embodiment of the present invention may include a display device including the organic electric device of the present invention described above, and an electronic device including a control unit for controlling the display device. At this time, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as mobile communication terminals such as mobile phones, PDAs, electronic dictionaries, PMPs, remote controls, navigation, game consoles, various TVs, and various computers.

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

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

[Formula 1]

또는

이며, 여기서 *은 A환이 인돌 형태의 화합물(인돌유도체)에 융합되는 위치를 나타낸다. 따라서, A환과 인돌유도체는 상기 화학식에서와 같이 한 변을 공유하도록 결합될 수 있다.In Formula 1, ring A is

or

Where * represents the position where the A ring is fused to the indole type compound (indole derivative). Accordingly, ring A and the indole derivative may be bonded to share one side as in the above formula.

In the ring A, X is O, S, NR ₁₁ , CR ₁₂ R ₁₃ or SiR ₁₄ R ₁₅ , and Y is O, NR ₁₆ , CR ₁₇ R ₁₈ or SiR ₁₉ R ₂₀ .

R ₁₁ to R ₂₀ are each independently hydrogen; C ₁ ~ C ₅₀ alkyl group; C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one hetero atom of P; And -L ₁ -N (Ar ₃ ) (Ar ₄ ); may be selected from the group consisting of. At this time, R ₁₂ and R ₁₃ and/or R ₁₇ and R ₁₈ may be bonded to each other to form a spiro compound. Specifically, R ₁₁ to R ₂₀ may each independently be methyl or phenyl.

R ₁ to R ₄ are each independently hydrogen; halogen; C ₆ ~ C ₆₀ aryl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; Fluorenyl group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; An alkoxyl group of C ₁ to C _30; And -L ₂ -N (Ar ₅ ) (Ar ₆ ); may be selected from the group consisting of.

In addition, R ₁ to R ₄ may form at least one ring by bonding adjacent groups to each other. Here,'neighboring groups combine with each other to form at least one ring' means that R ₁ and R ₂ are bonded to each other, R ₂ and R ₃ are bonded to each other, and/or R ₃ and R ₄ are bonded to each other to form at least one ring. It means to form a compound. At this time, since it is important that neighboring groups combine with each other to form a ring, the scope of the present invention is not limited by which substituents and through which reactions the rings are formed, and the rings are known reactions ( Heck reaction or Chem. Eur. J. 2009, 15, 742, Molecules. 2008, 13, 3236-3245, J. Am. Chem. Soc. 2008, 130, 472-480, Tetrahedron Letters. 1997, 38, 4761- 4764, etc.).

The _{ring formed by bonding of adjacent groups among R 1} to R ₄ may be a monocyclic or polycyclic aromatic ring or a hetero ring containing at least one hetero atom, as well as a form in which an aromatic ring and an aliphatic ring are fused. For example, _{neighboring groups among R 1} and R _{4 may} be bonded to each other to form an aromatic ring such as benzene, naphthalene, phenanthrene, and the like, and the number of carbon atoms of the aromatic ring formed at this time is preferably 6 to 60. For example, when R ₁ and R ₂ are bonded to each other to form a benzene ring, and R ₃ and R ₄ are bonded to each other to form a benzene ring, a phenanthrene form may be formed together with the benzene ring of the parent nucleus to which they are bonded.

In addition, _{neighboring groups among R 1} to R _{4 may} be bonded to each other to form a heterocycle such as thiophene, furan, pyridine, indole, quinoline, and the like, wherein the number of carbon atoms may be 2 to 60. In addition, in the case of a polycyclic ring, it may be a fused form or a form in which a plurality of rings are not fused to each other, or a ring in which a fused form and a non-fused form are mixed.

Ar ₁ and Ar ₂ are each independently a C ₆ ~ C ₆₀ aryl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; C ₁ ~ C ₅₀ alkyl group; -L ₃ -N(Ar ₇ )(Ar ₈ ); And fluorenyl group; may be selected from the group consisting of. Specifically, Ar ₁ and Ar ₂ may each independently be phenyl, biphenyl, naphthyl, fluorene, spirofluorene, fluorene, phenanthrene or carbazole.

The L and L ₁ to L ₃ are each independently a single bond; C ₆ ~ C ₆₀ arylene group; Fluorenylene group; C ₂ ~ C ₆₀ Heteroarylene group; C ₃ ~ C ₆₀ cycloalkylene 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 divalent aliphatic hydrocarbon group; may be selected from the group consisting of, and each of these (except a single bond) is a nitro group, a nitrile group, a halogen group, a C ₁ to C ₂₀ alkyl group, a C ₆ to C ₂₀ aryl group, It may be substituted with one or more substituents selected from the group consisting of a C ₂ ~ C ₂₀ heterocyclic group, a C ₁ ~ C _{20 alkoxy group and an amino group.} Specifically, L and L ₁ to L ₃ may each independently be phenyl, biphenyl, fluorene, dibenzothiophene or dibenzofuran.

On the other hand, the Ar ₃ to Ar ₈ are each independently, C ₆ ~ C ₆₀ aryl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; C ₁ ~ C ₅₀ alkyl group; And fluorenyl group; may be selected from the group consisting of.

When the R ₁ to R ₄ , Ar ₁ to Ar ₈ , R ₁₁ to R ₂₀ are aryl groups, each of them is deuterium, halogen, silane group, boron group, germanium group, cyano group, nitro group, C ₁ to C ₂₀ Import of an alkylthio, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ of alkenyl groups (alkenyl), an alkynyl of C ₂ ~ C ₂₀ group (alkynyl) a, C ₆ ~ C ₂₀ aryl group, C ₆ to C ₂₀ aryl group _{substituted with deuterium, C 2} to C ₂₀ heterocyclic group, C ₃ to C ₂₀ cycloalkyl group, C ₇ to C ₂₀ It may be substituted with one or more substituents selected from the group consisting of an arylalkyl group and a C ₈ ~ C _{20 arylalkenyl group,}

When R ₁ to R ₄ , Ar ₁ to Ar ₈ , R ₁₁ to R ₂₀ are heterocyclic groups, each of them is deuterium, halogen, silane group, cyano group, nitro group, C ₁ to C ₂₀ alkoxyl group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ heterocycle of the C ₂₀ of the alkenyl group _{(alkenyl), C 6 ~ C} 20 aryl group, a C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ substituted with deuterium atoms, C ₃ ~ C ₂₀ cycloalkyl group, C ₇ ~ C ₂₀ It may be substituted with one or more substituents selected from the group consisting of an arylalkyl group and a C ₈ ~ C _{20 arylalkenyl group.}

And, when R ₁ to R ₄ , Ar ₁ to Ar ₈ , R ₁₁ to R ₂₀ are alkyl groups, each of these is halogen, silane group, boron group, cyano group, C ₁ to C ₂₀ alkoxyl group, C ₁ to alkyl group of C _20, C ₂ ~ C ₂₀ of alkenyl groups _{(alkenyl), C 6 ~ C} 20 aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, C ₂ ~ C ₂₀ heterocyclic group, C of It may be substituted with one or more substituents selected from the group consisting of an _{arylalkyl group of 7} to C _{20 and} an arylalkenyl group of C ₈ to C _20,

When R ₁ to R ₄ , Ar ₁ to Ar ₈ , R ₁₁ to R ₂₀ are fluorenyl groups, each of them is deuterium, halogen, silane group, cyano group, C ₁ to C ₂₀ alkyl group, C ₂ to C ₂₀ the alkenyl group (alkenyl), the group consisting of a cycloalkyl group of C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ aryl group, C ₂ ~ C ₂₀ heterocyclic group and C ₃ ~ C ₂₀ substituted by deuterium It may be substituted with one or more substituents selected from.

In addition, when R ₁ to R ₄ are alkenyl groups, each of these is deuterium, halogen, silane group, cyano group, C ₁ to C ₂₀ alkoxyl group, C ₁ to C ₂₀ alkyl group, C ₂ to C ₂₀ alkene group _{(alkenyl), C 6 ~ C} 20 aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a heterocyclic group of C ₂ ~ C _20, a cycloalkyl group of _{C 3 ~ C 20, C 7} ~ C _{Of 20} It may be substituted with one or more substituents selected from the group consisting of an arylalkyl group and a C ₈ ~ C _{20 arylalkenyl group,}

R ₁ ~ R Case ₄ is an alkoxyl group, each of which is of a C ₆ ~ C ₂₀ substituted with heavy hydrogen, a halogen, a silane group, an aryl group, a heavy hydrogen of the C ₁ ~ C ₂₀ alkyl group, C ₆ ~ C ₂₀ aryl group , C ₂ ~ C ₂₀ It may be substituted with one or more substituents selected from the group consisting of a heterocyclic group and a C ₃ ~ C _{20 cycloalkyl group.}

On the other hand, in the case of the aryl group, the number of carbon atoms may be 6 to 60, preferably 6 to 30, more preferably 6 to 20 carbon atoms,

In the case of the heterocyclic group, the number of carbon atoms may be 2 to 60, preferably 2 to 30, more preferably 2 to 20 carbon atoms,

In the case of the arylene group, the number of carbon atoms may be 6 to 60, preferably 6 to 30, more preferably an arylene group having 6 to 20 carbon atoms,

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

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

<Formula 2> <Formula 3> <Formula 4> <Formula 5>

<Formula 6> <Formula 7> <Formula 8> <Formula 9>

<Formula 10> <Formula 11> <Formula 12> <Formula 13>

In Formulas 2 to 13, X, Y, L, Ar ₁ and Ar ₂ are the same as defined in Formula 1. Formulas 2 to 5 and Formulas 10 to 13 are

와

를 융합시켜 형성된 것이며, 화학식 6 내지 화학식 9는

와

를 융합시켜 형성된 것이다. 여기서 *는 오각고리와 인돌 형태의 화합물이 서로 융합되는 위치를 의미한다.

Wow

It is formed by fusing, and Chemical Formulas 6 to 9 are

Wow

It was formed by fusing them. Here, * means the position where the pentagonal ring and the indole type compound are fused to each other.

More specifically, the formula represented by Formula 1 may be one of the following compounds.

Hereinafter, examples for synthesizing the compound represented by Formula 1 and an organic electric device according to the present invention will be described in detail, but the present invention is not limited to the following examples.

Synthesis example

Illustratively, the compounds (final products) according to the present invention can be prepared by the following Scheme 1 or Scheme 1-1.

<Reaction Scheme 1>

<Reaction Scheme 1-1>

또는

의 형태를 이루고 있으며,At this time, the A ring in Scheme 1 is

or

Is in the form of

과 융합된다. 따라서, A환이 융합되는 형태에 따라 오각고리 내의 X 또는 Y의 위치가 변화될 수 있기 때문에, 상기 반응식 1-1과 같이 X₁ 또는 X₃에 X가 위치할 수 있으며, 또는 X₂에 Y가 위치할 수 있다 것을 나타내었다.

Is fused with Therefore, since the position of X or Y in the pentagonal ring may change depending on the form in which the ring A is fused, X may be located in X ₁ or X ₃ as in Scheme 1-1, or Y may be in X ₂ Indicated that it can be located.

For example, Sub 1 is the following formula (a) when X is located at the position of _{X 1, and} the following formula (b) when Y is located at the position of _{X 2 , X is located at the position of X 3} In the case of, it may be in the form of the following formula (c).

(a) (b) (c)

_{Therefore, any one of X 1} and X ₃ in the reaction formulas of the following examples is X or X ₂ is Y, and the resonance structure (position of a double bond), etc. is in the same form as a, b, and c in each case. You can have.

Hereinafter, a synthesis example of the present invention will be described in more detail through examples.

Sub Synthesis of 1

Sub 1 of Reaction Scheme 1 may be synthesized by the reaction route of Reaction Schemes 2 to 5.

One. Sub 1(A) Synthesis example

<Reaction Scheme 2>

(One) Sub 1-2 synthesis

Sub 1-1 (1 equivalent) and phenylboronic acid (1 equivalent) substituted _{with R 1} to R _{4 , Pd(PPh 3} ) ₄ (0.03 equivalent), K ₂ CO ₃ (3 equivalent), anhydrous THF and a small amount of water After dissolving in, it was refluxed for 24 hours. When the reaction was completed, the temperature of the reaction product was cooled to room temperature _{, extracted with CH 2} Cl ₂ , and washed with water. A small amount of water _{was removed with anhydrous MgSO 4} , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 1-2.

(2) Sub 1-3 synthesis

Sub 1-2 (1 equivalent) and triphenylphosphine (2.5 equivalent) obtained in the above synthesis were dissolved in o-dichlorobenzene, and refluxed for 24 hours. When the reaction was completed, the solvent was removed by distillation under reduced pressure, and the concentrated product was separated by column chromatography to obtain the desired Sub 1-3.

(3) Sub 1(A) synthesis

After dissolving Sub 1-3 (1 equivalent) obtained in the above synthesis with THF in a round bottom flask, IL-Br compound (1.5 equivalent), Pd ₂ (dba) ₃ (0.05 equivalent), P(t-Bu) ₃ ( 0.1 eq), NaO t -Bu (3 eq), and toluene (10.5 mL / 1 mmol) were added, and the reaction was proceeded at 100°C. When the reaction was completed, CH ₂ Cl ₂ and water were extracted, the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized in a silicagel column to obtain Sub 1 (A).

2. Sub 1(B) Synthesis example

<Reaction Scheme 3>

(One) Sub 1-4 synthesis

Sub 1-1 (1 equivalent) and R ₃ , R ₄ substituted naphthalen-2-ylboronic acid (1 equivalent), Pd(PPh ₃ ) ₄ (0.03 equivalent), K ₂ CO ₃ (3 equivalent) anhydrous THF And a small amount of water, and then refluxed for 24 hours. When the reaction was completed, the temperature of the reaction product was cooled to room temperature _{, extracted with CH 2} Cl ₂ , and washed with water. A small amount of water _{was removed with anhydrous MgSO 4} , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 1-4.

(2) Sub 1-5 synthesis

Sub 1-4 (1 equivalent) and triphenylphosphine (2.5 equivalents) obtained in the above synthesis were dissolved in o-dichlorobenzene and refluxed for 24 hours. When the reaction was completed, the solvent was removed by distillation under reduced pressure, and the concentrated product was separated by column chromatography to obtain the desired Sub 1-5.

(3) Sub 1(B) synthesis

After dissolving Sub 1-5 (1 equivalent) obtained in the above synthesis with THF in a round bottom flask, IL-Br compound (1.5 equivalent), Pd ₂ (dba) ₃ (0.05 equivalent), P(t-Bu) ₃ ( 0.1 eq), NaO t -Bu (3 eq), and toluene (10.5 mL / 1 mmol) were added, and the reaction was proceeded at 100°C. When the reaction was completed, CH ₂ Cl _{2 was} extracted with water and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized in a silicagel column to obtain Sub 1 (B).

3. Sub 1(C) Synthesis example

<Reaction Scheme 4>

(One) Sub 1-6 synthesis

Sub 1-1 (1 equivalent) and R ₁ , R ₂ substituted naphthalen-1-ylboronic acid (1 equivalent), Pd(PPh ₃ ) ₄ (0.03 equivalent), K ₂ CO ₃ (3 equivalent) anhydrous THF And a small amount of water, and then refluxed for 24 hours. When the reaction was completed, the temperature of the reaction product was cooled to room temperature _{, extracted with CH 2} Cl ₂ , and washed with water. A small amount of water _{was removed with anhydrous MgSO 4} , filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated by column chromatography to obtain the desired Sub 1-6.

(2) Sub 1-7 synthesis

Sub 1-6 (1 equivalent) and triphenylphosphine (2.5 equivalents) obtained in the above synthesis were dissolved in o-dichlorobenzene and refluxed for 24 hours. When the reaction was completed, the solvent was removed by distillation under reduced pressure, and the concentrated product was separated by column chromatography to obtain the desired Sub 1-7.

(3) Sub 1(C) synthesis

After dissolving Sub 1-7 (1 equivalent) obtained in the above synthesis with THF in a round bottom flask, IL-Br compound (1.5 equivalent), Pd ₂ (dba) ₃ (0.05 equivalent), P(t-Bu) ₃ ( 0.1 eq), NaO t -Bu (3 eq), and toluene (10.5 mL / 1 mmol) were added, and the reaction was proceeded at 100°C. When the reaction was completed, CH ₂ Cl _{2 was} extracted with water and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized in a silicagel column to obtain Sub 1 (C).

4. Sub 1(D) Synthesis example

<Reaction Scheme 5>

(One) Sub 1-8 synthesis

After dissolving Sub 1-1 (1 equivalent), phenanthren-9-ylboronic acid (1 equivalent), Pd(PPh ₃ ) ₄ (0.03 equivalent), and K ₂ CO ₃ (3 equivalent) in anhydrous THF and a small amount of water, , Refluxed for 24 hours. When the reaction was completed, the temperature of the reaction product was cooled to room temperature _{, extracted with CH 2} Cl ₂ , and washed with water. A small amount of water _{was removed with anhydrous MgSO 4} , filtered under reduced pressure, the organic solvent was concentrated, and the resulting product was separated using column chromatography to obtain the desired Sub 1-8.

(2) Sub 1-9 synthesis

Sub 1-8 (1 equivalent) and triphenylphosphine (2.5 equivalents) obtained in the above synthesis were dissolved in o-dichlorobenzene and refluxed for 24 hours. When the reaction was completed, the solvent was removed by distillation under reduced pressure, and the concentrated product was separated by column chromatography to obtain the desired Sub 1-9.

(3) Sub 1(D) synthesis

After dissolving Sub 1-9 (1 equivalent) obtained in the above synthesis in THF in a round bottom flask, IL-Br compound (1.5 equivalent), Pd ₂ (dba) ₃ (0.05 equivalent), P(t-Bu) ₃ ( 0.1 eq), NaO t -Bu (3 eq), and toluene (10.5 mL / 1 mmol) were added, and the reaction was proceeded at 100°C. When the reaction was completed, CH ₂ Cl ₂ and water were extracted, the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized in a silicagel column to obtain Sub 1 (D).

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

[Table 1]

Sub Synthesis example of 2

Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 6 below, but is not limited thereto.

<Reaction Scheme 6>

After dissolving Br-substituted Ar ₂ (1.1 equivalent) in toluene in a round bottom flask, NH ₂ substituted Ar ₃ (1 equivalent), Pd ₂ (dba) ₃ (0.3 equivalent), 50% P( t- Bu) ₃ (9 equivalents) and NaO t -Bu (3 equivalents) were added and stirred at 40°C. When the reaction was completed, CH ₂ Cl _{2 was} extracted with water and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting compound was recrystallized by silicagel column to obtain Sub 2.

Examples of Sub 2 are as follows, but are not limited thereto. FD-MS values for exemplary compounds of Sub 2 are shown in Table 2.

[Table 2]

Final product ( Final Product ) Synthesis

In a round bottom flask, Sub 1 compound (1.1 equivalent), Sub 2 compound (1 equivalent), Pd ₂ (dba) ₃ (0.05 equivalent), P(t-Bu) ₃ (0.1 equivalent), NaO t -Bu (3 equivalent) ), toluene (10.5mL / 1mmol) is added and the reaction proceeds at 100℃. When the reaction was completed, the organic layer was extracted with ether and water, dried with MgSO ₄ , concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain a final product.

1. Synthesis example of 1-28

In a round bottom flask, 4-(4-bromophenyl)-4H-thieno[3,2-b]indole (7.9g, 24mmol), di([1,1'-biphenyl]-4-yl)amine (6.4g, 20mmol), Pd ₂ (dba) ₃ (0.03~0.05 mmol), P(t-Bu) ₃ (0.1 equivalent), NaO t -Bu (3 equivalent), toluene (10.5mL / 1mmol) at 100℃ The reaction proceeds. When the reaction was completed, the product was extracted with ether and water, and the organic layer _{was dried with MgSO 4} and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 9.0 g (yield: 79%).

2. Synthesis example of 1-80

In a round bottom flask, 4-(4-bromophenyl)-4H-furo[3,2-b]indole (9.3g, 24mmol), di([1,1'-biphenyl]-4-yl)amine (6.4g, 20mmol), Pd ₂ (dba) ₃ (0.03~0.05 mmol), P(t-Bu) ₃ (0.1 equivalent), NaO t -Bu (3 equivalent), toluene (10.5mL / 1mmol) at 100℃ The reaction proceeds. When the reaction was completed, the product was extracted with ether and water, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 8.0 g (yield: 64%).

3. Synthesis example of 2-37

10-(8-bromodibenzo[b,d]thiophen-2-yl)-10H-benzo[g]thieno[3,2-b]indole (11.6g, 24mmol), di([1,1) in a round bottom flask. '-biphenyl]-4-yl)amine (6.4g, 20mmol), Pd ₂ (dba) ₃ (0.03~0.05 mmol), P(t-Bu) ₃ (0.1 equivalent), NaO t -Bu (3 equivalent) After adding toluene (10.5mL / 1mmol), the reaction proceeds at 100℃. When the reaction was completed, the product was extracted with ether and water, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 9.4 g (yield: 65%).

4. Synthesis example of 3-38

In round bottom flask, 7-(8-bromodibenzo[b,d]furan-2-yl)-7H-benzo[e]thieno[3,2-b]indole (11.2g, 24mmol), di([1,1) '-biphenyl]-4-yl)amine (6.4g, 20mmol), Pd ₂ (dba) ₃ (0.03~0.05 mmol), P(t-Bu) ₃ (0.1 equivalent), NaO t -Bu (3 equivalent) After adding toluene (10.5mL / 1mmol), the reaction proceeds at 100℃. When the reaction was completed, the product was extracted with ether and water, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 9.4 g (yield: 66%).

5. Synthesis example of 4-39

12-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-12H-dibenzo[e,g]thieno[3,2-b]indole (13.1g, 24mmol) in a round bottom flask, di([1,1'-biphenyl]-4-yl)amine (6.4g, 20mmol), Pd ₂ (dba) ₃ (0.03~0.05 mmol), P(t-Bu) ₃ (0.1 equivalent), NaO t After adding -Bu (3 equivalents) and toluene (10.5mL / 1mmol), the reaction proceeds at 100℃. When the reaction was completed, the product was extracted with ether and water, and the organic layer _{was dried with MgSO 4} and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 10.0 g (yield: 64%).

6. Synthesis example of 2-8

10-(4-bromophenyl)-10H-benzo[g]thieno[2,3-b]indole (9.1g, 24mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2- in a round bottom flask amine (5.7g, 20mmol), Pd ₂ (dba) ₃ (0.03~0.05mmol), P(t-Bu) ₃ (0.1 equivalent), NaO t -Bu (3 equivalent), toluene (10.5mL / 1mmol) After the addition, the reaction proceeds at 100°C. When the reaction was completed, the product was extracted with ether and water, and the organic layer _{was dried with MgSO 4} and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 9.4 g (yield: 67%).

7. Synthesis example of 1-45

8-(4-bromophenyl)-8H-furo[2,3-b]indole (7.5g, 24mmol), diphenylamine (3.4g, 20mmol), Pd ₂ (dba) ₃ (0.03~0.05mmol) in round bottom flask , P(t-Bu) ₃ (0.1 equivalent), NaO t -Bu (3 equivalent), and toluene (10.5 mL / 1 mmol) are added, and the reaction proceeds at 100°C. When the reaction was completed, the product was extracted with ether and water, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 6.2 g (yield: 64%).

8. Synthesis example of 1-49

In a round bottom flask, 4-(4-bromophenyl)-4H-furo[3,4-b]indole (7.5g, 24mmol), N,9-diphenyl-9H-carbazol-3-amine (6.7g, 20mmol), After _{adding Pd 2} (dba) ₃ (0.03~0.05mmol), P(t-Bu) ₃ (0.1 equivalent), NaO t -Bu (3 equivalent), toluene (10.5mL / 1mmol), the reaction proceeds at 100℃ do. When the reaction was completed, the product was extracted with ether and water, and the organic layer _{was dried with MgSO 4} and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 8.3 g (yield: 61%).

9. Synthesis example of 3-62

7-(4-bromophenyl)-9-phenyl-7,9-dihydrobenzo[e]pyrrolo[3,4-b]indole (10.5g, 24mmol), N-(naphthalen-1-yl)- in round bottom flask 9,9-diphenyl-9H-fluoren-2-amine (9.2g, 20mmol), Pd ₂ (dba) ₃ (0.03~0.05mmol), P(t-Bu) ₃ (0.1 equivalent), NaO t -Bu ( 3 equivalents) and toluene (10.5mL / 1mmol) were added and the reaction was proceeded at 100℃. When the reaction was completed, the product was extracted with ether and water, and the organic layer _{was dried over MgSO 4} and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 12.7 g (yield: 65%).

10. Synthesis example of 4-65

In a round bottom flask, 12-(4-bromophenyl)-9-phenyl-9,12-dihydrodibenzo[e,g]pyrrolo[3,2-b]indole (11.7g, 24mmol), N-([1,1' -biphenyl]-4-yl)naphthalen-2-amine (5.9g, 20mmol), Pd ₂ (dba) ₃ (0.03~0.05mmol), P(t-Bu) ₃ (0.1 equivalent), NaO t -Bu ( 3 equivalents) and toluene (10.5mL / 1mmol) were added and the reaction was proceeded at 100℃. When the reaction was completed, the product was extracted with ether and water, and the organic layer _{was dried with MgSO 4} and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 11.5 g (yield: 68%).

11. Synthesis example of 4-69

9-(4-bromophenyl)-10,10-dimethyl-9,10-dihydrodibenzo[e,g]cyclopenta[b]indole (10.5g, 24mmol), 9,9-dimethyl-N-(naphthalen) in round bottom flask -2-yl)-9H-fluoren-2-amine (6.7g, 20mmol), Pd ₂ (dba) ₃ (0.03~0.05mmol), P(t-Bu) ₃ (0.1 equivalent), NaO t -Bu ( 3 equivalents) and toluene (10.5mL / 1mmol) were added and the reaction was proceeded at 100℃. When the reaction was completed, the product was extracted with ether and water, and the organic layer _{was dried with MgSO 4} and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 9.8 g (yield: 59%).

12. Synthesis example of 4-81

12-(7-bromo-9,9-dimethyl-9H-fluoren-2-yl)-12H-dibenzo[e,g]thieno[3,2-b]indole (13.5g, 24mmol) in a round bottom flask, di([1,1'-biphenyl]-4-yl)amine (6.4g, 20mmol), Pd ₂ (dba) ₃ (0.03~0.05mmol), P(t-Bu) ₃ (0.1 equivalent), NaO t After adding -Bu (3 equivalents) and toluene (10.5mL / 1mmol), the reaction proceeds at 100℃. When the reaction was completed, the product was extracted with ether and water, and the organic layer _{was dried with MgSO 4} and concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 10.0 g (yield: 52%).

The results of measuring FD-MS of compounds 1-1 to 4-88 according to the present invention prepared by the above method are shown in Table 3 below.

[Table 3]

Manufacturing evaluation of organic electric devices

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

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention obtained through synthesis as a material for the hole transport layer.

First, on the ITO layer (anode) formed on the organic substrate, N ¹ -(naphthalen-2-yl)-N ⁴ ,N ⁴ -bis(4-(naphthalen-2-yl(phenyl)amino)phenyl)-N ^1- A phenylbenzene-1,4-diamine (hereinafter abbreviated as 2-TNATA) film was vacuum-deposited to form a hole injection layer having a thickness of 60 nm, and then Compound 1-30 of the present invention was vacuum-deposited to a thickness of 20 nm to form a hole transport layer. . Next, 4,4'-N,N'-dicarbazole-biphenyl (hereinafter abbreviated as CBP) as a host material on the hole transport layer, tris(2-phenylpyridine)-iridium (hereinafter, about _{Ir(ppy) 3)} Flag) was used as a dopant material and doped with a weight of 90:10 to deposit a light emitting layer having a thickness of 30 nm. Subsequently, (1,1'-bisphenyl)-4-oleato)bis(2-methyl-8-quinolinoleato)aluminum (hereinafter abbreviated as BAlq) was vacuum deposited to a thickness of 10 nm to form a hole blocking layer, Tris (8-quinolinol) aluminum (hereinafter _{abbreviated as Alq 3} ) was deposited to a thickness of 40 nm to form an electron transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited on the electron transport layer to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

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

Compounds 1-31, 1-35, 1-36, 1-39, 2-30, 2-31, 2-35, 2-36, 2 of the present invention shown in Table 4 in place of Compound 1-30 of the present invention -39, 3-30, 3-31, 3-35, 3-36, 3-39, 4-30, 4-31, 4-35, 4-36, 4-39 were used as the hole transport layer material. Except, an organic electroluminescent device was manufactured in the same manner as in Example 1.

[ Comparative example One]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 1 was used as a hole transport layer material instead of Compound 1-30 of the present invention.

<Comparative compound 1>

[ Comparative example 2]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 2 below was used as the hole transport layer material instead of Compound 1-30 of the present invention.

<Comparative compound 2>

[ Comparative example 3]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 3 below was used as the hole transport layer material instead of Compound 1-30 of the present invention.

<Comparative compound 3>

Electroluminescence (EL) characteristics by applying a forward bias DC voltage to the organic electroluminescent devices manufactured according to Examples 1 to 20 and Comparative Examples 1 to 3 of the present invention with PR-650 of photoresearch The measurement results are shown in Table 4 below. At this time, the life span was measured at 300 cd/m 2 by using a life measurement equipment manufactured by McScience at a standard luminance of 300 cd/m 2.

[Table 4]

As can be seen from the results of Table 4, the organic electroluminescent device using the material for the organic electroluminescent device of the present invention significantly improved luminous efficiency, lifespan, and color purity compared to the comparative example.

Compared to Comparative Compound 1, which is a bisdiarylamine compound, when Comparative Compound 2 with carbazole as the core was used as the hole transport layer, better results were obtained, and thienoindole was the core than Comparative Compound 2 in which carbazole was the core. When Comparative Compound 3 was used as the hole transport layer, it can be seen that higher efficiency, longer life, and lower driving voltage were exhibited.

On the other hand, when comparing the results of Comparative Compound 3 and the compound of the present invention, the compound of the present invention in which the amine group is substituted at the linking group is lower than that of Comparative Compound 3 in which the heterocycle containing N next to the linking group is substituted. It was confirmed that it showed high life and efficiency.

This means that when the heterocycle is substituted, the LUMO value is lower than when the amine group is substituted, and as a result, the ability to block electrons decreases, resulting in a decrease in efficiency, and the hole injection layer (HIL) and charge balance. This is not good, so mobility is slowed down, resulting in a need for a high driving voltage, and it can be explained that the lifetime of the device is deteriorated due to the high driving voltage.

In other words, the compound of the present invention substituted with an amine group improves the ability to block electrons with an appropriate LUMO value, thereby increasing the efficiency of the device, and increasing the mobility due to good charge balance with the neighboring layer. Therefore, a low driving voltage is required, and the life of the device can be improved due to the low driving voltage.

[ Example 21] Green organic light emitting device ( Light-emitting auxiliary layer )

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

First, a 2-TNATA film was vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 60 nm, and then 4,4-bis[N-(1-naphthyl)- on the hole injection layer. N-phenylamino]biphenyl (hereinafter abbreviated as -NPD) was vacuum deposited to a thickness of 20 nm to form a hole transport layer. Thereafter, the compound 1-1 of the present invention was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form a light emission auxiliary layer. After forming the light-emitting auxiliary layer, a light-emitting layer having a thickness of 30 nm was deposited on the light- _{emitting auxiliary layer by doping at 95:5 weight using CBP as a host material and Ir(ppy) 3 as a dopant material.} Subsequently, BAlq was vacuum deposited to a thickness of 10 nm on the emission layer to form a hole blocking layer, and Alq ₃ was deposited to a thickness of 40 nm to form an electron transport layer. Thereafter, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm to form an electron injection layer, and then Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

[ Example 22] to [ Example 372] Green Organic Light-Emitting Device ( Light-emitting auxiliary layer )

Instead of compound 1-1 of the present invention, compounds 1-2 to 1-88, 2-1 to 2-88, 3-1 to 3-88, and 4-1 to 4-88 of the present invention described in Table 5 below emit light An organic electroluminescent device was manufactured in the same manner as in Example 21, except that it was used as an auxiliary layer material.

[ Comparative example 4]

An organic electroluminescent device was manufactured in the same manner as in Example 21, except that the light emission auxiliary layer was not formed.

[ Comparative example 5]

An organic electroluminescent device was manufactured in the same manner as in Example 21, except that Comparative Compound 2 was used as a light emitting auxiliary layer material instead of the compound of the present invention.

[ Comparative example 6]

An organic electroluminescent device was manufactured in the same manner as in Example 21, except that Comparative Compound 3 was used as a light emitting auxiliary layer material instead of the compound of the present invention.

Electroluminescence (EL) characteristics by applying a forward bias direct current voltage to the organic electroluminescent devices manufactured according to Examples 21 to 372 and Comparative Examples 4 to 6 of the present invention with PR-650 of photoresearch The measurement results are shown in Table 5 below. At this time, the life span was measured at 300 cd/m 2 by using a life measurement equipment manufactured by McScience at a standard luminance of 300 cd/m 2.

[Table 5]

As can be seen from the results of Table 5, a device in which the compound of the present invention is used as a material for a light-emitting auxiliary layer compared to a device in which the light-emitting auxiliary layer is not used, and a device in which the comparative compound 2 and the comparative compound 3 are used as the material for the auxiliary light In the case of, the driving voltage of the device could be further lowered, and the luminous efficiency and lifetime could be significantly improved.

This can be explained as having a high T1 energy level when the compound of the present invention is used alone as a light emitting auxiliary layer, and improving the low voltage, high luminous efficiency, and device life of the organic electroluminescent device due to the deep HOMO energy level.

Even if the compounds of the present invention are used in other organic material layers of an organic electroluminescent device, for example, a hole injection layer, an electron injection layer, and an electron transport layer, it is obvious that the same effect can be obtained.

The above description is only illustrative of the present invention, and those of ordinary skill in the art to which the present invention pertains will be able to make various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention, but to describe the present invention, and the spirit and scope of the present invention are not limited by these embodiments.

The scope of protection of the present invention should be interpreted by the following claims, and all technologies within the scope equivalent thereto should be interpreted as being included in the scope of the present invention.

110: substrate 120: anode
130: hole injection layer 140: hole transport layer
141: buffer layer 150: light emitting layer
151: light emission auxiliary layer 160: electron transport layer
170: electron injection layer 180: cathode

Claims (10)

A compound represented by the following formula (1).
<Formula 1>

[In Formula 1,
A-hwan

or

And, X of ring A is CR ₁₂ R ₁₃ , Y is O, NR ₁₆ , CR ₁₇ R ₁₈ or SiR ₁₉ R ₂₀ ,
R _12, R _13, R ₁₆ to R ₂₀ are each independently hydrogen; C ₁ ~ C ₃₀ alkyl group; C ₆ ~ C ₃₀ aryl group; And fluorenyl group; is selected from the group consisting of, R ₁₂ and R ₁₃ or R ₁₇ and R ₁₈ may be bonded to each other to form a spiro compound,
R ₁ to R ₄ are independently of each other, i) hydrogen; or ii) adjacent groups are bonded to each other to form at least one ring (in this case, the group not forming a ring is the same as defined in i)) ,
Ar ₁ and Ar ₂ are each independently a C ₆ ~ C ₆₀ aryl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of P; C ₁ ~ C ₅₀ alkyl group; Or a fluorenyl group; and,
L is each independently a C ₆ ~ C ₃₀ arylene group; Fluorenylene group; And C ₂ ~ C ₃₀ heteroarylene group; is selected from the group consisting of, each of which is a C ₁ ~ C ₂₀ alkyl group, C ₆ ~ C ₂₀ aryl group and C ₂ ~ C _{20 from} the group consisting of a heterocyclic group May be substituted with one or more selected substituents,
When the R ₁ to R ₄ , Ar ₁ to Ar ₂ , R _12, R _13, R ₁₆ to R ₂₀ are aryl groups, each of them is deuterium, a C ₁ to C ₂₀ alkyl group, a C ₆ to C ₂₀ aryl group _{, C 6} ~ C ₂₀ aryl group substituted with deuterium _{and C 2} ~ C ₂₀ may be substituted with one or more substituents selected from the group consisting of a heterocyclic group,
When R ₁ to R ₄ , Ar ₁ to Ar ₂ , R _12, R _13, R ₁₆ to R ₂₀ are heterocyclic groups, each of them is deuterium, a C ₁ to C ₂₀ alkyl group, a C ₆ to C ₂₀ aryl group _{, C 6} ~ C ₂₀ aryl group substituted with deuterium _{and C 2} ~ C ₂₀ may be substituted with one or more substituents selected from the group consisting of a heterocyclic group,
When R ₁ to R ₄ , Ar ₁ to Ar ₂ , R _12, R _{13 and} R ₁₆ to R ₂₀ are fluorenyl groups, each of them is deuterium, a C ₁ to C ₂₀ alkyl group, a C ₆ to C ₂₀ aryl It may be substituted with one or more substituents selected from the group consisting of a group and a C ₆ ~ C _{20 aryl group substituted with deuterium.]} The method of claim 1,
A compound characterized in that it is represented by one of the following formulas.
<Formula 2><Formula3><Formula4><Formula5>

<Formula 6><Formula7><Formula8><Formula9>

<Formula 10><Formula11><Formula12><Formula13>

(In Formulas 2 to 13, X, Y, L, Ar ₁ and Ar ₂ are the same as defined in claim 1) The method of claim 1,
A compound, characterized in that one of the following compounds.

An organic electric device comprising the compound of any one of claims 1 to 3. The method of claim 4,
A first electrode; A second electrode; And an organic material layer positioned between the first electrode and the second electrode, wherein the compound is contained in the organic material layer. The method of claim 5,
The organic material layer is an organic electric device, characterized in that at least one of a light emitting layer, a hole injection layer, a hole transport layer, a light emission auxiliary layer, an electron injection layer and an electron transport layer. The method of claim 6,
The organic electric device, characterized in that the hole transport layer or the light emission auxiliary layer is formed of the compound. The method of claim 5,
Wherein the organic material layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, or a roll-to-roll process. A display device including the organic electric device of claim 4; And
Electronic device comprising a; a control unit for driving the display device. The method of claim 9,
The organic electroluminescent device is at least one of an organic electroluminescent device, an organic solar cell, an organic photoreceptor, an organic transistor, and a single color or white lighting device.

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