KR102154271B1 - 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 electronic 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 large-area, such efficiency and lifetime problems 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 shows a tendency to increase the lifespan.

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 the 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 for 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 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 characteristics against Joule heating generated when the device is driven, that is, high glass transition There is a need 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 influence on the device life. 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 materials for the light emitting auxiliary layer and the hole transport layer is urgently required.

The present invention uses a non-linear linking group (folded structure when combined with an amine group) in a carbazole core, which is widely used as an OLED hole transport material, and also uses a bulky fluorene in the nitrogen (N) of the carbazole. ) By introducing a substituent, it has a high T1 value, a wide band gab, and excellent charge balance, so that high luminous efficiency, low driving voltage, high heat resistance, color purity, and lifespan of the device can be improved. An object of the present invention is to provide a compound, 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, high luminous efficiency, low driving voltage, and high heat resistance of the device can be achieved, and color purity and lifetime of the device can be greatly improved.

1 is an exemplary diagram of an organic electroluminescent device according to 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) and (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”.

As used in the specification and appended claims, unless stated otherwise, the meaning of the following terms is as follows:

As used herein, the term "halo" or "halogen" is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I) unless otherwise specified.

As used herein, the term "alkyl" or "alkyl group" has a single bond of 1 to 60 carbon atoms unless otherwise specified, and is a straight-chain alkyl group, a branched-chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cyclo It means a radical of a saturated aliphatic functional group, including an alkyl group and 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 specified.

The term "heteroalkyl group" as used in the present invention means that one or more of the carbon atoms constituting the alkyl group has been replaced with a heteroatom.

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

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

The terms "alkenyl group", "alkenoxy group", "alkenyloxy group", or "alkenyloxy group" as used in the present invention mean an alkenyl group to which an oxygen radical is attached, and unless otherwise specified, 2 to 60 It has a carbon number of, but is not limited thereto.

The term "aryloxyl group" or "aryloxy group" used in the present invention refers to an aryl group to which an oxygen radical is attached, and has 6 to 60 carbon atoms, 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, unless otherwise specified. In the present invention, an aryl group or an arylene group means 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.

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

In addition, when prefixes are named consecutively, it means that the substituents are listed in the order described first. For example, in the case of an arylalkoxy group, it means an alkoxy group substituted with an aryl group, in the case of an alkoxylcarbonyl group, it means a carbonyl group substituted with an alkoxyl group, and in the case of an arylcarbonylalkenyl group, it means an alkenyl group substituted with an arylcarbonyl group. And the arylcarbonyl group is a carbonyl group substituted with an aryl 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 in the present invention means 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 No, it includes at least one of a single ring and multiple rings, and may be formed by combining adjacent functional groups.

The term "heterocyclic group" as used herein, unless otherwise specified, includes one or more heteroatoms, has 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, and includes heteroaliphatic rings and heterocyclic rings. It contains an aromatic ring. It may be formed by combining adjacent functional groups.

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

In addition, the "heterocyclic group" may also include a ring including SO ₂ instead of carbon forming a ring. For example, "heterocyclic group" includes the following compounds.

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.

Unless otherwise specified, the term "carbonyl" as used herein is represented by -COR', where R'is hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, and 3 to 30 carbon atoms. A cycloalkyl group, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

Unless otherwise specified, the term "ether" used in the present invention is represented by -RO-R', wherein R or R'are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, and 6 to 30 carbon atoms. An aryl group, a C3-C30 cycloalkyl group, a C2-C20 alkenyl group, a C2-C20 alkynyl group, or a combination thereof.

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 alkoxyl 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, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted by deuterium aryl group, a C ₈ ~ C ₂₀ aryl alkenyl group, a silane group, a boron 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.

In addition, unless there is an explicit explanation, the formula used in the present invention is applied in the same manner as the definition of the substituent group defined by the index definition of the following formula.

Here, when a is an integer of 0, the substituent R ¹ is absent, and when a is an integer of 1, one substituent R ¹ is bonded to any one of carbons forming a benzene ring, and a is an integer of 2 or 3 Each is bonded as follows, wherein R ¹ may be the same or different from each other, and when a is an integer of 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the hydrogen bonded to the carbon forming the benzene ring is indicated. Is omitted.

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 including the compound according to the present invention. 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 or a capping 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 hole injection layer 130, a hole transport layer 140, an electron transport layer 160, an electron injection layer 170, a host of the light emitting layer 150, or a dopant or a light efficiency improvement layer. It could be used as a material. Preferably, the compound of the present invention may be used as the light emitting layer 150, the hole transport layer 140 and/or the light emitting auxiliary layer 151.

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 the 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 different light emitting auxiliary layers. 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 forming a light emitting layer or a light emitting auxiliary layer using the compound represented by Formula 1, the energy level and T1 value between each organic material layer, the intrinsic properties of the material (mobility, interface properties, etc.) It is possible to improve the life and efficiency of the electric 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.

WOLED (White Organic Light Emitting Device) is easy to realize high resolution and excellent processability, while there is an advantage that can be manufactured using the existing LCD color filter technology. Various structures for white organic light emitting devices mainly used as backlight devices have been proposed and patented. Typically, R(Red), G(Green), B(Blue) light emitting parts are arranged side-by-side in a mutually planar way, and R, G, B light emitting layers are stacked up and down. In addition, there is a color conversion material (CCM) method that uses electroluminescence by the blue (B) organic light-emitting layer and photo-luminescence of an inorganic phosphor using light therefrom. May be applied to such WOLED.

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>

In Formula 1,

Ar ¹ and Ar ² are each C ₆ ~ C ₁₈ aryl group; Or a fluorenyl group; and,

로 이루어진 군에서 선택되며, 여기서 표시 *는 화학식 1의 질소(N)와 결합을 의미한다.L is

It is selected from the group consisting of, where * means a bond with nitrogen (N) of Formula 1.

R'and R" are selected from the group consisting of: i) independently of each other hydrogen; a C ₁ to C ₅₀ alkyl group; a C ₆ to C ₆₀ aryl group; or ii) R'and R" are bonded to each other so that they Together with the bound fluorene, a compound is formed as a spy.

m and p are integers from 0 to 3, n and o are integers from 0 to 4,

R ¹ to R ⁴ are i) independently of each other deuterium; halogen; C ₆ ~ C ₆₀ aryl group; Fluorenyl group; O, N, S, Si, and C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of 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 ; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C ₂₀ ; An alkoxyl group of C ₁ to C ₃₀ ; C ₆ ~ C ₃₀ aryloxy group; And -L'-N(R _a )(R _b ); or ii) neighboring substituents may be bonded to each other to form a ring. On the other hand, form a ring with each other group of neighboring bonded to each other m, n, o and p are R ⁴ to R ³ to each other, or adjacent to, each time two or more integer neighboring R ¹ to each other, adjacent R ² to each other, to a neighboring It means to form a ring by bonding with each other, the ring is a fused ring consisting of a C ₃ ~ C ₆₀ aliphatic ring, a C ₆ ~ C ₆₀ aromatic ring, a C ₂ ~ C ₆₀ hetero ring, or a combination thereof And includes saturated or unsaturated rings.

L'is each independently a single bond; C ₆ ~ C ₆₀ arylene group; 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 C ₂ ~ C ₆₀ of the heterocyclic group; is selected from the group consisting of,

R _a and R _b are each independently a C ₆ ~ C ₆₀ aryl group; 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 O, N, S, Si and P including at least one heteroatom C ₂ ~ C ₆₀ heterocyclic group; is selected from the group consisting of.

Here, the aryl group, fluorenyl group, heterocyclic group, fused ring group, alkyl group, alkenyl group, alkynyl group, alkoxyl group, aryloxy group, arylene group, and fluorenylene group are each deuterium; halogen; Silane group; Siloxane group; Boron group; Germanium group; Cyano group; Nitro group; -L'-N(R _a ) (R _b ); C ₁ ~ C ₂₀ alkylthio group; An alkoxyl group of C ₁ to C ₂₀ ; C ₁ ~ C ₂₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; Alkynyl group of C ₂ ~ C ₂₀ ; Of C ₆ ~ C ₂₀ Aryl group; A C ₆ ~ C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ ~ C ₂₀ Heterocyclic group; A C ₃ ~C ₂₀ cycloalkyl group; It may be further substituted with one or more substituents selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group and C ₈ ~ C ₂₀ arylalkenyl group.

Specifically, the compound represented by Formula 1 may be represented by the following Formulas 2 to 8.

<Formula 2> <Formula 3>

<Formula 4> <Formula 5> <Formula 6>

<Formula 7> <Formula 8>

In Formulas 2 to 8, Ar ¹ , Ar ² , R', R", R ¹ to R ⁴ , m, n, o and p are the same as those of Formula 1 above.

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

As another embodiment, the present invention provides a compound for an organic electric device represented by Formula 1 above.

In another embodiment, the present invention provides an organic electric device containing the compound represented by Formula 1.

In this case, the organic electric device includes a first electrode; A second electrode; And an organic material layer disposed between the first electrode and the second electrode, wherein the organic material layer may include a compound represented by Formula 1, wherein Formula 1 is a hole injection layer, a hole transport layer, and It may be contained in at least one of the light-emitting auxiliary layer or the light-emitting layer. That is, the compound represented by Formula 1 may be used as a material for a hole injection layer, a hole transport layer, a light emission auxiliary layer, or a light emission layer. Specifically, an organic electric device including one of the compounds represented by Chemical Formulas 2 to 8 is provided in the organic material layer, and more specifically, the present invention provides an organic electroluminescent device including a compound represented by the individual formula in the organic material layer. Device.

In another embodiment of the present invention, the present invention provides a light efficiency improvement layer formed on at least one of one side of the first electrode opposite to the organic material layer or one side of the second electrode opposite to the organic material layer. It provides an organic electric device further comprising.

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

Synthesis example

The compound (Final Product) according to the present invention is prepared by reacting Sub 1 and Sub 2 as in Scheme 1 below, but is not limited thereto.

<Reaction Scheme 1>

Ⅰ. Sub Synthesis of 1

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

<Reaction Scheme 2>

One. Sub Synthesis of 1

In a round bottom flask, Sub 1-1 (1 equivalent), Sub 1-2 (1 equivalent), Pd ₂ (dba) ₃ (0.05 equivalent), PPh ₃ (0.1 equivalent), NaO t -Bu (3 equivalent), toluene After adding (10.5mL/1mmol), the reaction proceeds at 100°C. When the reaction was complete, the reaction was completed, extracted with ether and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain Sub 1.

(1) Sub 1 (2) synthesis

3-bromo-9H-carbazole (4.9g, 20mmol), 1-iodo-9,9-diphenyl-9H-fluorene (8.9g, 20mmol), Pd ₂ (dba) ₃ (0.9g, 1mmol) in a round bottom flask After adding, PPh ₃ (0.5g, 2mmol), NaO t -Bu (5.8g, 60mmol), and toluene (210mL), 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 8.6 g (yield: 76%) of the product.

(2) Sub 1 (6) synthesis

3-bromo-9H-carbazole (4.9g, 20mmol), 2-iodo-9,9'-spirobi[fluorene] (8.8g, 20mmol), Pd ₂ (dba) ₃ (0.9g, 1mmol) in round bottom flask After adding, PPh ₃ (0.5g, 2mmol), NaO t -Bu (5.8g, 60mmol), and toluene (210mL), 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 9.2 g (yield: 82%).

(3) Sub 1(7) synthesis

3-bromo-9H-carbazole (4.9g, 20mmol), 3-iodo-9,9-dimethyl-9H-fluorene (6.4g, 20mmol), Pd ₂ (dba) ₃ (0.9g, 1mmol) in a round bottom flask After adding, PPh ₃ (0.5g, 2mmol), NaO t -Bu (5.8g, 60mmol), and toluene (210mL), 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 6.8 g (yield: 76%) of the product.

(4) Sub 1 (11) synthesis

3-bromo-9H-carbazole (4.9g, 20mmol), 4-iodo-9,9-diphenyl-9H-fluorene (8.9g, 20mmol), Pd ₂ (dba) ₃ (0.9g, 1mmol) in a round bottom flask After adding, PPh ₃ (0.5g, 2mmol), NaO t -Bu (5.8g, 60mmol), and toluene (210mL), 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 8.3 g (yield: 74%).

Meanwhile, examples of Sub 1 are as follows, but are not limited thereto, and their FD-MS is shown in Table 1 below.

[Table 1]

Ⅱ. Sub Synthesis of 2

Sub 2 of Scheme 1 may be synthesized by the reaction route of Scheme 3 below, but is not limited thereto.

<Reaction Scheme 3>

One. Sub Synthesis of 2-3

In a round bottom flask, Sub 2-1 (1 equivalent), Sub 2-2 (1 equivalent), Pd ₂ (dba) ₃ (0.05 equivalent), PPh ₃ (0.1 equivalent), NaO t -Bu (3 equivalent), toluene After adding (10.5mL/1mmol), the reaction proceeds at 100°C. When the reaction was completed, the reaction was completed, extracted with ether and water, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain Sub 2-3.

(1) Sub 2-3-1 synthesis

In a round bottom flask, 1-bromo-2-iodobenzene (5.7g, 20mmol), diphenylamine (3.4g, 20mmol), Pd ₂ (dba) ₃ (0.9g, 1mmol), PPh ₃ (0.5g, 2mmol), NaO t After adding -Bu (5.8g, 60mmol) and toluene (210mL), 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 4.9 g (yield: 76%) of the product.

(2) Sub 2-3-2 synthesis

1-bromo-3-iodobenzene (5.7g, 20mmol), N-phenyl-[1,1'-biphenyl]-4-amine (4.9g, 20mmol), Pd ₂ (dba) ₃ (0.9g) in a round bottom flask , 1mmol), PPh ₃ (0.5g, 2mmol), NaO t -Bu (5.8g, 60mmol), and toluene (210mL) were added and the reaction was proceeded 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: 78%) of the product.

(3) Sub 2-3-3 synthesis

In a round bottom flask, 2-bromo-2'-iodo-1,1'-biphenyl (7.2g, 20mmol), N-phenyl-[1,1':3',1''-terphenyl]-3-amine ( 6.4g, 20mmol), Pd ₂ (dba) ₃ (0.9g, 1mmol), PPh ₃ (0.5g, 2mmol), NaO t -Bu (5.8g, 60mmol), toluene (210mL) and reacted at 100℃ Proceed. 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 7.7 g (yield: 74%).

(4) Sub 2-3-4 synthesis

In a round bottom flask, 4-bromo-2'-iodo-1,1'-biphenyl (7.2g, 20mmol), 9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (5.7g, 20mmol), After adding Pd ₂ (dba) ₃ (0.9g, 1mmol), PPh ₃ (0.5g, 2mmol), NaO t -Bu (5.8g, 60mmol), and toluene (210mL), 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 8.1 g (yield: 78%).

(5) Sub 2-3-5 synthesis

In a round bottom flask, 4-bromo-3'-iodo-1,1'-biphenyl (7.2g, 20mmol), N-([1,1'-biphenyl]-4-yl)naphthalen-1-amine (5.9g) , 20mmol), Pd ₂ (dba) ₃ (0.9g, 1mmol), PPh ₃ (0.5g, 2mmol), NaO t -Bu (5.8g, 60mmol), toluene (210mL) was added and the reaction proceeded at 100℃ do. 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 7.8 g (yield: 74%).

(6) Sub 2-3-6 synthesis

In a round bottom flask, 4'-bromo-2-iodo-1,1'-biphenyl (7.2g, 20mmol), N-([1,1'-biphenyl]-4-yl)naphthalen-2-amine (5.9g) , 20mmol), Pd ₂ (dba) ₃ (0.9g, 1mmol), PPh ₃ (0.5g, 2mmol), NaO t -Bu (5.8g, 60mmol), toluene (210mL) was added and the reaction proceeded 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 7.6 g (yield: 72%) of the product.

(7) Sub 2-3-7 synthesis

In a round bottom flask, 4'-bromo-3-iodo-1,1'-biphenyl (7.2g, 20mmol), di([1,1'-biphenyl]-4-yl)amine (6.4g, 20mmol), Pd ₂ (dba) ₃ (0.9g, 1mmol), PPh ₃ (0.5g, 2mmol), NaO t -Bu (5.8g, 60mmol), toluene (210mL) was added, and the reaction was proceeded 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 8.6 g (yield: 78%).

2. Sub Synthesis of 2

Dissolve Sub 2-3 (1 equivalent) in anhydrous Ether, lower the temperature of the reactant to -78℃, add n-BuLi (2.5M in hexane) (1.1 equivalent) slowly dropwise, and then stir the reaction for 30 minutes. Made it. After that, the temperature of the reactant was again lowered to -78°C, and Triisopropylborate (1.5 equivalent) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. When the reaction was completed, ethyl acetate and water were extracted, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain Sub 2.

(1) Sub 2 (1) synthesis

Dissolve 2-bromo-N,N-diphenylaniline (6.5g, 20mmol) in anhydrous Ether, lower the temperature of the reactant to -78℃, and slowly add n-BuLi (2.5M in hexane) (1.4g, 22mmol) dropwise. After that, the reaction was stirred for 30 minutes. After that, the temperature of the reactant was again lowered to -78°C, and Triisopropyl borate (5.6g, 30mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. When the reaction was completed, ethyl acetate and water were extracted, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 3.2 g (yield: 56%) of the product.

(2) Sub 2(6) synthesis

Dissolve N-(3-bromophenyl)-N-phenyl-[1,1'-biphenyl]-4-amine (8.0g, 20mmol) in anhydrous Ether, lower the temperature of the reactant to -78℃, and n-BuLi ( 2.5M in hexane) (1.4g, 22mmol) was slowly added dropwise, and the reaction was stirred for 30 minutes. After that, the temperature of the reactant was again lowered to -78°C, and Triisopropyl borate (5.6g, 30mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. When the reaction was completed, ethyl acetate and water were extracted, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 4.2 g (yield: 58%) of the product.

(3) Sub 2 (11) synthesis

N-(2'-bromo-[1,1'-biphenyl]-2-yl)-N-phenyl-[1,1':3',1''-terphenyl]-3-amine (11.1g, 20mmol ) Was dissolved in anhydrous Ether, the temperature of the reaction mixture was lowered to -78°C, and n-BuLi (2.5M in hexane) (1.4g, 22mmol) was slowly added dropwise, and the reaction was stirred for 30 minutes. After that, the temperature of the reactant was again lowered to -78°C, and Triisopropyl borate (5.6g, 30mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. When the reaction was completed, ethyl acetate and water were extracted, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 5.4 g (yield: 52%) of the product.

(4) Sub 2 (18) synthesis

Dissolve N-(4'-bromo-[1,1'-biphenyl]-2-yl)-9,9-dimethyl-N-phenyl-9H-fluoren-2-amine (10.3g, 20mmol) in anhydrous Ether , The temperature of the reactant was lowered to -78°C, n-BuLi (2.5M in hexane) (1.4g, 22mmol) was slowly added dropwise, and the reactant was stirred for 30 minutes. After that, the temperature of the reactant was again lowered to -78°C, and Triisopropyl borate (5.6g, 30mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. When the reaction was completed, ethyl acetate and water were extracted, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 5.4 g (yield: 56%) of the product.

(5) Sub 2 (23) synthesis

N-([1,1'-biphenyl]-4-yl)-N-(4'-bromo-[1,1'-biphenyl]-3-yl)naphthalen-1-amine (10.5 g, 20 mmol) After dissolving in anhydrous Ether, the temperature of the reactant was lowered to -78°C, n-BuLi (2.5M in hexane) (1.4g, 22mmol) was slowly added dropwise, and the reaction was stirred for 30 minutes. After that, the temperature of the reactant was again lowered to -78°C, and Triisopropyl borate (5.6g, 30mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. When the reaction was completed, ethyl acetate and water were extracted, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 5.1 g (yield: 52%) of the product.

(6) Sub 2 (28) synthesis

N-([1,1'-biphenyl]-4-yl)-N-(4'-bromo-[1,1'-biphenyl]-2-yl)naphthalen-2-amine (10.5 g, 20 mmol) After dissolving in anhydrous Ether, the temperature of the reactant was lowered to -78°C, n-BuLi (2.5M in hexane) (1.4g, 22mmol) was slowly added dropwise, and the reaction was stirred for 30 minutes. After that, the temperature of the reactant was again lowered to -78°C, and Triisopropyl borate (5.6g, 30mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. When the reaction was completed, ethyl acetate and water were extracted, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 5.4 g (yield: 55%) of the product.

(7) Sub 2 (32) synthesis

N,N-di([1,1'-biphenyl]-4-yl)-4'-bromo-[1,1'-biphenyl]-3-amine (11.1g, 20mmol) was dissolved in anhydrous Ether, and the reactant The temperature of was lowered to -78°C, n-BuLi (2.5M in hexane) (1.4g, 22mmol) was slowly added dropwise, and the reaction was stirred for 30 minutes. After that, the temperature of the reactant was again lowered to -78°C, and Triisopropyl borate (5.6g, 30mmol) was added dropwise. After stirring at room temperature, dilute with water and add 2N HCl. When the reaction was completed, ethyl acetate and water were extracted, the organic layer was dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized with a silicagel column to obtain 6.2 g (yield: 60%) of the product.

Meanwhile, examples of Sub 2 are as follows, but are not limited thereto, and their FD-MS is shown in Table 2 below.

[Table 2]

Ⅲ. Final product ( Final Product ) Synthesis

In a round bottom flask, add Sub 1 (1 equivalent), Sub 2 (1 equivalent), Pd(PPh ₃ ) ₄ (0.03 equivalent), NaOH (3 equivalent), THF (3mL/1mmol), and water (1.5mL/1mmol). Put it in. Then, it is heated to reflux at 80°C to 90°C. When the reaction is completed, distilled water is added at room temperature to dilute, and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized with a silicagel column to obtain a final product.

(1) 1-1 synthesis

In a round bottom flask, 3-bromo-9-(9,9-dimethyl-9H-fluoren-1-yl)-9H-carbazole (8.8g, 20mmol), (2-(diphenylamino)phenyl)boronic acid (5.8g, 20mmol), Pd(PPh ₃ ) ₄ (0.7g, 0.6mmol), NaOH (2.4g, 60mmol), THF (60mL), and water (30mL) are added. Then, it is heated to reflux at 80°C to 90°C. When the reaction is complete, distilled water is added at room temperature to dilute, and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was recrystallized with a silicagel column to obtain 7.7 g (yield: 64%) of the product.

(2) 2-6 synthesis

In a round bottom flask, add 3-bromo-9-(9,9-diphenyl-9H-fluoren-1-yl)-9H-carbazole (11.3g, 20mmol), and (3-(naphthalen-1-yl(phenyl)) Add amino)phenyl)boronic acid (6.8g, 20mmol), Pd(PPh ₃ ) ₄ (0.7g, 0.6mmol), NaOH (2.4g, 60mmol), THF (60mL), and water (30mL). Then, it is heated to reflux at 80°C to 90°C. When the reaction is complete, distilled water is added at room temperature to dilute, and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized with a silicagel column to obtain 10.6g (yield: 68%) of the product.

(3) 3-11 synthesis

3-bromo-9-(9,9-diphenyl-9H-fluoren-2-yl)-9H-carbazole (11.3g, 20mmol) was added to the round bottom flask, and (2'-([1,1':2 ',1''-terphenyl]-2-yl(phenyl)amino)-[1,1'-biphenyl]-2-yl)boronic acid (10.3g, 20mmol), Pd(PPh ₃ ) ₄ (0.7g, 0.6mmol), NaOH (2.4g, 60mmol), THF (60mL), and water (30mL). Then, it is heated to reflux at 80°C to 90°C. When the reaction is completed, distilled water is added at room temperature to dilute, and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized in a silicagel column to obtain 11.8 g (yield: 62%) of the product.

(4) 4-16 synthesis

3-bromo-9-(9,9-diphenyl-9H-fluoren-3-yl)-9H-carbazole (11.3g, 20mmol) was added to the round bottom flask, and (3'-([1,1':4 ',1''-terphenyl]-3-yl(phenyl)amino)-[1,1'-biphenyl]-2-yl)boronic acid (10.3g, 20mmol), Pd(PPh ₃ ) ₄ (0.7g, 0.6mmol), NaOH (2.4g, 60mmol), THF (60mL), and water (30mL). Then, it is heated to reflux at 80°C to 90°C. When the reaction is completed, distilled water is added at room temperature to dilute, and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized with a silicagel column to obtain 12.4g (yield: 65%) of the product.

(5) 5-17 synthesis

3-bromo-9-(9,9-diphenyl-9H-fluoren-4-yl)-9H-carbazole (11.3g, 20mmol) was added to the round bottom flask, and (4'-([1,1':2) ',1''-terphenyl]-4-yl(phenyl)amino)-[1,1'-biphenyl]-2-yl)boronic acid (10.3g, 20mmol), Pd(PPh ₃ ) ₄ (0.7g, 0.6mmol), NaOH (2.4g, 60mmol), THF (60mL), and water (30mL). Then, it is heated to reflux at 80°C to 90°C. When the reaction is completed, distilled water is added at room temperature to dilute, and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized in a silicagel column to obtain 11.8 g (yield: 62%) of the product.

(6) 6-22 synthesis

In a round bottom flask, add 3-bromo-9-(9,9-diphenyl-9H-fluoren-1-yl)-9H-carbazole (11.3g, 20mmol), and (2'-((9,9-dimethyl- 9H-fluoren-2-yl)(phenyl)amino)-[1,1'-biphenyl]-4-yl)boronic acid (9.6g, 20mmol), Pd(PPh ₃ ) ₄ (0.7g, 0.6mmol), Add NaOH (2.4g, 60mmol), THF (60mL), and water (30mL). Then, it is heated to reflux at 80°C to 90°C. When the reaction is completed, distilled water is added at room temperature to dilute, and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized with a silicagel column to obtain 11.0 g (yield: 60%) of the product.

(7) 7-27 synthesis

3-bromo-9-(9,9-diphenyl-9H-fluoren-2-yl)-9H-carbazole (11.3g, 20mmol) was added to the round bottom flask, and (3'-([1,1'-biphenyl ]-4-yl(naphthalen-1-yl)amino)-[1,1'-biphenyl]-4-yl)boronic acid (9.8g, 20mmol), Pd(PPh ₃ ) ₄ (0.7g, 0.6mmol) , NaOH (2.4g, 60mmol), THF (60mL), and water (30mL) are added. Then, it is heated to reflux at 80°C to 90°C. When the reaction is completed, distilled water is added at room temperature to dilute, and extracted with methylene chloride and water. The organic layer was dried over MgSO ₄ , concentrated, and the resulting compound was recrystallized with a silicagel column to obtain 12.1g (yield: 65%) of the product.

[Table 3]

Manufacturing evaluation of organic electric devices

[ Experimental example Ⅰ] Green organic light emitting device ( Hole transport layer )

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 -phenylbenzene- 1,4-diamine (hereinafter abbreviated as "2-TNATA") was vacuum deposited to a thickness of 60 nm to form a hole injection layer, and then the compound of the present invention was vacuum deposited on the hole injection layer to a thickness of 60 nm to A transport layer was formed. Next, 4,4'-N,N'-dicarbazole-biphenyl (hereinafter, abbreviated as "CBP") on the hole transport layer as a host material of the emission layer, tris(2-phenylpyridine)-iridium (hereinafter, " Ir(ppy) ₃ ") was used as a dopant material for the light-emitting layer and doped at 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 on the light emitting layer. Thus, a hole blocking layer was formed, and tris(8-quinolinol) aluminum (hereinafter abbreviated as "Alq ₃ ") was vacuum deposited to a thickness of 40 nm on the hole blocking layer 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.

[ Comparative example Ⅰ] Comparative example (1) ~ (3)

Comparative example (One)

An organic electroluminescent device was manufactured in the same manner as in Experimental Example I, except that the following Comparative Compound A was used instead of the compound of the present invention as the hole transport layer.

<Comparative compound A> NPB

Comparative example (2)

An organic electroluminescent device was manufactured in the same manner as in Experimental Example I, except that the following Comparative Compound B was used instead of the compound of the present invention as the hole transport layer.

<Comparative compound B>

Comparative example (3)

An organic electroluminescent device was manufactured in the same manner as in Experimental Example I, except that the following Comparative Compound C was used instead of the compound of the present invention as the hole transport layer.

<Comparative compound C>

A forward bias DC voltage was applied to the organic electroluminescent devices according to Experimental Example I (Experimental Example (1) to Experimental Example (84)) and Comparative Example I (Comparative Example (1) to Comparative Example (3)) thus prepared. In addition, electroluminescence (EL) characteristics were measured with a PR-650 of photoresearch, and T95 life was measured using a life measurement equipment manufactured by McScience at a luminance of 5000 cd/m2.

Table 4 below shows device fabrication for Experimental Example I (Experimental Examples (1) to (84)) and Comparative Example I (Comparative Examples (1) to (3)) to which the compound according to the present invention was applied, and The evaluation result is shown.

[Table 4]

As can be seen from the results of Table 4, it can be seen that the organic electroluminescent device using the compound of the present invention as a material for the hole transport layer can significantly improve luminous efficiency and lifespan.

In other words, the amine group is non-linear than the organic electroluminescent device in which the NPB, comparative compound A, and the amine group are linearly connected to the p-position. An organic electroluminescent device using the compound of the present invention connected as a material for a hole transport layer shows excellent device results.

When the amine group is connected non-linearly, the conjugation length becomes shorter than when it is connected in a linear manner, resulting in a wider band gap, a deep HOMO energy level, and a high T1 value. . Therefore, it is determined that holes are smoothly transported to the emission layer due to the deep HOMO energy level, and excitons are more easily generated in the emission layer by improving the ability to block electrons with a high T1 value, thereby improving efficiency and lifespan.

[ Experimental example Ⅱ] Red organic light emitting device ( Light-emitting auxiliary layer )

On the ITO layer (anode) formed on the organic substrate, 2-TNATA was vacuum deposited to a thickness of 60 nm to form a hole injection layer, followed by 4,4-bis[N-(1-naphthyl)-N on the hole injection layer. -Phenylamino]biphenyl (hereinafter abbreviated as "NPD") was vacuum deposited to a thickness of 60 nm to form a hole transport layer. Next, a light emission auxiliary layer was formed by vacuum depositing the compound of the present invention to a thickness of 20 nm on the hole transport layer, and CBP as a host material of the emission layer on the emission auxiliary layer, bis-(1-phenylisoquinolyl)iridium(III ) Acetylacetonate (hereinafter abbreviated as "(piq) ₂ Ir(acac)") was used as a dopant material for the light-emitting layer and doped with a weight of 95:5 to deposit a light-emitting layer having a thickness of 30 nm. 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 vacuum-deposited to a thickness of 40 nm on the hole blocking layer 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.

[ Comparative example Ⅱ] Comparative example (4) ~ (7)

Comparative example (4)

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

Comparative example (6)

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

Comparative example (7)

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

The forward bias DC voltage was applied to the organic electroluminescent devices according to Experimental Example II (Experimental Examples (85) to (154)) and Comparative Example II (Comparative Examples (4) to (7)) thus prepared. In addition, electroluminescence (EL) characteristics were measured with a PR-650 of photoresearch, and T95 life was measured using a life measurement equipment manufactured by McScience at a luminance of 2500 cd/m2.

Table 5 below shows device fabrication for Experimental Example II (Experimental Examples (85) to (154)) and Comparative Example II (Comparative Examples (4) to (7)) to which the compound according to the present invention was applied. The evaluation result is shown.

[Table 5]

[ Experimental example Ⅲ] Green organic light emitting device ( Light-emitting auxiliary layer )

On the ITO layer (anode) formed on the organic substrate, 2-TNATA was vacuum deposited to a thickness of 60 nm to form a hole injection layer, and then NPD was vacuum deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer. Next, a light emission auxiliary layer was formed by vacuum depositing the compound of the present invention to a thickness of 20 nm on the hole transport layer, and on the light emission auxiliary layer, CBP is used as the host material of the emission layer, and Ir(ppy) ₃ is the dopant of the emission layer. As a material, a light emitting layer having a thickness of 30 nm was deposited by doping with 95:5 weight. 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 vacuum-deposited to a thickness of 40 nm on the hole blocking layer 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.

[ Comparative example Ⅲ] Comparative example (8) ~ (11)

Comparative example (8)

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

Comparative example (9)

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

Comparative example (10)

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

Comparative example (11)

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

The forward bias DC voltage was applied to the organic electroluminescent devices according to Experimental Example III (Experimental Examples 155 to 224) and Comparative Example III (Comparative Examples (8) to (11)) thus prepared. In addition, electroluminescence (EL) characteristics were measured with a PR-650 of photoresearch, and T95 life was measured using a life measurement equipment manufactured by McScience at a luminance of 5000 cd/m2.

Table 6 below shows device fabrication for Experimental Example III (Experimental Examples (155) to Experimental Examples (224)) and Comparative Example III (Comparative Examples (8) to (11)) to which the compound according to the present invention was applied. The evaluation result is shown.

[Table 6]

[ Experimental example Ⅳ] Blue organic light emitting device ( Light-emitting auxiliary layer )

On the ITO layer (anode) formed on the organic substrate, 2-TNATA was vacuum deposited to a thickness of 60 nm to form a hole injection layer, and then NPD was vacuum deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer. Next, a light emitting auxiliary layer was formed by vacuum depositing the compound of the present invention to a thickness of 20 nm on the hole transport layer, and 9, 10-di(naphthalen-2-yl)anthracene was used as a host material of the light emitting layer. As a result, BD-052X (manufactured by Idemitsukosan) was used as a dopant material for the light-emitting layer and doped at 93:7 weight to deposit a light-emitting layer having a thickness of 30 nm. 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 vacuum-deposited to a thickness of 40 nm on the hole blocking layer 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.

[ Comparative example Ⅳ] Comparative example (12) ~ (15)

Comparative example (12)

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

Comparative example (13)

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

Comparative example (14)

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

Comparative example (15)

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

A forward bias DC voltage was applied to the organic electroluminescent devices according to Experimental Examples IV (Experimental Examples 225 to 294) and Comparative Examples IV (Comparative Examples 12 to 15) thus prepared. In addition, electroluminescence (EL) characteristics were measured with a PR-650 of photoresearch, and T95 life was measured using a life measurement equipment manufactured by McScience at a luminance of 500 cd/m2.

Table 7 below shows device fabrication and device fabrication for Experimental Example IV (Experimental Examples 225 to 294) and Comparative Example IV (Comparative Examples 12 to 15) to which the compound according to the present invention was applied. The evaluation result is shown.

[Table 7]

As can be seen from the results of Tables 5 to 7 above, it can be seen that the organic electroluminescent device using the compound of the present invention as a material of the light emitting auxiliary layer can significantly improve the luminous efficiency and lifetime.

This is because the amine groups are non-linearly connected, as described in Experimental Example I, to have a deep HOMO energy level and a high T1 value, whereby holes are smoothly transported to the light emitting layer and the ability to block electrons is improved. It is believed that the lifespan is improved. In addition, by introducing a bulky substituent called fluorene into the nitrogen (N) of carbazole, the packing density between the materials in the light emitting auxiliary layer was lowered, thereby lowering the hole mobility. It is believed that the efficiency and lifespan are improved by achieving a charge balance.

The above description is merely 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. Therefore, the embodiments disclosed in the present specification are not intended to limit the present invention, but to explain 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 construed as being included in the scope of the present invention.

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

Claims (10)

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

[In Formula 1,
Ar ¹ and Ar ² are each C ₆ ~ C ₁₈ aryl group; Or a fluorenyl group; and,
L is

It is selected from the group consisting of (indicated * means a bond with nitrogen (N) of Formula 1),
R'and R" are selected from the group consisting of: i) independently of each other hydrogen; C ₁ to C ₂₀ alkyl group; C ₆ to C ₂₀ aryl group; or ii) R'and R" are bonded to each other to Forms a compound as a spy with the bound fluorene,
m and p are integers from 0 to 3,
n and o are integers from 0 to 4,
R ¹ to R ⁴ are deuterium.
(Wherein the aryl group, fluorenyl group, and alkyl group are each deuterium; C ₁ ~ C ₂₀ alkyl group; C ₆ ~ C ₂₀ Aryl group; A C ₆ ~ C ₂₀ aryl group substituted with deuterium; Fluorenyl group; And C ₂ ~ C ₂₀ heterocyclic group; may be further substituted with one or more substituents selected from the group consisting of.)] The method of claim 1,
Compounds characterized in that represented by the following formulas 2 to 8.
<Formula 2><Formula3>

<Formula 4><Formula5><Formula6>

<Formula 7><Formula8>

[In Chemical Formulas 2 to 8,
Ar ¹ , Ar ² , R', R", R ¹ to R ⁴ , m, n, o and p are the same as defined in Formula 1.] The method of claim 1,
A compound, characterized in that any 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 compound is an organic electroluminescent device, characterized in that contained in at least one of a hole injection layer, a hole transport layer, a light emission auxiliary layer or a light emitting layer of the organic material layer. The method of claim 5,
An organic electric device further comprising a light efficiency improving layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer. The method of claim 5,
The organic material layer is formed by any one of a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process, and 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 electric device is at least 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.

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