KR102399009B1 - 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 the luminous efficiency, stability and lifespan of a device, an organic electric device using the same, and an electronic device thereof.

Description

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

A material used as an organic material layer in an organic electric device may be classified into a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc. according to their function.

Lifespan and efficiency are the most problematic for organic electric devices, and as displays become larger, these problems of efficiency and lifespan must be resolved.

Efficiency, lifespan, and driving voltage are related to each other, and when the efficiency is increased, the driving voltage is relatively decreased. It shows a tendency to increase the lifespan. However, the efficiency cannot be maximized simply by improving the organic material layer. This is because, when the energy level and T ₁ value between each organic material layer, and the intrinsic properties of the material (mobility, interfacial properties, etc.) are optimally combined, long lifespan and high efficiency can be achieved at the same time. Because.

In general, electrons are transferred from the electron transport layer to the emission layer, and holes are transferred from the hole transport layer to the emission layer, and excitons are generated by recombination.

However, when holes move faster than electrons and excitons generated in the light emitting layer pass to the electron transport layer, as a result, charge unbalance occurs in the light emitting layer to emit light at the electron transport layer interface.

When light is emitted from the electron transport layer interface, there is a problem in that the color purity and efficiency of the organic electroluminescent device are lowered. Therefore, it is necessary to develop an electron transport material that has high temperature stability and high electron mobility while improving hole blocking ability with a high T1 value.

KR 1020090028852 A1

The present invention provides an organic electric device with high efficiency, high lifespan and high color purity through the development of a compound having high electron mobility and high temperature stability, and more efficient hole blocking ability with a high T ₁ value, and its An object of the present invention is to provide an electronic device.

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 lifespan of the device can be greatly improved.

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

Hereinafter, it will be described in detail with reference to embodiments of the present invention. In describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

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

As used in this specification and the appended claims, unless otherwise indicated, the following terms have the following meanings:

As used herein, the term “halo” or “halogen” refers to 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, a straight chain alkyl group, a branched chain alkyl group, a cycloalkyl (alicyclic) group, an alkyl-substituted cyclo means a radical of saturated aliphatic functional groups including alkyl groups and cycloalkyl-substituted alkyl groups.

As used herein, the term “haloalkyl group” or “halogenalkyl group” refers to an alkyl group substituted with halogen unless otherwise specified.

As used herein, the term "heteroalkyl group" means that at least one of the carbon atoms constituting the alkyl group is replaced with a hetero atom.

As used herein, the terms "alkenyl group", "alkenyl group" or "alkynyl group" have a double or triple bond of 2 to 60 carbon atoms, respectively, unless otherwise specified, and include a straight or branched chain group, , but not limited thereto.

As used herein, the term “cycloalkyl” refers to an alkyl forming a ring having 3 to 60 carbon atoms, unless otherwise specified, and is not limited thereto.

As used herein, the term "alkoxyl group", "alkoxy group", or "alkyloxy group" refers to an alkyl group to which an oxygen radical is attached, and has 1 to 60 carbon atoms unless otherwise specified, and is limited thereto. it is not

As used herein, the terms "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" refer to 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.

As used herein, the term “aryloxyl group” or “aryloxy group” refers to an aryl group to which an oxygen radical is attached, and has 6 to 60 carbon atoms unless otherwise specified, but is not limited thereto.

The terms "aryl group" and "arylene group" used in the present invention have 6 to 60 carbon atoms, respectively, unless otherwise specified, and are not limited thereto. In the present invention, an aryl group or an arylene group means a single ring or multiple ring aromatic, and includes an aromatic ring formed by a neighboring substituent joining or participating in a 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” refers to 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 the radical substituted with an aryl group has the number of carbon atoms described herein.

Also, when prefixes are named consecutively, it is meant that the substituents are listed in the order listed first. For example, an arylalkoxy group means an alkoxy group substituted with an aryl group, an alkoxylcarbonyl group means a carbonyl group substituted with an alkoxyl group, and an arylcarbonylalkenyl group means an alkenyl group substituted with an arylcarbonyl group and wherein 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. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 2 to 60 carbon atoms each containing at least one heteroatom, unless otherwise specified, No, it includes at least one of a single ring and a multiple ring, and may be formed by combining adjacent functional groups.

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

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

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

Unless otherwise specified, as used herein, the term "aliphatic" 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" as used herein refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocycle having 2 to 60 carbon atoms, or a combination thereof, Contains saturated or unsaturated rings.

Other heterocompounds or heteroradicals other than the above-mentioned heterocompounds include one or more heteroatoms, but are not limited thereto.

Unless otherwise specified, the term "carbonyl" used in the present invention 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. of 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, as used herein, the term "ether" is represented by -R-O-R', wherein R or R' are each independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an alkyl group having 6 to 30 carbon atoms. An aryl group, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, or a combination thereof.

In addition, unless explicitly stated otherwise, in the term "substituted or unsubstituted" used in the present invention, "substitution" means deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ Alkoxyl group, C ₁ ~ C 20 Alkylamine group, C ₁ ~ C ₂₀ Alkylthiophene group, C ₆ ~ C _{20 Arylthiophene} group, C ₂ ~ C ₂₀ Alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₂₀ 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, but 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 by the exponent 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 carbon of the carbons forming the benzene ring, and when 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 omitted.

Hereinafter, a compound according to an aspect of the present invention and an organic electric device including the same will be described.

According to a specific example of the present invention, there is provided a compound represented by the following formula (1).

<Formula (1)>

{In the formula (1),

1) Ar ^{1 , 2} are each independently a C ₆ ~ C ₆₀ aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₂ ~ C ₂₀ Alkynyl group; C ₁ ~ C ₃₀ An alkoxyl group; C ₆ ~ C ₃₀ Aryloxy group; and _{-L' -} N( _{R a} )(R _b ) _; It is selected from the group consisting of an aliphatic ring and a C ₆ -C ₆₀ fused ring group of an aromatic ring, and a C ₂ -C ₆₀ heterocyclic group, wherein R _a and R _b are each independently C ₆ -C ₆₀ Aryl group; Fluorenyl group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ fused ring of aromatic ring C ₂ containing at least one hetero atom and ~C ₆₀ A heterocyclic group; selected from the group consisting of),

2) Ar ^{3 , 4} are each independently a C ₆ ~ C ₆₀ aryl group,

3) X ¹ to X ³ is CR ¹ or N (provided that at least one is N),

4) R ¹ is independently hydrogen, deuterium; halogen; C ₆ ~ C ₆₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₂ ~ C ₂₀ Alkynyl group; C ₁ ~ C ₃₀ An alkoxyl group; C ₆ ~ C ₃₀ Aryloxy group; and -L'-N(R _a )(R _b ); or adjacent R ¹ may be bonded to each other to form a ring.

(Wherein, the aryl group, heteroaryl group, fluorenyl group, arylene group, heterocyclic group, and fused ring 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; C ₁ ~ C ₂₀ Alkoxy group; C ₁ ~ C ₂₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₆ ~ C ₂₀ aryl group; C ₆ ~ C ₂₀ aryl group substituted with deuterium; fluorenyl group; C ₂ ~ C ₂₀ heterocyclic group; C ₃ ~ C ₂₀ cyclo Alkyl group: may be further substituted with one or more substituents selected from the group consisting of a C ₇ ~ C ₂₀ arylalkyl group and a C ₈ ~ C ₂₀ arylalkenyl group, and these substituents may be bonded to each other to form a ring, where 'Ring' refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocycle having 2 to 60 carbon atoms, or a combination thereof, including saturated or unsaturated rings)}

As another specific example of the present invention, there is provided a compound in which Chemical Formula (1) is represented by the following Chemical Formulas (2) to (7).

Chemical formula (2) Chemical formula (3) Chemical formula (4)

Chemical formula (5) Chemical formula (6) Chemical formula (7)

In Formulas (2) to (7), Ar ^{1 to 4} are the same as Ar ^{1 to 4} defined in Formula (1) of claim 1 above.

As a more specific example, the present invention includes a compound represented by the following formula.

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 120 and a second electrode formed on a substrate 110 . An organic material layer including the compound represented by Formula 1 is provided between (180). 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 sequentially include a hole injection layer 130 , a hole transport layer 140 , a light emitting layer 150 , an electron transport layer 160 , and an electron injection layer 170 on the first electrode 120 . In this case, the remaining layers except for the emission layer 150 may not be formed. It may further include a hole blocking layer, an electron blocking layer, a light emission auxiliary layer 151 , a buffer layer 141 , and the like, and the electron transport layer 160 and the like may serve as a hole blocking layer.

In addition, 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.

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

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a PVD (physical vapor deposition) method. For example, an anode is formed by depositing a metal or a metal oxide having conductivity 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 160 and After forming the organic material layer including the electron injection layer 170, it can be manufactured by depositing a material that can be used as a cathode thereon.

Accordingly, the present invention provides a first electrode; a second electrode; and an organic material layer positioned between the first electrode and the second electrode, wherein the organic material layer contains the compound represented by Formula (1).

In addition, the present invention further comprises a light efficiency improving layer formed on at least one of one side of the first electrode in the organic electric device opposite to the organic material layer or one side of the second electrode opposite to the organic material layer in the organic electric device. An organic electric device is provided.

In addition, in the present invention, the organic 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, and the organic layer is an electron transporting material containing the compound It provides an organic electric device, characterized in that.

As another specific example, the present invention provides an organic electric device, characterized in that the same or different compounds of the compound represented by the formula (1) are mixed and used in the organic material layer.

In addition, the present invention is a display device comprising the above-described organic electric device; and a controller for driving the display device.

In another aspect, the present invention provides an electronic device, wherein 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. In this case, the electronic device may be a current or future wired/wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote control, a navigation system, a game machine, various TVs, and various computers.

Hereinafter, a synthesis example of the compound represented by Formula 1 of the present invention and a manufacturing example of an organic electric device of the present invention will be described in detail with reference to Examples, but the present invention is not limited to the following Examples.

[ Synthesis example One]

The compound (final product) represented by Formula (1) according to the present invention is prepared by reacting Sub 1 and Sub 2 as shown in Scheme 1 below.

<Scheme 1>

Sub 1 Synthesis example

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

<Scheme 2>

Sub 1(1) Synthesis example

Sub Synthesis of 1-3-1

Sub 1-1 (14.8g, 80mmol), THF 360mL, Sub 1-2-1 (16.3g, 80mmol), Pd(PPh ₃ ) ₄ (2.8g, 2.4mmol), NaOH (9.6g, 240mmol) ), 180 mL of water is added, and the mixture is stirred and refluxed. When the reaction was completed, the organic layer was extracted with ether and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 12.3 g (68%) of the product.

Sub Synthesis of 1(1)

Sub 1-3-1 (12.2 g, 54 mmol) and Sub 1-4-1 (11.0 g, 54 mmol) were synthesized and recrystallized in the same manner as in Sub 1-3-1 above to obtain 9.5 g (66%) of the product. ) was obtained.

Sub 1(2) Synthesis example

Sub Synthesis of 1-3-2

Sub 1-1 (14.8 g, 80 mmol) and Sub 1-2-2 (20.3 g, 80 mmol) were synthesized and recrystallized in the same manner as in Sub 1-3-1 to obtain 15.2 g (69%) of the product. .

Sub Synthesis of 1(2)

Sub 1-3-2 (15.2 g, 54 mmol) and Sub 1-4-2 (14.0 g, 54 mmol) were synthesized and recrystallized in the same manner as in Sub 1-3-1 above to obtain 13.1 g (65%) of the product. ) was obtained.

An example of Sub 1 is as follows, but is not limited thereto.

compound FD-MS compound FD-MS Sub 1(1) m/z=267.06 (C ₁₅ H ₁₀ ClN ₃ =267.71) Sub 1(2) m/z=367.09 (C ₂₃ H ₁₄ ClN ₃ =367.83) Sub 1(3) m/z=419.12 (C ₂₇ H ₁₈ ClN ₃ =419.90) Sub 1(4) m/z=317.07 (C ₁₉ H ₁₂ ClN ₃ =317.77) Sub 1(5) m/z=419.12 (C ₂₇ H ₁₈ ClN ₃ =419.90)

Sub 2 Synthesis example

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

<Scheme 3>

Sub 2(1) Synthesis example

Sub Synthesis of 2-3-1

Sub 2-1 (25.2 g, 80 mmol), THF 360 mL, Sub 2-2-1 (9.1 g, 80 mmol), Pd(PPh ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol) ), 180 mL of water is added, and the mixture is stirred and refluxed. When the reaction was completed, the organic layer was extracted with ether and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 17.3 g (69%) of the product.

Sub Synthesis of 2-5-1

Sub 2-3-1 (17.2 g, 55 mmol) and Sub 2-4-1 (14.6 g, 55 mmol) were synthesized and recrystallized in the same manner as in Sub 2-3-1 above to give 16.3 g (64%) of the product. ) got

Sub Synthesis of 2(1)

After dissolving Sub 1-5-1 (6.5 g, 14 mmol) in 98 mL of DMF, Bispinacolborate (3.6 g, 15 mmol), PdCl ₂ (dppf) catalyst (0.3 g, 0.4 mmol), KOAc (4.1 g, 42 mmol) After adding in order and stirring for 24 hours, the obtained compound was separated through silicagel column and recrystallization, and 5.0 g (70%) of borate compound Sub 2(1) was obtained.

Sub 2(7) Synthesis Example

Sub Synthesis of 2-3-2

Sub 2-1 (25.2 g, 80 mmol) and Sub 2-2-2 (9.1 g, 80 mmol) were synthesized and recrystallized in the same manner as in Sub 2-3-1 to obtain 16.8 g (67%) of the product. .

Sub Synthesis of 2-5-7

Sub 2-3-2 (16.9 g, 54 mmol) and Sub 2-4-2 (20.0 g, 54 mmol) were synthesized and recrystallized in the same manner as in Sub 2-3-1 to give 20.3 g (66%) of the product. ) got

Sub Synthesis of 2(7)

Sub 2-5-7 (19.9 g, 35 mmol) and Bispinacolborate (8.9 g, 35 mmol) were synthesized and recrystallized in the same manner as in Sub 2(1) to obtain 15.3 g (71%) of Sub 2(7).

Sub 2(12) synthesis example

Sub Synthesis of 2-3-5

Sub 2-1 (25.2 g, 80 mmol) and Sub 2-2-5 (9.2 g, 80 mmol) were synthesized and recrystallized in the same manner as in Sub 2-3-1 to obtain 16.3 g (65%) of the product. .

Sub Synthesis of 2-5-12

Sub 2-3-5 (16.3 g, 52 mmol) and Sub 2-4-12 (21.7 g, 52 mmol) were synthesized and recrystallized in the same manner as in Sub 2-3-1 above to obtain 21.8 g (68%) of the product. ) got

Sub Synthesis of 2(12)

Sub 2-5-12 (21.5 g, 35 mmol) and Bispinacolborate (8.9 g, 35 mmol) were synthesized and recrystallized in the same manner as in Sub 2(1) to obtain 16.0 g (69%) of Sub 2(12).

An example of Sub 2 is as follows, but is not limited thereto.

compound FD-MS compound FD-MS Sub 2(1) m/z=509.25 (C ₃₅ H ₃₂ BNO ₂ =509.45) Sub 2(2) m/z=559.27 (C ₃₉ H ₃₄ BNO ₂ =559.50) Sub 2(3) m/z=559.27 (C ₃₉ H ₃₄ BNO ₂ =559.50) Sub 2(4) m/z=585.28 (C ₄₁ H ₃₆ BNO ₂ =585.54) Sub 2(5) m/z=749.35 (C ₅₄ H ₄₄ BNO ₂ =749.74) Sub 2(6) m/z=748.33 (C ₅₃ H ₄₁ BN ₂ O ₂ =748.72) Sub 2(7) m/z=615.24 (C ₄₁ H ₃₄ BNO ₂ S=615.59) Sub 2(8) m/z=599.26 (C ₄₁ H ₃₄ BNO ₃ =599.52) Sub 2(9) m/z=510.25 (C ₃₄ H ₃₁ BN ₂ O ₂ =510.43) Sub 2(10) m/z=609.28 (C ₄₃ H ₃₆ BNO ₂ =609.56) Sub 2(11) m/z=692.27 (C ₄₆ H ₃₇ BN ₂ O ₂ S=692.67) Sub 2(12) m/z=662.31 (C ₄₆ H ₃₉ BN ₂ O ₂ =662.63)

Final Products Synthesis example

1-2 synthesis example

Sub 1(1) (21.4 g, 80 mmol), THF 360 mL, Sub 2(13) (44.8 g, 80 mmol), Pd(PPh ₃ ) ₄ (2.8 g, 2.4 mmol), NaOH (9.6 g, 240 mmol) ), 180 mL of water is added, and the mixture is stirred and refluxed. When the reaction was completed, the organic layer was extracted with ether and water, dried over MgSO ₄ , concentrated, and the resulting organic material was recrystallized by silicagel column to obtain 36.2 g (68%) of the product.

Synthesis example of 1-6

Sub 1 (1) (21.4 g, 80 mmol) and Sub 2 (14) (59.8 g, 80 mmol) were synthesized and recrystallized in the same manner as in 1-2 to obtain 43.7 g (64%) of the product.

Synthesis example of 2-1

Sub 1 (1) (21.4 g, 80 mmol) and Sub 2 (1) (40.8 g, 80 mmol) were synthesized and recrystallized in the same manner as in 1-2 to obtain 33.0 g (67%) of the product.

Synthesis example of 2-11

Sub 1 (1) (21.4 g, 80 mmol) and Sub 2 (15) (55.3 g, 80 mmol) were synthesized and recrystallized in the same manner as in 1-2 to obtain 42.1 g (66%) of the product.

Synthesis example of 3-14

Sub 1 (3) (33.6 g, 80 mmol) and Sub 2 (16) (44.8 g, 80 mmol) were synthesized and recrystallized in the same manner as in 1-2 to obtain 40.0 g (61%) of the product.

Synthesis example of 4-1

Sub 1 (1) (21.4 g, 80 mmol) and Sub 2 (17) (40.8 g, 80 mmol) were synthesized and recrystallized in the same manner as in 1-2 to obtain 31.0 g (63%) of the product.

Synthesis example of 4-9

Sub 1 (1) (21.4 g, 80 mmol) and Sub 2 (18) (40.9 g, 80 mmol) were synthesized and recrystallized in the same manner as in 1-2 to obtain 29.6 g (60%) of the product.

compound FD-MS compound FD-MS 1-1 m/z=614.25 (C ₄₄ H ₃₀ N ₄ =614.74) 1-2 m/z=664.26 (C ₄₈ H ₃₂ N ₄ =664.79) 1-3 m/z=664.26 (C ₄₈ H ₃₂ N ₄ =664.79) 1-4 m/z=690.28 (C ₅₀ H ₃₄ N ₄ =690.83) 1-5 m/z=854.34 (C ₆₃ H ₄₂ N ₄ =855.03) 1-6 m/z=852.33 (C ₆₃ H ₄₀ N ₄ =853.02) 1-7 m/z=720.23 (C ₅₀ H ₃₂ N ₄ S=720.88) 1-8 m/z=704.26 (C ₅₀ H ₃₂ N ₄ O=704.82) 1-9 m/z=615.24 (C ₄₃ H ₂₉ N ₅ =615.72) 1-10 m/z=714.28 (C ₅₂ H ₃₄ N ₄ =714.85) 1-11 m/z=796.27 (C ₅₆ H ₃₆ N ₄ S=796.98) 1-12 m/z=766.31 (C ₅₆ H ₃₈ N ₄ =766.93) 1-13 m/z=714.28 (C ₅₂ H ₃₄ N ₄ =714.85) 1-14 m/z=816.33 (C ₆₀ H ₄₀ N ₄ =816.99) 1-15 m/z=714.28 (C ₅₂ H ₃₄ N ₄ =714.85) 1-16 m/z=766.31 (C ₅₆ H ₃₈ N ₄ =766.93) 2-1 m/z=614.25 (C ₄₄ H ₃₀ N ₄ =614.74) 2-2 m/z=664.26 (C ₄₈ H ₃₂ N ₄ =664.79) 2-3 m/z=664.26 (C ₄₈ H ₃₂ N ₄ =664.79) 2-4 m/z=690.28 (C ₅₀ H ₃₄ N ₄ =690.83) 2-5 m/z=854.34 (C ₆₃ H ₄₂ N ₄ =855.03) 2-6 m/z=852.33 (C ₆₃ H ₄₀ N ₄ =853.02) 2-7 m/z=720.23 (C ₅₀ H ₃₂ N ₄ S=720.88) 2-8 m/z=704.26 (C ₅₀ H ₃₂ N ₄ O=704.82) 2-9 m/z=615.24 (C ₄₃ H ₂₉ N ₅ =615.72) 2-10 m/z=714.28 (C ₅₂ H ₃₄ N ₄ =714.85) 2-11 m/z=796.27 (C ₅₆ H ₃₆ N ₄ S=796.98) 2-12 m/z=766.31 (C ₅₆ H ₃₈ N ₄ =766.93) 2-13 m/z=714.28 (C ₅₂ H ₃₄ N ₄ =714.85) 2-14 m/z=816.33 (C ₆₀ H ₄₀ N ₄ =816.99) 2-15 m/z=714.28 (C ₅₂ H ₃₄ N ₄ =714.85) 2-16 m/z=766.31 (C ₅₆ H ₃₈ N ₄ =766.93) 3-1 m/z=614.25 (C ₄₄ H ₃₀ N ₄ =614.74) 3-2 m/z=664.26 (C ₄₈ H ₃₂ N ₄ =664.79) 3-3 m/z=664.26 (C ₄₈ H ₃₂ N ₄ =664.79) 3-4 m/z=690.28 (C ₅₀ H ₃₄ N ₄ =690.83) 3-5 m/z=854.34 (C ₆₃ H ₄₂ N ₄ =855.03) 3-6 m/z=852.33 (C ₆₃ H ₄₀ N ₄ =853.02) 3-7 m/z=720.23 (C ₅₀ H ₃₂ N ₄ S=720.88) 3-8 m/z=704.26 (C ₅₀ H ₃₂ N ₄ O=704.82) 3-9 m/z=615.24 (C ₄₃ H ₂₉ N ₅ =615.72) 3-10 m/z=714.28 (C ₅₂ H ₃₄ N ₄ =714.85) 3-11 m/z=796.27 (C ₅₆ H ₃₆ N ₄ S=796.98) 3-12 m/z=766.31 (C ₅₆ H ₃₈ N ₄ =766.93) 3-13 m/z=714.28 (C ₅₂ H ₃₄ N ₄ =714.85) 3-14 m/z=816.33 (C ₆₀ H ₄₀ N ₄ =816.99) 3-15 m/z=714.28 (C ₅₂ H ₃₄ N ₄ =714.85) 3-16 m/z=766.31 (C ₅₆ H ₃₈ N ₄ =766.93) 4-1 m/z=615.24 (C ₄₃ H ₂₉ N ₅ =615.72) 4-2 m/z=665.26 (C ₄₇ H ₃₁ N ₅ =665.78) 4-3 m/z=665.26 (C ₄₇ H ₃₁ N ₅ =665.78) 4-4 m/z=691.27 (C ₄₉ H ₃₃ N ₅ =691.82) 4-5 m/z=855.34 (C ₆₂ H ₄₁ N ₅ =856.02) 4-6 m/z=853.32 (C ₆₂ H ₃₉ N ₅ =854.01) 4-7 m/z=721.23 (C ₄₉ H ₃₁ N ₅ S=721.87) 4-8 m/z=705.25 (C ₄₉ H ₃₁ N ₅ O=705.80) 4-9 m/z=616.24 (C ₄₂ H ₂₈ N ₆ =616.71) 4-10 m/z=715.27 (C ₅₁ H ₃₃ N ₅ =715.84) 4-11 m/z=797.26 (C ₅₅ H ₃₅ N ₅ S=797.96) 4-12 m/z=767.30 (C ₅₅ H ₃₇ N ₅ =767.92) 4-13 m/z=715.27 (C ₅₁ H ₃₃ N ₅ =715.84) 4-14 m/z=817.32 (C ₅₉ H ₃₉ N ₅ =817.97) 4-15 m/z=715.27 (C ₅₁ H ₃₃ N ₅ =715.84) 4-16 m/z=767.30 (C ₅₅ H ₃₇ N ₅ =767.92)

Manufacturing evaluation of organic electric devices

[ Example I] Green organic light emitting device ( electron transport layer )

First, on the ITO layer (anode) formed on a glass substrate, 4,4',4''-Tris[2-naphthyl(phenyl)amino]triphenylamine (hereinafter abbreviated as 2-TNATA) was vacuum-deposited to a thickness of 60 nm. After forming the injection layer, 4,4-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (hereinafter abbreviated as NPD) was vacuum-deposited to a thickness of 60 nm on the hole injection layer to form a hole transport layer was formed. Next, on the hole transport layer, CBP [4,4'-N,N'-dicarbazole-biphenyl] as a host material, Ir(ppy) ₃ [tris(2-phenylpyridine)-iridium] as a dopant material 95: A light emitting layer having a thickness of 30 nm was deposited by doping in a weight ratio of 5. Then, (1,1'bisphenyl)-4-oleato)bis(2-methyl-8-quinolineoleato)aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited on the light emitting layer to a thickness of 10 nm to block the holes. A layer was formed, and one of the compounds of the present invention 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 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.

By applying a forward bias DC voltage to the organic electroluminescent devices of Examples and Comparative Examples prepared in this way, electroluminescence (EL) characteristics were measured with a PR-650 manufactured by photoresearch. The T95 lifespan was measured using a lifespan measuring device manufactured by Science. The table below shows the device fabrication and evaluation results.

[ comparative example One]

An organic electroluminescent device was manufactured in the same manner as in Example I, except that <Comparative Compound 1> was used instead of the compound according to the present invention as the electron transport layer material.

[ comparative example 2]

An organic electroluminescent device was manufactured in the same manner as in Example I, except that <Comparative Compound 2> was used instead of the compound according to the present invention as the electron transport layer material.

[ comparative example 3]

An organic electroluminescent device was manufactured in the same manner as in Example I, except that <Comparative Compound 3> was used as the electron transport layer material instead of the compound according to the present invention.

<Comparative compound 1> <Comparative compound 2> <Comparative compound 3>

compound Voltage Current Density Brightness
(cd/m ² ) Efficiency Lifetime
T(95) CIE
(x, y) Comparative Example (1) Compound (A) 5.7 12.8 500.0 3.9 89.4 (0.15, 0.13) Comparative Example (2) compound (B) 5.1 11.6 500.0 4.3 83.2 (0.14, 0.14) Comparative Example (3) compound (C) 5.2 10.9 500.0 4.6 88.3 (0.15, 0.14) Example (1) Compound (1-1) 4.5 9.3 500.0 5.4 112.9 (0.14, 0.14) Example (2) Compound (1-2) 4.7 9.2 500.0 5.4 118.5 (0.15, 0.13) Example (3) compound (1-3) 4.5 9.2 500.0 5.5 118.9 (0.15, 0.16) Example (4) compound (1-4) 4.6 9.3 500.0 5.4 113.5 (0.15, 0.14) Example (5) Compound (1-5) 4.6 9.1 500.0 5.5 114.7 (0.15, 0.13) Example (6) Compound (1-6) 4.6 9.3 500.0 5.4 112.9 (0.14, 0.14) Example (7) Compound (1-7) 4.6 9.2 500.0 5.4 114.1 (0.15, 0.14) Example (8) compound (1-8) 4.7 9.2 500.0 5.4 116.8 (0.15, 0.13) Example (9) compound (1-9) 4.5 9.2 500.0 5.5 114.8 (0.15, 0.14) Example (10) compound (1-10) 4.5 9.3 500.0 5.4 118.1 (0.15, 0.13) Example (11) compound (1-11) 4.6 9.3 500.0 5.4 116.2 (0.14, 0.14) Example (12) compound (1-12) 4.7 9.2 500.0 5.4 113.3 (0.14, 0.14) Example (13) compound (1-13) 4.7 9.4 500.0 5.3 118.1 (0.14, 0.14) Example (14) compound (1-14) 4.6 9.1 500.0 5.5 118.1 (0.15, 0.13) Example (15) compound (1-15) 4.5 9.2 500.0 5.4 117.7 (0.15, 0.14) Example (16) compound (1-16) 4.7 9.3 500.0 5.4 111.9 (0.15, 0.14) Example (17) Compound (2-1) 4.4 8.7 500.0 5.7 119.9 (0.15, 0.13) Example (18) Compound (2-2) 4.4 8.6 500.0 5.8 120.7 (0.15, 0.13) Example (19) compound (2-3) 4.4 8.7 500.0 5.7 120.0 (0.14, 0.14) Example (20) compound (2-4) 4.4 8.6 500.0 5.8 120.0 (0.15, 0.14) Example (21) compound (2-5) 4.4 8.9 500.0 5.6 119.9 (0.15, 0.14) Example (22) compound (2-6) 4.3 8.8 500.0 5.7 120.0 (0.14, 0.14) Example (23) compound (2-7) 4.3 8.7 500.0 5.7 119.7 (0.15, 0.13) Example (24) compound (2-8) 4.4 8.7 500.0 5.7 119.5 (0.15, 0.16) Example (25) compound (2-9) 4.4 8.8 500.0 5.7 120.3 (0.15, 0.14) Example (26) compound (2-10) 4.4 8.6 500.0 5.8 121.0 (0.15, 0.13) Example (27) compound (2-11) 4.3 8.9 500.0 5.6 119.2 (0.14, 0.14) Example (28) compound (2-12) 4.3 8.6 500.0 5.8 120.1 (0.15, 0.14) Example (29) compound (2-13) 4.4 8.8 500.0 5.7 119.1 (0.15, 0.13) Example (30) compound (2-14) 4.3 8.7 500.0 5.7 120.9 (0.15, 0.14) Example (31) compound (2-15) 4.3 8.7 500.0 5.7 120.4 (0.15, 0.13) Example (32) compound (2-16) 4.4 8.9 500.0 5.6 119.5 (0.14, 0.14) Example (33) Compound (3-1) 4.5 9.3 500.0 5.4 116.3 (0.14, 0.14) Example (34) compound (3-2) 4.5 9.4 500.0 5.3 116.6 (0.14, 0.14) Example (35) compound (3-3) 4.5 9.4 500.0 5.3 111.7 (0.15, 0.13) Example (36) compound (3-4) 4.6 9.4 500.0 5.3 117.8 (0.15, 0.14) Example (37) compound (3-5) 4.6 9.3 500.0 5.4 116.7 (0.15, 0.14) Example (38) compound (3-6) 4.6 9.3 500.0 5.4 110.0 (0.15, 0.13) Example (39) compound (3-7) 4.7 9.4 500.0 5.3 117.0 (0.15, 0.13) Example (40) compound (3-8) 4.6 9.2 500.0 5.5 116.1 (0.14, 0.14) Example (41) compound (3-9) 4.6 9.2 500.0 5.4 118.5 (0.15, 0.14) Example (42) compound (3-10) 4.6 9.1 500.0 5.5 114.9 (0.15, 0.14) Example (43) compound (3-11) 4.6 9.2 500.0 5.5 119.2 (0.14, 0.14) Example (44) compound (3-12) 4.7 9.3 500.0 5.4 112.2 (0.15, 0.13) Example (45) compound (3-13) 4.6 9.3 500.0 5.4 111.4 (0.15, 0.16) Example (46) compound (3-14) 4.5 9.2 500.0 5.5 115.4 (0.15, 0.14) Example (47) compound (3-15) 4.6 9.3 500.0 5.4 113.0 (0.15, 0.13) Example (48) compound (3-16) 4.5 9.3 500.0 5.4 118.9 (0.14, 0.14) Example (49) Compound (4-1) 4.8 9.8 500.0 5.1 108.1 (0.15, 0.14) Example (50) compound (4-2) 4.8 9.7 500.0 5.2 102.8 (0.14, 0.14) Example (51) compound (4-3) 4.9 9.9 500.0 5.1 106.3 (0.15, 0.14) Example (52) compound (4-4) 4.9 9.9 500.0 5.1 104.8 (0.14, 0.14) Example (53) compound (4-5) 4.9 9.8 500.0 5.1 106.9 (0.15, 0.15) Example (54) compound (4-6) 4.8 9.9 500.0 5.0 105.6 (0.15, 0.13) Example (55) compound (4-7) 4.9 9.6 500.0 5.2 106.9 (0.15, 0.14) Example (56) compound (4-8) 4.9 10.0 500.0 5.0 105.2 (0.15, 0.16) Example (57) compound (4-9) 4.9 9.8 500.0 5.1 107.9 (0.15, 0.14) Example (58) compound (4-10) 4.9 9.7 500.0 5.1 108.9 (0.14, 0.14) Example (59) compound (4-11) 4.9 9.8 500.0 5.1 100.6 (0.14, 0.14) Example (60) compound (4-12) 4.9 9.9 500.0 5.1 100.8 (0.15, 0.13) Example (61) compound (4-13) 4.8 9.8 500.0 5.1 109.3 (0.15, 0.15) Example (62) compound (4-14) 4.8 9.8 500.0 5.1 100.4 (0.15, 0.16) Example (63) compound (4-15) 4.8 10.0 500.0 5.0 101.3 (0.15, 0.14) Example (64) compound (4-16) 4.9 9.7 500.0 5.2 108.7 (0.15, 0.14)

As can be seen from the results of Table 4, when the material for an organic light emitting device of the present invention is used as an electron transport layer, it can be confirmed that the driving voltage, efficiency and lifespan are significantly improved.

In other words, when the region in which phenyl is substituted in triazine is viewed as the core, Comparative Compounds 2 and 3, in which pyridine is substituted on one side, showed better device results than Comparative Compound 1, in which aryl groups are substituted on both sides, and pyridine Comparative Compound 3 substituted with an aryl group showed better results than Comparative Compound 2, in which a heterocyclic group was substituted on the other unsubstituted side. However, the company's invention compound in which a specific substituent called terphenyl connected at the m-position is substituted rather than a general aryl group showed the best results.

The energy level value can be controlled by the substituent, and the charge balance in the light emitting layer is increased because the substituent such as the inventive compound has an appropriate energy level, and the hole blocking ability is improved as it has a particularly high T ₁ value. Rather, it is considered that this is because the probability that excitons can stay well in the light emitting layer is relatively increased.

Even for the same core, it is very difficult even for a person skilled in the art to easily infer the characteristics of a device exhibited by a combination of a core and a substituent because the energy level such as LUMO changes as the type of substituent changes and the characteristics significantly change. will be.

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. Accordingly, the embodiments disclosed in the present specification are intended to illustrate, not to limit the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be construed by the following claims, and all descriptions 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 (anode) 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 (cathode)

Claims (10)

A compound represented by the following formula (1)
Formula (1)

{In the formula (1),
1) Ar ¹ and Ar ² are each independently a C ₆ ~ C ₆₀ aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; And C ₂ ~ C ₂₀ Alkynyl group; is selected from the group consisting of, with the proviso that when the heterocycle includes N, except for carbazole,
2) Ar ³ and Ar ⁴ are each independently a C ₆ ~ C ₆₀ aryl group,
3) X ¹ to X ³ are CR ¹ or N (provided that at least one is N),
4) R ¹ is independently hydrogen, deuterium; halogen; C ₆ ~ C ₆₀ Aryl group; fluorenyl group; O, N, S, Si and P containing at least one heteroatom C ₂ ~ C ₆₀ A heterocyclic group; C ₃ ~ C ₆₀ A fused ring group of an aliphatic ring and a C ₆ ~ C ₆₀ aromatic ring; C ₁ ~ C ₅₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₂ ~ C ₂₀ Alkynyl group; And C ₁ ~ C ₃₀ An alkoxyl group; selected from the group consisting of, or adjacent R ¹ may be bonded to each other to form a ring,
Here, the aryl group, the heteroaryl group, the fluorenyl group, the arylene group, the heterocyclic group, the fused ring group is each deuterium; halogen; cyano group; Nitro group; C ₁ ~ C ₂₀ Alkoxyl group; C ₁ ~ C ₂₀ Alkyl group; C ₂ ~ C ₂₀ Alkenyl group; C ₂ ~ C ₂₀ Alkynyl group; C ₆ ~ C ₂₀ Aryl group; C ₆ ~ C ₂₀ Aryl group substituted with deuterium; fluorenyl group; C ₂ ~ C ₂₀ A heterocyclic group and a C ₃ ~ C ₂₀ cycloalkyl group; may be further substituted with one or more substituents selected from the group consisting of, and these substituents may be combined with each other to form a ring, where ' The 'ring' refers to a fused ring consisting of an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocycle having 2 to 60 carbon atoms, or a combination thereof, and includes a saturated or unsaturated ring.}
The method of claim 1,
The compound characterized in that the formula (1) is represented by any one of the following formulas (2) to (7)
Chemical formula (2) Chemical formula (3) Chemical formula (4)

Chemical formula (5) Chemical formula (6) Chemical formula (7)

(In Formulas (2) to (7), Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are as defined in Formula (1) of claim 1 above.)
The method of claim 1,
A compound, characterized in that the compound represented by the formula (1) is selected from the following compounds.

a first electrode; a second electrode; and an organic material layer positioned between the first electrode and the second electrode,
The organic material layer is an organic electric device, characterized in that it contains the compound according to claim 1
5. The method of claim 4,
An organic electric device further comprising a light efficiency improving 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
5. The method of claim 4,
The organic material layer is an organic electric device, characterized in that 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
5. The method of claim 4,
The organic material layer is an organic electric device, characterized in that it contains the compound as an electron transport material
5. The method of claim 4,
An organic electric device, characterized in that the same or two types of compounds of the compound according to claim 1 are mixed and used in the organic material layer
A display device comprising the organic electric device of claim 4; and a control unit for driving the display device;
10. The method of claim 9,
The organic electric device is an electronic device, characterized in that 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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