KR102093186B1 - 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 electrical device using the same, and an electronic device thereof.

Description

Compounds for organic electrical devices, organic electrical devices using the same, and electronic devices thereof {COMPOUND FOR ORGANIC ELECTRONIC ELEMENT, ORGANIC ELECTRONIC ELEMENT USING THE SAME, AND AN ELECTRONIC DEVICE THEREOF}

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

In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy 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 composed of a multi-layer structure composed of different materials in order to increase the efficiency and stability of the organic electric device, and may be formed of, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

Materials used as the organic material layer in the organic electrical 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., depending on the function.

The most important issues in organic electric devices are life and efficiency. As the display becomes larger, these efficiency and life problems must be solved.

Efficiency, life, and driving voltage are related to each other. When the efficiency increases, the driving voltage decreases relatively, and as the driving voltage decreases, crystallization of organic substances due to Joule heating generated during driving decreases, resulting in a lifetime. This tends to increase. However, simply improving the organic layer does not maximize efficiency. Because long energy and high efficiency can be achieved at the same time when the energy level and T ₁ value between each organic material layer and the intrinsic properties of materials (mobility, interfacial properties, etc.) are optimally combined. Because.

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 to generate excitons by recombination.

However, holes move faster than electrons, and excitons generated in the light-emitting layer pass to the electron transport layer, resulting in charge unbalance in the light-emitting layer, thereby emitting light at the electron transport layer interface.

When emitting light at the interface of the electron transport layer, there is a problem in that the color purity and efficiency of the organic electroluminescent device is deteriorated. In particular, when manufacturing the organic electroluminescent device, high temperature stability is lowered, resulting in a shortening of the life of the organic electroluminescent device. Therefore, it is time to develop an electron transport material that improves hole blocking ability with a high T1 value while having high temperature stability and high electron mobility.

The present invention provides a compound having high electron mobility and high temperature stability, and having a more efficient electron transport ability with a high T ₁ value, and at the same time, an organic electric device having improved efficiency, lifetime, and color purity using these compounds, and electrons including the same It is an object to provide a device.

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 using the compound represented by the formula and an electronic device thereof.

According to the present invention, a compound having high electron mobility and high temperature stability, and having a more efficient electron transport ability with a high T ₁ value can be provided, and the efficiency, lifespan, and color purity of the device can be improved using the compound.

1 is an exemplary view 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.

It should be noted that in adding reference numerals to the components of each drawing, the same components have the same reference numerals as possible even though they are displayed on different drawings. In addition, in describing the present invention, when it is determined that detailed descriptions of related well-known configurations or functions may obscure the subject matter of the present invention, detailed descriptions thereof will be omitted.

In addition, in describing the components of the present invention, terms such as first, second, A, B, (a), and (b) may be used. These terms are only for distinguishing 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, that component may be directly connected to or connected to the other component, but another component between each component It should be understood that elements may be "connected", "coupled" or "connected".

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

The terms "halo" or "halogen" as used herein are fluorine (F), bromine (Br), chlorine (Cl) or iodine (I), unless otherwise noted.

The term "alkyl" or "alkyl group" used in the present invention 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 cycle. By radicals of saturated aliphatic functional groups, including alkyl groups, cycloalkyl-substituted alkyl groups.

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" used in the present invention means that at least one of the carbon atoms constituting the alkyl group is replaced with a heteroatom.

The term "alkenyl group" or "alkynyl group" used in the present invention has a double or triple bond having 2 to 60 carbon atoms, and includes straight or branched chain groups, and is not limited thereto, unless otherwise specified. It is not.

As used herein, the term "cycloalkyl" means an alkyl forming a ring having 3 to 60 carbon atoms, unless otherwise specified, but is not limited thereto.

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

As used herein, the terms "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, and 2 to 60 unless otherwise specified. It has a carbon number, and is not limited thereto.

The term "aryloxyl group" or "aryloxy group" used in the present invention means an aryl group to which an oxygen radical is attached, and has a carbon number of 6 to 60 unless otherwise specified, and is not limited thereto.

The terms "aryl group" and "arylene group" used in the present invention have 6 to 60 carbon atoms, respectively, and are not limited thereto unless otherwise specified. In the present invention, an aryl group or an arylene group means a single ring or multi-ring aromatic, and includes an aromatic ring formed by adjacent substituents participating in a bond or reaction. For example, the aryl group may be a phenyl group, biphenyl group, fluorene group, or 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 a carbon number described herein.

Also, when the prefix is named in succession, 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 alkoxycarbonyl group, it means a carbonyl group substituted with an alkoxyl group, and in the case of an arylcarbonyl alkenyl group, it means an alkenyl group substituted with an arylcarbonyl group. Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

As used herein, the term "heteroalkyl" means alkyl containing one or more heteroatoms, unless otherwise specified. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or an arylene group having 2 to 60 carbon atoms, each of which contains one or more heteroatoms, unless otherwise specified. No, it includes at least one of a single ring and multiple rings, and may be formed by combining adjacent functional devices.

The term "heterocyclic group" used in the present invention includes at least one heteroatom, has 2 to 60 carbon atoms, includes at least one of a single ring and multiple rings, heteroaliphatic ring and hetero, unless otherwise specified. Aromatic rings. Adjacent functional groups may also be formed by bonding.

The term “heteroatom” as used herein refers to N, O, S, P or Si, unless otherwise stated.

In addition, "heterocyclic group" may include a ring containing 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" means an aliphatic hydrocarbon ring having 3 to 60 carbon atoms.

Unless otherwise specified, the term "ring" used in the present invention refers to an aliphatic ring having 3 to 60 carbon atoms, an aromatic ring having 6 to 60 carbon atoms, a heterocyclic ring having 2 to 60 carbon atoms or a combination thereof, and Saturated or unsaturated rings.

Other hetero compounds or hetero radicals other than the above-described hetero compounds include one or more hetero atoms, 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, 3 to 30 carbon atoms. Is 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, or 6 to 30 carbon atoms. It is 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.

Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" used in the present invention is 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, substituted with deuterium C ₆ ~ C ₂₀ aryl group, C ₈ ~ C ₂₀ aryl alkenyl group, silane group, boron Means a group, a germanium group, and one or more substituents selected from the group consisting of C ₂ to C ₂₀ heterocyclic groups, and is not limited to these substituents.

In addition, unless expressly stated, the formula used in the present invention is applied in the same manner as the substituent definition 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 bound to any one of carbons forming a benzene ring, and when a is an integer of 2 or 3 Each of them 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 binds to the carbon of the benzene ring in a similar manner, while indicating the hydrogen bound to the carbon forming the benzene ring. 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 the substrate 110. ) Between the organic material layer comprising the compound according to the present invention. At this time, 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, a light emitting layer 150, an electron transport layer 160 and an electron injection layer 170 sequentially on the first electrode 120. At this time, layers other than the emission layer 150 may not be formed. A hole blocking layer, an electron blocking layer, a light-emitting auxiliary layer 151, a buffer layer 141, and the like may be further included, and the electron transport layer 160 may also 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 or a light efficiency improving layer (Capping layer) formed on one surface opposite to the organic material layer among at least one surface of the first electrode and the second electrode.

The compound according to the present invention applied to the organic material layer is a host or dopant or light efficiency improving layer of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, the light emitting layer 150 It could be used as a material. Preferably, the compound of the present invention may be used as the light emitting layer 150 or / and the electron transport layer 160 material.

On the other hand, even in the same core, the band gap, electrical properties, and interfacial properties may vary depending on which substituents are attached to which positions, so the selection of the core and the combination of sub-substituents coupled thereto are also very good. It is important, especially when the energy level and T1 value between each organic material layer and the intrinsic properties of materials (mobility, interfacial properties, etc.) are optimally combined, long life and high efficiency can be achieved simultaneously.

Accordingly, by forming a light emitting layer, an electron transport layer, and the like using the compound of the present invention, the energy level (level) and T1 value between each organic material layer, and the intrinsic properties (mobility, interfacial properties, etc.) of the material are optimized to optimize the life of the organic electric device and Efficiency can be improved at the same time.

On the other hand, in order to solve the light emission problem in the hole transport layer in the recent organic electroluminescent device, it is preferable to form a light-emitting auxiliary layer between the hole transport layer and the light emitting layer, and different light emission according to each light emitting layer (R, G, B) It is time to develop the auxiliary layer. On the other hand, in the case of the light-emitting auxiliary layer, since it is necessary to grasp the relationship between the hole transport layer and the light-emitting layer (host), even if a similar core is used, it will be very difficult to infer the characteristics of the organic layer used.

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a physical vapor deposition (PVD) method. For example, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form the anode 120, and a hole injection layer 130, a hole transport layer 140, a light emitting layer 150, and an electron transport layer are formed thereon. 160) and after forming an organic material layer including the electron injection layer 170, it can be prepared 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 (e.g., spin coating process), nozzle printing process, inkjet printing process, slot coating process, dip coating process, roll-to-roll process, doctor blade using various polymer materials It can be produced with fewer layers by a method such as a ding process, a screen printing process, or a thermal transfer method. Since the organic material layer according to the present invention can be formed in various ways, the scope of the present invention is not limited by the formation method.

The organic electric device according to the present invention may be a front emission type, a back emission type, or a double-sided emission type depending on the material used.

WOLED (White Organic Light Emitting Device) has the advantage of being easy to realize high resolution and excellent processability, and can be manufactured using the color filter technology of the existing LCD. Various structures for a white organic light emitting device mainly used as a backlight device have been proposed. Typically, the R (Red), G (Green), B (Blue) light emitting units are arranged in a mutually planar side-by-side manner, and the stacking method in which the R, G, and B light-emitting layers are stacked up and down. There is, there is a color conversion material (CCM) method using electroluminescence of the blue (B) organic light-emitting layer and photo-luminescence of the inorganic phosphor using light therefrom, the present invention Can 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 photoreceptor (OPC), an organic transistor (organic TFT), a monochromatic or white lighting device.

Another embodiment of the present invention may include an electronic device including a display device including the above-described organic electric element of the present invention and 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 machines, various TVs, and various computers.

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

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

<Formula 1>

In the above formula, X ¹ , X ³ , X ⁵ and X ⁷ are N, X ² , X ⁴ , X ⁶ and X ⁸ are C or CR ^a , X ² and X ⁴ At least one of X and at least one of X ⁶ and X ⁸ is CR ^a , and R ^a in CR ^a may be identical to or different from each other. That is, R ^a is independently of each other hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; And C ₆ to C ₃₀ aryloxy group; It may be selected from the group consisting of, for example, when X ² and X ⁶ are both CR ^a , R ^a of X ² may be hydrogen and R ^a of X ⁶ may be phenyl.

In Formula 1, R ¹ and R ² are independently of each other deuterium; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; And C ₆ ~ C ₃₀ Aryloxy group; It is selected from the group consisting of. For example, R ¹ and R ² may be each independently phenyl, biphenyl, triphenyl, naphthyl, phenanthrene, triphenylene, and the like.

In Formula 1, m and n are each an integer of 0-4. At this time, when m and n are 0, it means that hydrogen is bonded to the carbon of the benzene ring or the linking group L is connected.

이다. 여기서, R^b 및 R^c는 서로 독립적으로, 수소; C₆~C₆₀의 아릴기; O, N, S, Si 및 P 중 적어도 하나의 헤테로원자를 포함하는 C₂~C₆₀의 헤테로고리기; C₁~C₅₀의 알킬기; C₂~C₂₀의 알켄일기; C₁~C₃₀의 알콕시기; 및 플루오렌일기;로 이루어진 군에서 선택되거나, 또는 R^b 및 R^c가 서로 결합하여 이들이 결합된 플루오렌과 함께 스파이로 화합물을 형성할 수 있다.In Chemical Formula 1, L is an unsubstituted C ₆ ~ C ₆₀ arylene group or

to be. Here, R ^b and R ^c are, independently of each other, hydrogen; C ₆ ~ C ₆₀ Aryl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₁ ~ C ₃₀ Alkoxy group; And a fluorenyl group; or R ^b and R ^c may combine with each other to form a spiro compound together with the fluorene to which they are attached.

The linking group L is bonded to one of X ² and X ⁴ when C or one of X ⁶ and X ⁸ is C, and carbon of the benzene ring when X ² , X ⁴ , X ⁶ and X ⁸ are all CR ^a Combine with That is, when X ² , X ⁴ , X ⁶ and X ⁸ are all CR ^a , the linking group L is bonded to one of carbons of the benzene ring to which R ¹ and R ² are bonded. Therefore, at this time, m and n may be integers of 0 to 3.

When L is a fluorenylene group or an unsubstituted arylene group, device characteristics may be improved because L exhibits relatively high thermal stability and electron mobility as compared to a substituted arylene group.

Meanwhile, when R ^a , R ¹ and / or R ² are an aryl group, a fluorenyl group, an alkyl group, an alkenyl group, an alkynyl group, an alkoxyl group, and / or an aryloxy group, each of these is deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; C ₁ ~ C ₂₀ alkylthio; 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 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₂₀ cycloalkyl group; It may be 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. For example, when R ¹ and R ² are aryl groups, each of these may be further substituted with aryl such as one or more phenyl, naphthyl, phenanthrene, triphenylene and the like.

In addition, when R ¹ and / or R ² is a heterocyclic group and / or a fused ring group, each of these is deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; C ₁ ~ C ₂₀ alkylthio; 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 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₂₀ cycloalkyl group; It may be 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.

When L is an arylene group, it may be selected from the following groups.

Specifically, Chemical Formula 1 may be represented as follows. However, when represented by the following formula, R is R ^a or a single bond, and in the case of a single bond, it is bonded to the linking group L.

In addition, in Chemical Formula 1, X ² and X ⁴ When one of X and one of X ⁶ and X ⁸ is C and the other is CR ^a , it may be represented by the following Chemical Formula 1-1. That is, L is X ² and X ⁴ At the same time as being combined with the one of C, since it is combined with the one of C of X ⁶ and X ⁸ , the connector L is coupled to the N-containing ring.

<Formula 1-1>

In Formula 1-1, X ¹ to X ⁸ , L, R ¹ , R ² , m and n are the same as defined in Formula 1.

Illustratively, Formula 1 may be represented by one of the following Formulas 2 to 4.

In Chemical Formulas 2 to 4, X ² , X ⁴ , X ⁶ , and X ⁸ are CR ^a , and L, R ¹ , R ² , m, and n are the same as defined in Chemical Formula 1.

Specifically, the compound according to the present invention may be one of the following compounds.

Hereinafter, synthesis examples of the compounds according to the present invention will be described. The following synthesis method is only an example for synthesizing the compound of the present invention, and the scope of the present invention is not limited thereby.

[ Synthetic example ]

Illustratively, the compounds according to the present invention (Final Product: Product A-1 to C-230) may be prepared by a reaction as in Scheme 1 below.

<Scheme 1>

(In the above scheme, X ¹ to X ⁸ , L, R ¹ , R ² , m and n are the same as defined in Formula 1)

I. Sub  Synthesis of 1

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

<Reaction Scheme 2>

Synthesis examples of specific compounds belonging to Sub 1 are as follows.

One. Sub  1-1 Synthetic example

<Scheme 3>

After dissolving the starting material 2-chloro-4-phenylquinazoline (7.3g, 30.3mmol) in a round bottom flask with 100ml of THF, 1,4-bis (4,4,5,5-tetramethyl-1,3,2- dioxaborolan-2-yl) benzene (10.0g, 30.3mmol), Pd (PPh ₃ ) ₄ (1.4g, 1.2mmol), K ₂ CO ₃ (12.6g, 90.9mmol), 50ml of water was added and at 70 ° C It was stirred. After the reaction was completed, the mixture was extracted with CH ₂ Cl ₂ and water, and the organic layer was dried over MgSO ₄ and concentrated, and then the resulting compound was silicagel column and recrystallized to obtain 9.3 g of product (yield: 75%).

2. Sub  1-7 Synthetic example

<Reaction Scheme 4>

Starting material 4-([1,1'-biphenyl] -3-yl) -2-chloroquinazoline (9.6g, 30.3mmol) with 1,4-bis (4,4,5,5-tetramethyl-1,3 Above, 2-dioxaborolan-2-yl) benzene (10g, 30.3mmol), Pd (PPh ₃ ) ₄ (1.4g, 1.2mmol), K ₂ CO ₃ (12.6g, 90.9mmol), THF 100ml, water 50ml above 9.5 g of product (yield: 65%) was obtained using the Sub 1-1 synthesis method.

Examples of compounds belonging to Sub 1 are as follows, but are not limited thereto, and the FD-MS values for these are shown in Table 1.

[Table 1]

Hereinafter, a method of synthesizing a compound according to the present invention using Sub 1 will be exemplarily described.

II . Final product ( Final Product Synthesis of)

(1.2 당량), Pd(PPh₃)₄(0.05 당량), K₂CO₃ (3 당량), 물을 첨가하고 95°C에서 교반하였다. 반응이 완료되면 CH₂Cl₂와 물로 추출한 후 유기층을 MgSO₄로 건조하고 농축한 후 생성된 화합물을 silicagel column 및 재결정하여 Final products를 얻었다.
After dissolving Sub 1 (1 eq.) In a round bottom flask with Toluene,

(1.2 eq), Pd (PPh ₃ ) ₄ (0.05 eq), K ₂ CO ₃ (3 eq), water was added and stirred at 95 ° C. After the reaction was completed, the organic layer was extracted with CH ₂ Cl ₂ and water, dried over MgSO ₄ and concentrated, and the resulting compound was silicagel column and recrystallized to obtain final products.

One. Product  A-1 Synthetic example

<Scheme 5>

After dissolving Sub 1-1 (4.4 g, 10.8 mmol) obtained in the above synthesis in 40 ml of Toluene in a round bottom flask, 2-chloro-4-phenylquinazoline (2.6 g, 10.8 mmol), Pd (PPh ₃ ) ₄ (0.5 g , 0.4mmol), K ₂ CO ₃ 4.5g, 32.7mmol), 20ml of water was added and stirred at 95 ° C. After the reaction was completed, extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was silicagel column and recrystallized to obtain 4.5 g of product (yield: 85%).

2. Product  A-7 Synthetic example

<Scheme 6>

4-([1,1'-biphenyl] -3-yl) -2-chloroquinazoline (3.4g, 10.8mmol), Pd (PPh ₃ ) _{4 to} Sub 1-7 (5.3g, 10.8mmol) obtained in the above synthesis (0.5g, 0.4mmol), K ₂ CO ₃ (4.5g, 32.7mmol), Toluene 40ml, and water 50ml were obtained using the A-1 synthesis method to give 4.5g of product (yield: 65%).

3. Product  B-1 Synthetic example

<Scheme 7>

4-chloro-2-phenylquinazoline (2.6g, 10.8mmol), Pd (PPh ₃ ) ₄ (0.5g, 0.4mmol), K ₂ CO ₃ 4.5 to Sub 2-1 (4.4g, 10.8mmol) obtained in the above synthesis g, 32.7mmol), 40ml of Toluene and 20ml of water to obtain 4.3g of product (yield: 82%) using the A-1 synthesis method.

4. Product  B-7 Synthetic example

<Scheme 8>

2-([1,1'-biphenyl] -3-yl) -4-chloroquinazoline (3.4g, 10.8mmol), Pd (PPh ₃ ) _{4 to} Sub 2-7 (5.3g, 10.8mmol) obtained in the above synthesis (0.5g, 0.4mmol), K ₂ CO ₃ (4.5g, 32.7mmol), Toluene 40ml, and water 50ml were obtained using the A-1 synthesis method to give 4.1g of product (yield: 60%).

5. Product  C-1 Synthetic example

<Scheme 9>

2-chloro-4-phenylquinazoline (2.6g, 10.8mmol), Pd (PPh ₃ ) ₄ (0.5g, 0.4mmol), K ₂ CO ₃ 4.5 to Sub 1-1 (4.4g, 10.8mmol) obtained in the above synthesis g, 32.7mmol), 40ml of Toluene and 20ml of water to obtain 3.9g of product (yield: 75%) using the A-1 synthesis method.

6. Product  C-7 Synthetic example

<Reaction Scheme 10>

2-([1,1'-biphenyl] -3-yl) -4-chloroquinazoline (3.4g, 10.8mmol), Pd (PPh ₃ ) _{4 to} Sub 1-7 (5.3g, 10.8mmol) obtained in the above synthesis (0.5g, 0.4mmol), K ₂ CO ₃ (4.5g, 32.7mmol), Toluene 40ml, and 50ml of water were obtained 3.8g (yield: 55%) using the A-1 synthesis method.

On the other hand, although the above described exemplary synthetic examples of the present invention represented by Formula 1, they are all based on Miyaura boration reaction and Suzuki cross-coupling reaction, etc., and other substituents defined in Formula 1 in addition to the substituents specified in the specific synthesis example (X ¹ to X ⁸ , L, R ¹ , a substituent such as R ^2, etc.), it will be easily understood by those skilled in the art that the reaction proceeds. For example, in <Reaction Scheme 2>, the starting material-> Sub 1 reaction is based on the Miyaura boration reaction, and <Scheme 5> to <Reaction Scheme 10> are based on the Suzuki cross-coupling reaction. The above reactions will proceed even if substituents not specifically specified are bound to them.

The FD-MS values of the compounds A-1 to A-214, B-1 to B-215 and C-1 to C-230 of the present invention prepared according to the above synthesis examples are shown in Table 2.

[Table 2]

Hereinafter, Examples 1 to 659 in which device characteristics are measured by applying the compound according to the present invention to an organic electric device will be described.

Manufacturing evaluation of organic electric devices

[ Example  1] Green organic electroluminescent device ( Electron transport layer )

An organic electroluminescent device was manufactured according to a conventional method using the compound of the present invention as an electron transport layer material.

First, 4,4 ', 4''-Tris [2-naphthyl (phenyl) amino] triphenylamine (hereinafter abbreviated as 2-TNATA) on an ITO layer (anode) formed on a glass substrate is vacuum deposited to a thickness of 60 nm. After forming the hole injection layer, 4,4-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (hereinafter abbreviated as NPD) is vacuum deposited on the hole injection layer to a thickness of 60 nm to form a hole transport layer. Was formed. Next, CBP [4,4'-N, N'-dicarbazole-biphenyl] as a host material on the hole transport layer and 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 at a weight ratio of 5. Subsequently, (1,1 'bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) is vacuum-deposited to a thickness of 10 nm on the light emitting layer to block holes. An electron transport layer was formed by forming a layer and vacuum-depositing Compound A-1 of the present invention to a thickness of 40 nm on the hole blocking layer. Subsequently, an organic electroluminescent device was manufactured by depositing LiF, an alkali metal halide, on the electron transport layer to a thickness of 0.2 nm to form an electron injection layer, and then depositing Al to a thickness of 150 nm to form a cathode.

[ Example  2] ~ [ Example  659] Green Organic Electroluminescent Device ( Electron transport layer )

Except for using the compound A-2 to A-214, B-1 to B-215 and C-1 to C-230 of the present invention shown in Table 3 below instead of the compound A-1 of the present invention as the electron transport layer material In the same manner as in Example 1, an organic electroluminescent device was manufactured.

[ Comparative example  One]

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

<Comparative Compound 1> Alq ₃

[ Comparative example  2]

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

<Comparative Compound 2>

[ Comparative example  3]

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

<Comparative Baggage 3>

[ Comparative example  4]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 4 was used instead of Compound A-1 of the present invention as the electron transport layer material.

<Comparative compound 4>

[ Comparative example  5]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 5 was used instead of Compound A-1 of the present invention as the electron transport layer material.

<Comparative compound 5>

[ Comparative example  6]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 6 was used instead of Compound A-1 of the present invention as the electron transport layer material.

<Comparative Compound 6>

[ Comparative example  7]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that Comparative Compound 7 was used instead of Compound A-1 of the present invention as the electron transport layer material.

<Comparative Compound 7>

Electroluminescence (EL) characteristics with PR-650 of photoresearch by applying a net bias DC voltage to the organic electroluminescent elements manufactured by Examples 1 to 659 and Comparative Examples 1 to 7 of the present invention Was measured, and the T95 life was measured through a life measurement equipment manufactured by Max Science at a luminance of 5000 cd / m ² . The results are shown in Table 3 below.

[Table 3]

As can be seen from the results of [Table 3], the organic electroluminescent device using the compound of the present invention as the material for the electron transport layer is compared with the organic electroluminescent device using the comparative compounds 1 to 7 as the material for the electron transport layer. This low, luminous efficiency was not only improved, but also the life and the like were remarkably improved.

This is of use as a dopant in the light emitting layer Ir (ppy) Comparative compound used as the electron transport layer than the T ₁ value (2.4 eV) of ₃ 1 (Alq ₃₎ to Comparative Compound 4 T ₁ value (2.0 eV) have a significantly lower T ₁ value In contrast, in the case of the compounds of the present invention, the excitons in the light emitting layer can be maintained well by exhibiting a T ₁ value (2.5 ev to 2.6 ev) that is generally higher than the T ₁ value of Ir (ppy) ₃ (2.4 eV). This is because the probability is relatively high.

In addition, even if they have the same bis type (bis type) quinazoline core, the unsubstituted compound of the present invention showed better device results than the comparative compounds 5 to 7 with the alkyl group substituted on the linking group L, which is unsubstituted. The compound of the present invention having a linked linking group L exhibits relatively high thermal stability and faster electron mobility than the compound having a substituted L, so that holes and electrons in the light-emitting layer form charge balance to efficiently recombine It can be explained that it is possible to realize the optimal luminous efficiency through.

Combining the aforementioned characteristics (high T1 value, fast electron mobility, and high thermal stability), band gap, electrical properties, and interfacial properties are largely dependent on whether a substituent is introduced into the bis type quinazoline core. It can be changed, and it can be confirmed that it acts as a major factor in improving the performance of the device.

The above description is merely illustrative of the present invention, and those skilled in the art to which the present invention pertains will be capable of various modifications without departing from the essential characteristics of the present invention. Therefore, the embodiments disclosed herein 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 equivalent range should be interpreted as being included in the scope of the present invention.

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

Claims (11)

Compound represented by the formula (1):
<Formula 1>

In the above formula,
X ¹ , X ³ , X ⁵ and X ⁷ are N, X ² , X ⁴ , X ⁶ and X ⁸ are C or CR ^a , at least one of X ² and X ⁴ and at least one of X ⁶ and X ⁸ Is CR ^a , and when C is bonded to L,
R ^a is independently of each other hydrogen; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; And C ₆ ~ C ₃₀ Aryloxy group; It is selected from the group consisting of,
L is

Where R ^b and R ^c are, independently of each other, an aryl group of C ₆ to C ₆₀ or an alkyl group of C ₁ to C ₅₀ , and R ^b and R ^c are bonded to each other to spy together with fluorene to which they are bonded. Can form a compound,
R ¹ and R ² are independently of each other deuterium; halogen; C ₆ ~ C ₆₀ Aryl group; Fluorenyl group; C ₂ ~ C ₆₀ heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₆₀ aliphatic ring and C ₆ ~ C ₆₀ aromatic ring fused ring group; C ₁ ~ C ₅₀ alkyl group; C ₂ ~ C ₂₀ alkenyl group; C ₂ ~ C ₂₀ alkynyl group; C ₁ ~ C ₃₀ Alkoxy group; And C ₆ ~ C ₃₀ Aryloxy group; is selected from the group consisting of, m and n are each an integer of 0 to 4,
The aryl group of R ^a , R ¹ and R ² , fluorenyl group, alkyl group, alkenyl group, alkynyl group, alkoxyl group and aryloxy group, each of the heterocyclic group and fused ring group of R ¹ and R ² is deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; C ₁ ~ C ₂₀ alkylthio; 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 heterocyclic group containing at least one heteroatom of O, N, S, Si and P; C ₃ ~ C ₂₀ cycloalkyl group; C ₇ ~ C ₂₀ Arylalkyl group; And C ₈ ~ C ₂₀ aryl alkenyl group; It may be substituted with one or more substituents selected from the group consisting of. According to claim 1,
Formula 1 is a compound characterized in that represented by one of the following formula:

In Chemical Formulas 2 to 4, X ² , X ⁴ , X ⁶ , and X ⁸ are CR ^a , and L, R ¹ , R ² , R ^a , m, and n are the same as defined in claim 1. Compound represented by one of the following formulas 2 to 4:

In Chemical Formulas 2 to 4,
L is

And
X ² , X ⁴ , X ⁶ and X ⁸ are C (R ^a ),
R ¹ and R ² are hydrogen, m and n are each 0,
The R ^a is a C ₆ ~ C ₁₈ aryl group, wherein R ^a may be further substituted with ^a C ₆ ~ C ₂₀ aryl group. According to claim 1,
The compound represented by Formula 1 is one of the following compounds:

. Compounds characterized by being one of the following compounds:

. A first electrode; A second electrode; And an organic material layer positioned between the first electrode and the second electrode, wherein the organic electric device comprises:
The organic layer is an organic electrical device, characterized in that it contains the compound of any one of claims 1 to 5. The method of claim 6,
The organic material layer includes a light emitting layer and an electron transport layer,
An organic electric device, characterized in that the compound is contained in at least one of the light emitting layer and the electron transport layer. The method of claim 6,
The organic material layer further comprises an emission layer, and an emission auxiliary layer formed between the emission layer and the first electrode or between the emission layer and the second electrode. The method of claim 6,
An organic electric device further comprising a light efficiency improving layer formed on at least one surface opposite to the organic material layer among one surface of the first electrode and the second electrode. A display device comprising the organic electroluminescent element of claim 6; And
An electronic device comprising; a control unit for driving the display device. The method of claim 10,
The organic electrical 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 monochromatic or white lighting device.

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