WO2015083974A1 - Compound for organic electric element, organic electric element using same, and electronic device thereof - Google Patents

Abstract

Disclosed is a compound represented by formula 1. Also, disclosed is an organic electric element, comprising a first electrode, a second electrode, and an organic layer between the first electrode and the second electrode, wherein the organic layer comprises a compound represented by formula 1. If the organic layer comprises a compound represented by formula 1, luminous efficiency, stability and lifespan, etc. of an organic electric element can be improved.

Description

Compound for organic electric element, organic electric element using same and 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, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic electric element using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. In this case, 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, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer.

The material used as the organic material layer in the 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 and the like according to a function.

The biggest problem for organic electric devices is life and efficiency. As the display becomes larger, these efficiency and life problems must be solved.

Efficiency, lifespan, and driving voltage are related to each other.As the efficiency increases, the driving voltage decreases relatively, and as the driving voltage decreases, crystallization of organic materials due to Jouleheating generated during driving decreases, resulting in a lifetime. This tends to be higher. However, simply improving the organic layer may not maximize the efficiency. Because of the optimal combination of energy level, T ₁ value, and intrinsic properties (mobility, interfacial properties, etc.) between organic layers, long life and high efficiency can be achieved simultaneously. 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 emission layer are transferred to the electron transport layer, resulting in charge unbalance in the emission layer, thereby emitting light at the electron transport layer interface.

When emitting light at the electron transport layer interface, there is a problem that the color purity and efficiency of the organic electroluminescent device is deteriorated, and in particular, when the organic electroluminescent device is manufactured, a problem arises that the lifetime of the organic electroluminescent device is shortened due to the high temperature stability. Therefore, it is time to develop an electron transport material that has high temperature stability and high electron mobility and improves hole blocking ability with a high T1 value.

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 using the compound, an organic electric device having improved efficiency, lifetime and color purity, and an electron 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 electronic device using the compound represented by the above formula and an electronic device thereof.

According to the present invention, it is possible to provide a compound having high electron mobility and high temperature stability and more efficient electron transport ability with a high T ₁ value, and by using such a compound, it is possible to improve the efficiency, lifespan and color purity of the device.

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

[Description of the code]

100: organic electric element 110: substrate

120: first electrode 130: hole injection layer

140: hole transport layer 141: buffer layer

150: light emitting layer 151: light emitting auxiliary layer

160: electron transport layer 170: electron injection layer

180: second electrode

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

In adding reference numerals to the components of each drawing, it should be noted that the same reference numerals are assigned to the same components as much as possible even though they are shown in different drawings. In addition, in describing the present invention, when it is determined that the detailed description of the related well-known configuration or function may obscure the gist of the present invention, the detailed description thereof will be omitted.

In addition, in describing the component of this invention, terms, such as 1st, 2nd, A, B, (a), (b), can be used. These terms are only for distinguishing the components from other components, and the nature, order or order of the components are not limited by the terms. If a component is described as being "connected", "coupled" or "connected" to another component, that component may be directly connected to or connected to that other component, but there may be another configuration between each component. It is to be understood that the elements may be "connected", "coupled" or "connected".

As used in this specification and the appended claims, unless otherwise indicated, the meanings of the following terms are as follows:

The term "halo" or "halogen" as used herein is fluorine (F), bromine (Br), chlorine (Cl) or iodine (I) unless otherwise indicated.

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

As used herein, the term "haloalkyl group" or "halogenalkyl group" means an alkyl group substituted with halogen unless otherwise specified.

As used herein, the term "alkenyl group" or "alkynyl group", unless stated otherwise, has a double or triple bond of 2 to 60 carbon atoms, and includes a straight or branched chain group, and is not limited thereto. It is not.

The term "cycloalkyl" as used herein, unless otherwise stated, refers to alkyl forming a ring having 3 to 60 carbon atoms, without being limited thereto.

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

As used herein, the term "alkenoxyl group", "alkenoxy group", "alkenyloxyl group", or "alkenyloxy group" means an alkenyl group to which an oxygen radical is attached, and unless otherwise stated, it is 2 to 60 It has carbon number of, It is not limited to this.

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

As used herein, the terms "aryl group" and "arylene group" have a carbon number of 6 to 60 unless otherwise stated, but is not limited thereto. In the present invention, an aryl group or an arylene group means an aromatic of a single ring or multiple rings, and includes an aromatic ring formed by neighboring substituents participating in a bond or a reaction. For example, the aryl group may be a phenyl group, a biphenyl group, a fluorene group, 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 the radical substituted with an aryl group has the carbon number described herein.

Also, when prefixes are named consecutively, it means that the substituents are listed in the order described 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. Wherein the arylcarbonyl group is a carbonyl group substituted with an aryl group.

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 one or more heteroatoms, unless otherwise specified. It may include at least one of a single ring and multiple rings, and may be formed by combining adjacent functional groups.

As used herein, the term “heterocyclic group” includes one or more heteroatoms, unless otherwise indicated, and has from 2 to 60 carbon atoms, and includes at least one of single and multiple rings, heteroaliphatic rings and hetero Aromatic rings. Adjacent functional groups may be formed in combination.

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

"Heterocyclic groups" may also include rings comprising SO ₂ in place of the carbon forming the ring. For example, a "heterocyclic group" includes the following compounds.

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

Unless otherwise stated, the term "ring" as used herein 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. Saturated or unsaturated rings.

Other heterocompounds or heteroradicals other than the aforementioned heterocompounds include, but are not limited to, one or more heteroatoms.

Also, unless expressly stated, the term "substituted" in the term "substituted or unsubstituted" refers to deuterium, halogen, amino groups, nitrile groups, nitro groups, C ₁ -C ₂₀ alkyl groups, 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, C ₃ -C ₂₀ cycloalkyl group, C ₆ -C ₂₀ aryl group, of a C ₆ -C ₂₀ aryl group substituted with a heavy hydrogen, C ₈ -C ₂₀ aryl alkenyl group, a silane group, a boron Substituted by at least one substituent selected from the group consisting of a group, a germanium group, and a C ₂ -C ₂₀ heterocyclic group containing at least one heteroatom selected from the group consisting of O, N, S, Si and P It is not limited to these substituents.

Also, unless otherwise stated, the formulas used in the present invention apply equally to the definitions of substituents based on the exponential definition of the following formulas.

Herein, when a is an integer of 0, the substituent R ¹ is absent, when a is an integer of 1, one substituent R ¹ is bonded to any one of carbons forming the benzene ring, and a is an integer of 2 or 3 Are each bonded as follows, where R ¹ may be the same or different from each other, and when a is an integer from 4 to 6, it is bonded to the carbon of the benzene ring in a similar manner, while the indication of hydrogen bonded 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, a first electrode 110, and a second electrode 180 formed on a substrate 110. ) Is provided with an organic material layer containing a 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 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 on the first electrode 120 in sequence. At this time, the remaining layers except for the light emitting layer 150 may not be formed. The hole blocking layer, the electron blocking layer, the light emitting auxiliary layer 151, the buffer layer 141 may be further included, and the electron transport layer 160 may serve as the 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 of the 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 of the hole injection layer 130, the hole transport layer 140, the electron transport layer 160, the electron injection layer 170, the host of the dopant or light efficiency improvement layer of the light emitting layer 150 It may be used as a material. Preferably, the compound of the present invention may be used as the light emitting layer 150 or / and electron transport layer 160 material.

Meanwhile, even in the same core, band gaps, electrical characteristics, and interface characteristics may vary depending on which substituents are bonded at which positions. Therefore, the selection of cores and the combination of sub-substituents bound thereto are also very significant. Importantly, long life and high efficiency can be achieved at the same time when an optimal combination of energy level and T1 value and intrinsic properties (mobility, interfacial properties, etc.) of each organic material layer is achieved.

Therefore, by using the compound of the present invention to form a light emitting layer, an electron transport layer, etc. by optimizing the energy level (level) and T1 value of each organic material layer, the intrinsic properties (mobility, interfacial characteristics, etc.) of the organic material layer, Efficiency can be improved at the same time.

On the other hand, in the recent organic electroluminescent device, in order to solve the light emission problem in the hole transport layer, 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. Meanwhile, in the case of the light emitting auxiliary layer, it is difficult to infer the characteristics of the organic material layer used even if a similar core is used, since the correlation between the hole transport layer and the light emitting layer (host) must be understood.

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

The organic electric element according to the present invention may be a top emission type, a bottom emission type or a double-sided emission type depending on the material used.

WOLED (White Organic Light Emitting Device) has the advantage that can be manufactured using the color filter technology of the existing LCD while being easy to realize high resolution and excellent processability. Various structures for white organic light emitting diodes mainly used as backlight devices have been proposed. Representatively, a side-by-side method in which R (Red), G (Green), and B (Blue) light emitting parts are mutually planarized, and a stacking method in which R, G, and B light emitting layers are stacked up and down. And a color conversion material (CCM) method using photo-luminescence of an inorganic phosphor by using electroluminescence by a blue (B) organic light emitting layer and light therefrom. May also be applied to these WOLEDs.

In addition, the organic electroluminescent 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), a monochromatic or white illumination device.

Another embodiment of the present invention may include a display device including the organic electric element of the present invention described above, and an electronic device including a control unit for controlling the display device. In this case, the electronic device may be a current or future wired or wireless communication terminal, and includes all electronic devices such as a mobile communication terminal such as a mobile phone, a PDA, an electronic dictionary, a PMP, a remote controller, a navigation device, a game machine, various TVs, and various computers.

Hereinafter, the compound which concerns on one aspect of this invention is demonstrated.

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

<Formula 1>

In Chemical Formula 1, 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 X ⁶ and At least one of X ⁸ is CR ^a , and R ^a in CR ^a may be the same as or different from each other. That is, R ^a is independently of each other hydrogen; halogen; C ₆ -C ₆₀ aryl group; Fluorenyl group; A fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ ; An alkyl group of C ₁ -C ₅₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And an aryloxy group of C ₆ -C ₃₀ ; For example, when X ² and X ⁶ are both CR ^a , R ^a of X ² is hydrogen and R ^a of X ⁶ may be phenyl.

In Formula 1, R ¹ and R ² are independently from each other deuterium; halogen; C ₆ -C ₆₀ aryl group; Fluorenyl group; C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ ; An alkyl group of C ₁ -C ₅₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And C ₆ -C ₃₀ An aryloxy group; It is selected from the group consisting of. For example, R ¹ and R ² may be, independently of one another, phenyl, biphenyl, triphenyl, naphthyl, phenanthrene, triphenylene, or the like.

In formula 1, m and n are each an integer of 0-4. In this case, 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.

In Formula 1, L is an unsubstituted C ₆ -C ₆₀ arylene group or

to be. Wherein R ^b and R ^c are, independently from each other, hydrogen; C ₆ -C ₆₀ aryl group; C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; An alkyl group of C ₁ -C ₅₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkoxy group of C ₁ -C ₃₀ ; And a fluorenyl group; or R ^b and R ^c may be bonded to each other to form a spiro compound together with fluorene to which they are bonded.

The linker L is bonded to one of X ² and X ⁴ if C or one of X ⁶ and X ⁸ is C, and carbon of the benzene ring if 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 the carbons of the benzene ring to which R ¹ and R ² are bonded. Therefore, m and n may be an integer of 0 to 3 at this time.

When L is a fluorenylene group or an unsubstituted arylene group, the device characteristics may be improved since L shows relatively high thermal stability and electron mobility compared with the case of substituted arylene.

Meanwhile, when R ^a , R ¹ and / or R ² are an aryl group, fluorenyl group, alkyl group, alkenyl group, alkynyl group, alkoxyl group and / or aryloxy group, each of these is deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C ₁ -C _20; An alkoxyl group of C ₁ -C ₂₀ ; An alkyl group of C ₁ -C ₂₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; Aryl group of C ₆ -C ₂₀ ; C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C ₃ -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group; And an arylalkenyl group of C ₈ -C ₂₀ It may be substituted with one or more substituents selected from the group consisting of. For example, when R ¹ and R ² are aryl groups, each of them may be further substituted with one or more aryl such as 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 them is deuterium; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C ₁ -C _20; An alkoxyl group of C ₁ -C ₂₀ ; An alkyl group of C ₁ -C ₂₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; Aryl group of C ₆ -C ₂₀ ; C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C ₃ -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group; And an arylalkenyl group of C ₈ -C ₂₀ It may be substituted with one or more substituents selected from the group consisting of.

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

Specifically, Formula 1 may be represented as follows. However, when represented by the formula below, 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 Formula 1, when one of X ² and X ⁴ and one of X ⁶ and X ⁸ is C and the other is CR ^a , it may be represented by the following Formula 1-1. That is, L is bonded to the C of X ² and X ⁴ and at the same time is bonded to the C of X ⁶ and X ⁸ , so that the linking group L is bonded to the N-containing ring.

<Formula 1-1>

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

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

<Formula 2>

<Formula 3>

<Formula 4>

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

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

Hereinafter, the synthesis example of the compound which concerns on this invention is demonstrated. The following synthetic method is only an example for synthesizing the compound of the present invention, and the scope of the present invention is not limited thereto.

Synthesis Example

By way of example, 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 and the like are the same as defined in formula 1)

I. Synthesis of Sub 1

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

<Scheme 2>

Specific examples of the compound belonging to Sub 1 are as follows.

1.Sub 1-1 Synthesis Example

<Scheme 3>

After dissolving the starting material 2-chloro-4-phenylquinazoline (7.3g, 30.3mmol) with 100ml THF in a round bottom flask, 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 water was added and stirred at 70 ℃ It was. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallized to obtain 9.3 g (yield: 75%) of the product.

2. Sub 1-7 Synthesis Example

<Scheme 4>

1,4-bis (4,4,5,5-tetramethyl-1,3) in 4-([1,1'-biphenyl] -3-yl) -2-chloroquinazoline (9.6 g, 30.3 mmol) , 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 9.5 g (yield: 65%) of product was obtained using Sub 1-1 synthesis.

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

TABLE 1

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

II. Synthesis of Final Product

After dissolving Sub 1 (1 equivalent) in a round bottom flask with Toluene,

(1.2 equiv), Pd (PPh ₃ ) ₄ (0.05 equiv), K ₂ CO ₃ (3 equiv), water were added and stirred at 95 ° C. After completion of the reaction, the mixture was extracted with CH ₂ Cl ₂ and water, the organic layer was dried over MgSO ₄ and concentrated, and the resulting compound was purified by silicagel column and recrystallization to obtain final products.

1.Product A-1 Synthesis Example

Scheme 5

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

2.Product A-7 Synthesis Example

<Scheme 6>

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

3.Product B-1 Synthesis Example

Scheme 7

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

4.Product B-7 Synthesis Example

Scheme 8

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

5. Product C-1 Synthesis Example

Scheme 9

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

6.Product C-7 Synthesis Example

Scheme 10

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

On the other hand, in the above described an exemplary synthesis example of the present invention represented by the formula (1), these are all based on the Miyaura boration reaction and Suzuki cross-coupling reaction, etc., in addition to the substituents specified in the specific synthesis example other substituents (X) ^It will be readily understood by those skilled in the art that the reaction proceeds even when the substituents of ¹ to X ⁸ , L, R ¹ , R ^2, etc.) are combined. For example, the starting material-> Sub 1 reaction in <Scheme 2> is based on the Miyaura boration reaction, and <Scheme 5> to <Scheme 10> are based on the Suzuki cross-coupling reaction. The reactions will proceed even if substituents not specifically specified in these are attached.

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

TABLE 2

Hereinafter, Examples 1 to 659 in which the 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 Electrical Device

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) was vacuum-deposited on an ITO layer (anode) formed on a glass substrate. After the hole injection layer was formed, 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. 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 were 95: A light emitting layer having a thickness of 30 nm was deposited by doping at a weight ratio of 5 nm. Subsequently, (1,1'bisphenyl) -4-oleito) bis (2-methyl-8-quinoline oleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm on the light emitting layer by hole blocking. A layer was formed, and the electron transport layer was formed by vacuum depositing Compound A-1 of the present invention on the hole blocking layer in a thickness of 40 nm. Subsequently, LiF, which is an alkali metal halide, was deposited to a thickness of 0.2 nm on the electron transport layer to form an electron injection layer, and then an Al was deposited to a thickness of 150 nm to form a cathode, thereby manufacturing an organic electroluminescent device.

Example 2 to Example 659 Green Organic Electroluminescent Device (electron transport layer)

Except for using the compounds 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. The organic electroluminescent device was manufactured in the same manner as in Example 1.

Comparative Example 1

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 an 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 an 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 an electron transport layer material.

Comparative Compound 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 an 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 an 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 an 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 an electron transport layer material.

Comparative Compound 7

Electroluminescence (EL) characteristics by PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent devices prepared by Examples 1 to 659 and Comparative Examples 1 to 7 of the present invention The T95 lifetime was measured using a life-time measuring instrument manufactured by McScience Inc. at 5000 cd / m ² reference luminance. The results are shown in Table 3 below.

TABLE 3

As can be seen from the result of [Table 3], the organic electroluminescent device using the compound of the present invention as the material of the electron transport layer is the driving voltage compared to the organic electroluminescent device using the comparative compound 1 to Comparative Compound 7 as the material of the electron transport layer. It was low, and not only the luminous efficiency was improved but also the life and the like markedly 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 On the contrary, in the case of the compounds of the present invention, the T ₁ value (2.5 eV to 2.6 eV) is generally higher than the T ₁ value of Ir (ppy) ₃ (2.4 eV), so that excitons can stay well in the light emitting layer. This is because the probability is relatively increased.

In addition, even when the same bis type (quine type) quinazoline cores, the compound of the present invention unsubstituted than Comparative Compound 5 to Comparative Compound 7 in which the alkyl group is substituted in the linking group L showed better device results, which is unsubstituted Compounds of the present invention having a linked L group exhibit relatively higher thermal stability and faster electron mobility than compounds having a substituted L group, so that holes and electrons charge balance in the light emitting layer, resulting in efficient recombination. It can be described that the implementation of the optimum luminous efficiency through.

In view of the above characteristics (high T1 value, fast electron mobility and high thermal stability), the band gap, electrical characteristics, and interface characteristics are greatly increased depending on whether a substituent is introduced into the bis type quinazoline core. It can be seen that it can be changed, which is 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 may various modifications without departing from the essential characteristics of the present invention. Accordingly, the embodiments disclosed herein are not intended to limit the present invention but to describe the present invention, and the spirit and scope of the present invention are not limited by these embodiments. The protection scope of the present invention should be interpreted by the following claims, and all the technologies within the equivalent scope should be interpreted as being included in the scope of the present invention.

CROSS-REFERENCE TO RELATED APPLICATION

This patent application claims priority under Patent Application No. 10-2013-0149083, filed in Korea on December 03, 2013, pursuant to Article 119 (a) (35 USC § 119 (a)). All content is incorporated by reference in this patent application. In addition, if this patent application claims priority for the same reason for countries other than the United States, all its contents are incorporated into this patent application by reference.

Claims (11)

1. Compound represented by the following formula (1):

   <Formula 1>

   

   In Chemical Formula 1,

   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 if C, combines with L,

   R ^a is independently of each other hydrogen; halogen; C ₆ -C ₆₀ aryl group; Fluorenyl group; An alkyl group of C ₁ -C ₅₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And C ₆ -C ₃₀ An aryloxy group; selected from the group consisting of,

   L is an unsubstituted C ₆ -C ₆₀ arylene group or

   

   Wherein R ^b and R ^c are each independently a C ₆ -C ₆₀ aryl group; C ₂ -C ₆₀ comprising at least one heteroatom selected from the group consisting of O, N, S, Si and P Heterocyclic group; C ₁ -C ₅₀ alkyl group; C ₂ -C ₂₀ alkenyl group; C ₁ -C ₃₀ alkoxy group; and fluorenyl group; or R ^b and R ^c are Combine with each other to form a spiro compound with the fluorene to which they are attached),

   R ¹ and R ² independently of each other deuterium; halogen; C ₆ -C ₆₀ aryl group; Fluorenyl group; C ₂ -C ₆₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A fused ring group of an aliphatic ring of C ₃ -C ₆₀ and an aromatic ring of C ₆ -C ₆₀ ; An alkyl group of C ₁ -C ₅₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; An alkoxyl group of C ₁ -C ₃₀ ; And C ₆ -C ₃₀ An aryloxy group; It is selected from the group consisting of, m and n are each an integer of 0 to 4,

   Wherein R ^a, R ¹ and R ² of the aryl group, fluorene group, alkyl group, alkenyl group, alkynyl group, alkoxy group and aryloxy group, a heterocyclic group of R ¹ and R ^2, and a fused ring group each of which heavy hydrogen; halogen; Silane group; Siloxane groups; Boron group; Germanium group; Cyano group; Nitro group; Import alkylthio of C ₁ -C _20; An alkoxyl group of C ₁ -C ₂₀ ; An alkyl group of C ₁ -C ₂₀ ; Alkenyl groups of C ₂ -C ₂₀ ; An alkynyl group of C ₂ -C ₂₀ ; Aryl group of C ₆ -C ₂₀ ; C ₆ -C ₂₀ aryl group substituted with deuterium; Fluorenyl group; C ₂ -C ₂₀ heterocyclic group including at least one heteroatom selected from the group consisting of O, N, S, Si and P; A cycloalkyl group of C ₃ -C ₂₀ ; C ₇ -C ₂₀ arylalkyl group; And an arylalkenyl group of C ₈ -C ₂₀ It may be substituted with one or more substituents selected from the group consisting of.
2. The method of claim 1,

   Compounds characterized in that represented by one of the following formula:

   <Formula 2>

   

   <Formula 3>

   

   <Formula 4>

   

   In Formulas 2 to 4, X ² , X ⁴ , X ⁶ , X ⁸ are CR ^a , and L, R ¹ , R ² , m and n are the same as defined in claim 1.
3. The method of claim 1,

   When L is an unsubstituted arylene group, the compound characterized in that it is selected from the group:

   

   .
4. The method of claim 1,

   Compounds characterized in that one of the following compounds:

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   

   .
5. A first electrode; Second electrode; And an organic material layer positioned between the first electrode and the second electrode.

   The organic material layer is an organic electroluminescent device comprising the compound of claim 1.
6. The method of claim 5,

   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.
7. The method of claim 5,

   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.
8. The method of claim 5,

   And an optical efficiency improving layer formed on at least one surface of the first electrode and the second electrode opposite to the organic material layer.
9. The method of claim 5,

   The organic material layer is formed by a spin coating process, a nozzle printing process, an inkjet printing process, a slot coating process, a dip coating process or a roll-to-roll process.
10. A display device comprising the organic electroluminescent device of claim 5; And

    And a controller for driving the display device.
11. The method of claim 10,

    The organic electronic device is at least one of an organic electroluminescent device, an organic solar cell, an organic photosensitive member, an organic transistor, and a device for monochrome or white illumination.

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