WO2014010897A1 - Compound, organic electric element using same, and electronic device thereof - Google Patents

Abstract

The present invention relates to a novel compound, an organic electric element using the same, and an electronic device thereof. According to the present invention, it is possible to improve luminous efficiency, color purity and lifetime of an element and lower a driving voltage.

Description

Compounds, Organic Electrical Devices And Electronic Devices Using The Same

The present invention relates to a compound, an organic electric element comprising 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. The organic layer is often made of a multi-layer 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 element may be classified into a light emitting material and a charge transport material such as a hole injection material, a hole transport material, an electron transport material, an electron injection material and the like according to a function.

On the other hand, it delays the diffusion of metal oxide into the organic layer from the anode electrode (ITO), which is one of the causes of shortening the life of the organic electronic device, and stable characteristics, that is, high glass transition even for Joule heating generated when driving the device. There is a need for development of a hole injection layer material having a temperature. In addition, the low glass transition temperature of the hole transport layer material has been reported to have a significant effect on the device life, depending on the characteristics of the uniformity of the surface of the thin film when driving the device. In addition, the deposition method is the mainstream in the formation of the OLED device, a situation that requires a material that can withstand a long time, that is, a material having a strong heat resistance characteristics.

In order to fully exhibit the excellent characteristics of the above-described organic electroluminescent device, a material constituting the organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc., is supported by a stable and efficient material. Although this should be preceded, the development of a stable and efficient organic material layer for an organic electric element has not yet been made sufficiently, and therefore, the development of new materials is continuously required.

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

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

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

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 life of the device can be greatly improved.

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

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".

On the other hand, the terms "halo" or "halogen" as used herein include fluorine, chlorine, bromine, and iodine unless otherwise stated.

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

As used herein, the term "alkenyl" or "alkynyl" has a double bond or a triple bond having 2 to 60 carbon atoms, respectively, unless otherwise specified, but is not limited thereto.

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.

The term "alkoxy group" used in the present invention has a carbon number of 1 to 60 unless otherwise stated, it 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 a monocyclic or polycyclic aromatic, 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.

As used herein, the term “heteroalkyl” means an alkyl including one or more heteroatoms unless otherwise indicated. As used herein, the term "heteroaryl group" or "heteroarylene group" means an aryl group or arylene group having 3 to 60 carbon atoms, each of which includes one or more heteroatoms, unless otherwise specified. In addition, it includes not only single ring but also multiple rings, and adjacent groups may be formed by combining.

As used herein, the terms "heterocycloalkyl", "heterocyclic group" includes one or more heteroatoms, unless otherwise indicated, having from 2 to 60 carbon atoms, including single rings as well as multicycles. Adjacent groups may be formed in combination. In addition, "heterocyclic group" may mean an alicyclic and / or aromatic including a heteroatom.

As used herein, the term “heteroatom” refers to N, O, S, P, and Si unless otherwise indicated.

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 "saturated or unsaturated ring" as used herein means a saturated or unsaturated aliphatic ring or an aromatic ring or heterocyclic ring having 6 to 60 carbon atoms.

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

Also, unless stated otherwise, the term "substituted" in the term "substituted or unsubstituted" as used in the present invention is deuterium, halogen, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy groups, C ₁ to C ₂₀ alkylamine groups, C ₁ to C ₂₀ alkylthiophene groups, C ₆ to C ₂₀ arylthiophene groups, C ₂ to C ₂₀ alkenyl groups, C ₂ to C ₂₀ alkynyl group, C ₃ ~ C ₂₀ cycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₆ ~ C ₂₀ aryl group substituted with deuterium, C ₈ ~ C ₂₀ aryl alkenyl group, silane group, boron Group, germanium group, and C ₅ ~ C _{20 It} is meant to be substituted with one or more substituents selected from the group consisting of, but not limited to these substituents.

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

Referring to FIG. 1, the organic electric device 100 according to the present invention includes a first electrode 120, a second electrode 180, a first electrode 110, and a second electrode 180 formed on a substrate 110. An organic material layer containing a compound represented by the formula (1) between) is provided. 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 electronic device according to the present invention may further include a protective layer formed on one surface of the first electrode and the second electrode opposite to the organic material layer.

The compound according to the present invention applied to the organic material layer is a hole injection layer 130, a hole transport layer 140, an electron transport layer 160, the electron injection layer 170, the host of the light emitting layer 150 or the material of the dopant or capping layer Can be used as

The organic electroluminescent device according to an embodiment of the present invention may be manufactured using a 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 using a variety of polymer materials is less by a solution process or solvent process, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing or thermal transfer method, rather than deposition It can be prepared in a number of layers. 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.

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 Formula 1, A represents a benzene ring fused to each other by sharing two sides with two adjacent rings, it may be represented by the following formula (2).

Formula 2

In Formula 1, B is a pentagonal ring condensed with A, including X and Y, and may be represented by the following Formula 3.

Formula 3

In Formula 3, * represents a part condensed with an adjacent ring, X is selected from NR ', O, S, CR'R "and SiR'R", and Y is N or CR'. In this case, R 'and R "are each independently of each other, hydrogen; C_One~ C₂₀Alkyl group, C_One~ C₂₀Alkoxy group, C_One~ C₂₀Alkylamine groups, C_One~ C₂₀Alkylthiophene groups, C₆~ C₂₀Arylthiophene group, C₂~ C₂₀Alkenyl, C₂~ C₂₀Alkynyl, C₃~ C₂₀Cycloalkyl group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₈~ C₂₀Aryl alkenyl group, silane group, boron group, germanium group and C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of heterocyclic groups₆~ C₆₀Aryl group; Hydrogen, deuterium, halogen, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Arylamine group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₂₀C which is unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group and includes at least one heteroatom of O, N, S, Si and P₂~ C₆₀Heterocyclic group of; And C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group_One~ C₅₀An alkyl group; selected from the group consisting of.

For example, Chemical Formula 3 may be represented by one of the following Chemical Formulas, and * represents a part condensed with an adjacent ring.

Meanwhile, in Chemical Formulas 1 to 3, R_One To R₆Are each independently of the other hydrogen; heavy hydrogen; Tritium; Halogen group; Hydrogen, deuterium, tritium, halogen, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group_One~ C₅₀Alkyl groups; Hydrogen, deuterium, tritium, halogen, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Arylamine group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₂₀C which is unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group and includes at least one heteroatom of O, N, S, Si and P₂~ C₆₀Heterocyclic group of; Hydrogen, deuterium, tritium, halogen, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Arylamine group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group₂~ C₂₀Alkenyl group; Hydrogen, deuterium, tritium, halogen, C_One~ C₂₀Alkyl group, C_One~ C₂₀Alkoxy group, C_One~ C₂₀Alkylamine groups, C_One~ C₂₀Alkylthiophene groups, C₆~ C₂₀Arylamine group, C₆~ C₂₀Arylthiophene group, C₂~ C₂₀Alkenyl, C₂~ C₂₀Alkynyl, C₃~ C₂₀Cycloalkyl group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₈~ C₂₀Aryl alkenyl group, silane group, boron group, germanium group and C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of heterocyclic groups₆~ C₆₀Aryl group; And Hydrogen, deuterium, tritium, halogen group, amino group, nitrile group, nitro group, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₃~ C₃₀Cycloalkyl group, C₂~ C₃₀Heterocycloalkyl group, C₆~ C₆₀Aryl group, C₂~ C₆₀C unsubstituted or substituted with a substituent selected from the group consisting of heterocyclic groups₆~ C₆₀An arylamine group; may be selected from the group consisting of.

remind R_One To R₄May each combine with a neighboring group to form a substituted or unsubstituted alicyclic, aromatic or hetero ring. For example, R₂Is neighboring R_One Or R₃And may form an alicyclic, aromatic or heterocyclic ring.

In addition, in Formula 2, n may be an integer of 0 to 2. When n is 2, a plurality of R ₆ may be the same or different from each other, and adjacent R ₆ may combine with each other to form a substituted or unsubstituted alicyclic, aromatic or heterocycle.

In Formula 1, L is nitro, nitrile, halogen, C_One~ C₂₀Alkyl group, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Aryl group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group and an amino group of₆~ C₆₀Arylene group; Hydrogen, deuterium, tritium, halogen, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C_One~ C₅₀Alkyl group, C₂~ C₂₀A fluorenylene group unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group; And Nitro, nitrile, halogen, C_One~ C₂₀Alkyl group, C_One~ C₂₀Alkoxy group C₆~ C₂₀Aryl group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group and an amino group of₃~ C₆₀It is selected from the group consisting of; hetero arylene group.

In addition, in Formula 1, Ar ₁ and Ar ₂ are each independently hydrogen, deuterium, tritium, a halogen group, a C ₁ ~ C ₂₀ alkyl group, C ₁ ~ C ₂₀ alkoxy group, C ₁ ~ C ₂₀ alkyl amine group, C ₁ ~ C ₂₀ alkyl thiophene group, C ₆ ~ C ₂₀ aryl thiophene group, C ₂ ~ C ₂₀ alkenyl group, C ₂ ~ C ₂₀ alkynyl group, C ₃ ~ C ₂₀ of the cycloalkyl of alkyl group, C ₆ ~ C ₂₀ aryl group, of a C ₆ ~ C ₂₀ substituted with a heavy hydrogen aryl, C ₈ ~ C ₂₀ arylalkenyl group, a silane group, a boron group, a germanium group, and a C ₂ ~ C ₂₀ of C ₆ ~ C ₆₀ aryl group unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group; Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and C ₂ ~ C ₆₀ heterocyclic group which is unsubstituted or substituted with a substituent selected from the group consisting of acetylene groups and containing at least one hetero atom of O, N, S, Si and P; Hydrogen, deuterium, tritium, halogen group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ arylamine group, C ₆ ~ C An aryl group of ₆₀ , a C ₆ to C ₂₀ aryl group substituted with deuterium, a C ₇ to C ₂₀ arylalkyl group, an aryl alkenyl group of C ₈ to C ₂₀ , a heterocyclic group of C ₂ to C ₂₀ , a nitrile group and C ₂ ~ C ₂₀ alkenyl group unsubstituted or substituted with a substituent selected from the group consisting of an acetylene group; Hydrogen, deuterium, tritium, a halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, a C ₆ ~ C ₂₀ substituted with a heavy hydrogen of the aryl group, C ₁ ~ C ₅₀ unsubstituted or substituted with a substituent selected from the group consisting of C ₇ ~ C ₂₀ arylalkyl group, C ₈ ~ C ₂₀ aryl alkenyl group, C ₂ ~ C ₂₀ heterocyclic group, nitrile group and acetylene group Alkyl groups; Hydrogen, deuterium, tritium, halogen group, amino group, nitrile group, nitro group, C ₁ ~ C ₂₀ alkyl group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₃ ~ C ₃₀ cycloalkyl group, C ₂ ~ C ₃₀ of the heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, C ₂ ~ C ₆₀ heterocyclic group the group the substituents a substituted or unsubstituted C ₆ ~ C ₆₀ aryl amine selected from the consisting of group; And hydrogen, deuterium, tritium, halogen group, C ₂ ~ C ₂₀ alkenyl group, C ₁ ~ C ₂₀ alkoxy group, C ₆ ~ C ₂₀ aryl group, C ₆ ~ C ₂₀ aryl group substituted with deuterium Substituted with a substituent selected from the group consisting of: C ₇ -C ₂₀ arylalkyl group, C ₈ -C ₂₀ arylalkenyl group, C ₁ -C ₅₀ alkyl group, C ₂ -C ₂₀ heterocyclic group, nitrile group and acetylene group Or an unsubstituted fluorene group (wherein the substituents of the fluorene group may be bonded to each other to form a ring if possible). In this case, each of Ar ₁ and Ar ₂ may be bonded to an adjacent group to form a substituted or unsubstituted alicyclic, aromatic or hetero ring.

More specifically, the compound represented by Formula 1 may be one of the following compounds 1-1 to 3-25.

Hereinafter, the synthesis examples of the compound represented by the formula (1) according to the present invention and the production examples of the organic electric device will be described in detail by way of examples, but the present invention is not limited to the following examples.

Synthesis Example

Compound (Final product) according to the present invention was synthesized by reacting Sub 3 synthesized by Scheme 1 and the following Scheme 2 and Sub 4 synthesized by the following Scheme 3.

<Scheme 1> Synthesis Example of Sub 1

<Scheme 2> Synthesis Example of Sub 3

<Scheme 3> Synthesis Example of Sub 4

<Scheme 4> Synthesis Example

 Example 1

Sub 1 Synthesis Example

(1) Sub 1-2 synthesis method

Sub 1-1 was dissolved in anhydrous THF, the temperature of the reaction was lowered to -78 ° C, n-BuLi (2.5 M in hexane) was slowly added dropwise, and the reaction was stirred at 0 ° C for 1 hour. Then, the temperature of the reaction was lowered to -78 ℃, trimethyl borate was added dropwise and stirred at room temperature for 12 hours. After the reaction was completed, 2N-HCl aqueous solution was added, stirred for 30 minutes, and extracted with ether. Water in the reaction was removed with anhydrous MgSO ₄ , filtered under reduced pressure, and the resulting product was concentrated by separation of the organic solvent using column chromatography to obtain the desired product.

Examples of Sub 1-1 are as follows, but are not limited thereto.

(2) Sub 1-3 synthesis method

Sub 1-2, 1-bromo-2-nitrobenzene, Pd (PPh ₃ ) ₄ and K ₂ CO ₃ substituted with R ₁ to R ₄ were dissolved in anhydrous THF and a small amount of water and refluxed for 24 hours. After the reaction was completed, the temperature of the reactant was cooled to room temperature, extracted with CH ₂ Cl ₂ , and washed with water. A small amount of water was removed with anhydrous MgSO ₄ and filtered under reduced pressure, and then the organic solvent was concentrated and the resulting product was separated using column chromatography to obtain the desired product.

(3) Sub 1 synthesis

Sub 1-3 and triphenylphosphine were dissolved in o-dichlorobenzene and refluxed for 24 hours. After the reaction was completed, the solvent was removed by distillation under reduced pressure, and then the concentrated product was separated using column chromatography to obtain the desired product.

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

Table 1

 Example 2

Sub 3 Synthesis Example

As described in Scheme 2, Sub 1 (1 equiv), Sub 2 (1.1 equiv), Pd ₂ (dba) ₃ (0.05 mol%), PPh ₃ (0.1 equiv), NaO t -Bu ( 3 equivalents) and toluene (10.5 mL / 1 mmol) were added and the reaction was carried out at 100 ° C. After the reaction was completed, the organic layer extracted with ether and water was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain the product Sub 3.

Examples of Sub 3 are as follows, but are not limited thereto, and their FD-MS are shown in Table 2 below.

TABLE 2

 Example 3

Sub 4 Synthesis Example

Amine compound (1 equiv), Bromine compound (1.1 equiv), Pd ₂ (dba) ₃ (0.05 mol%), P (t-Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv) , toluene (10.5 mL / 1 mmol) was added and the reaction proceeded at 100 ° C. After the reaction was completed, the organic layer extracted with ether and water was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to give the product Sub 4.

Examples of Sub 4 are as follows, but are not limited thereto, and their FD-MS are shown in Table 3 below.

TABLE 3

 Example 4

Product synthesis

Sub 3 (1.1 equiv), Sub 4 (1 equiv), Pd ₂ (dba) ₃ (0.05 mol%), P (t-Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv) , toluene (10.5 mL / 1 mmol) was added and the reaction proceeded at 100 ° C. After the reaction was completed, the organic layer extracted with ether and water was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to obtain a product product.

(1) Product 1-1 Synthesis Example

Scheme 5

10- (4'-bromo- [1,1'-biphenyl] -4-yl) -1-phenyl-1,10-dihydropyrrolo [2,3-a] carbazole (12.3 g, 24 mmol) in a round bottom flask, di ([1,1'-biphenyl] -4-yl) amine (6.4 g. 20 mmol), Pd ₂ (dba) ₃ (0.05 mol%), P (t-Bu) ₃ (0.1 equiv), NaO t- After adding Bu (3 equivalents) and toluene (10.5 mL / 1 mmol), the reaction was performed at 100 ° C. After the reaction was completed, the organic layer extracted with ether and water was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to give 8.0g (yield: 60%).

(2) Product 2-12 Synthesis Example

<Scheme 6>

6- (4'-bromo- [1,1'-biphenyl] -4-yl) -6H-thieno [3,2-c] carbazole (10.9 g, 24 mmol), N-([1, 1'-biphenyl] -4-yl) -9,9-dimethyl-9H-fluoren-2-amine (7.2 g. 20 mmol), Pd ₂ (dba) ₃ (0.05 mol%), P (t-Bu) ₃ (0.1 equiv), NaO ( t- Bu) (3 equiv) and toluene (10.5 mL / 1 mmol) were added, and the reaction was carried out at 100 ° C. When the reaction was completed, the organic layer extracted with ether and water was dried over MgSO ₄ and concentrated, and the resulting organic material was silicagel column and recrystallized to give 9.1g the product (yield: 62%).

(3) Product 3-1 Synthesis Example

Scheme 7

10- (4'-bromo- [1,1'-biphenyl] -4-yl) -10H-furo [2,3-a] carbazole (10.5 g, 24 mmol), di ([1,1] '-biphenyl] -4-yl) amine (6.4 g. 20 mmol), Pd ₂ (dba) ₃ (0.05 mol%), P (t-Bu) ₃ (0.1 equiv), NaO ( t -Bu) (3 equiv ), toluene (10.5 mL / 1 mmol) was added and the reaction proceeded at 100 ° C. After the reaction was completed, the organic layer extracted with ether and water was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to give 8.0g (yield: 59%).

(4) Product 3-7 Synthesis Example

Scheme 8

9- (4'-bromo- [1,1'-biphenyl] -4-yl) -1,1-diphenyl-1,9-dihydrosilolo [2,3-b] carbazole (14.5 g, 24 mmol) in a round bottom flask ), N-([1,1'-biphenyl] -4-yl)-[1,1 ': 3', 1 ''-terphenyl] -4-amine (8.0 g. 20 mmol), Pd ₂ (dba) ₃ (0.05 mol%), P (t-Bu) ₃ (0.1 equiv), NaO t -Bu (3 equiv), toluene (10.5 mL / 1 mmol) were added thereto, and the reaction was performed at 100 ° C. After the reaction was completed, the organic layer extracted with ether and water was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to give 11.1g (yield: 60%).

(5) Product 3-19 Synthesis Example

Scheme 9

In a round bottom flask, 5- (7-bromo-9,9-dimethyl-9H-fluoren-2-yl) -5H-thiazolo [5,4-b] carbazole (11.9 g, 24 mmol), N-([1, 1'-biphenyl] -4-yl) -9,9'-spirobi [fluoren] -2-amine (9.7 g. 20 mmol), Pd ₂ (dba) ₃ (0.05 mol%), P (t-Bu) ₃ (0.1 equiv), NaO ( t- Bu) (3 equiv) and toluene (10.5 mL / 1 mmol) were added, and the reaction was carried out at 100 ° C. After the reaction was completed, the organic layer extracted with ether and water was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to give 10.4g (yield: 58%).

(6) Example of Product 3-21 Synthesis

Scheme 10

6- (2-bromo-9,9'-spirobi [fluoren] -7-yl) -6H-oxazolo [4,5-c] carbazole (14.4 g, 24 mmol), di ([1,1] '-biphenyl] -4-yl) amine (6.4 g. 20 mmol), Pd ₂ (dba) ₃ (0.05 mol%), P (t-Bu) ₃ (0.1 equiv), NaO ( t -Bu) (3 equiv ), toluene (10.5 mL / 1 mmol) was added and the reaction proceeded at 100 ° C. After the reaction was completed, the organic layer extracted with ether and water was dried over MgSO ₄ and concentrated, and the resulting organic material was purified by silicagel column and recrystallized to give 9.6g (yield: 57%).

Table 4

Manufacturing Evaluation of Organic Electrical Device

 Example 5

First, 4,4 ', 4 "-tris (N- (2-naphthyl) -N-phenylamino) -triphenylamine (hereinafter abbreviated as 2T-NATA) on an ITO layer (anode) formed on a glass substrate. The film was vacuum deposited to form a hole injection layer having a thickness of 10 nm, and then the compound according to the present invention was vacuum deposited to a thickness of 30 nm to form a hole transport layer on the hole injection layer. , 10-di (naphthalene-2-anthracene (AND)) was used, and BD-052X (Idemitus Co., Ltd.) was added at a concentration of 7% by weight as a blue fluorescent dopant material to form a light emitting layer by vacuum deposition at a thickness of 45 nm. Then, (1,1'-bisphenyl) -4-oleito) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a hole blocking layer at a thickness of 10 nm. After forming tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) to a thickness of 40nm with an electron injection layer, LiF which is an alkali metal halide is 0.2 nm The organic EL device was fabricated using Al / LiF formed as a cathode by depositing a layer with a thickness of 150 nm.

Comparative Example 1

An organic electroluminescent device was manufactured in the same manner as in Example 5, except that Comparative Compound 1 (NPB) was used instead of the compound of the present invention as a material for the hole transport layer.

<Compound 1 (NPB)>

Comparative Example 2

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

<Compound A>

As a result of measuring the characteristics of the electroluminescent device with the PR-650 of photoresearch by applying a forward bias DC voltage to the organic electroluminescent device manufactured in Example 5, Comparative Example 1 and Comparative Example 2 as described above Table 5 is as follows. At this time, the T90 life was measured through the life measurement equipment manufactured by McScience Inc. at 300 cd / m ² reference luminance.

Table 5

As can be seen from the results of Table 5, when the compound according to the present invention is used as a hole transport layer material, the driving voltage of the organic electric device is lowered compared to Comparative Example 1 using NPB as the hole transport layer and Comparative Example 2 to which Comparative Compound A is applied. In addition, the efficiency and lifespan can be significantly improved.

 Example 6

First, a copper phthalocyanine (hereinafter abbreviated as CuPc) is vacuum-deposited on an ITO layer (anode) formed on a glass substrate to form a hole injection layer having a thickness of 40 nm, followed by 4,4-bis [on the hole injection layer. N- (1-naphthyl) -N -phenylamino] biphenyl (hereinafter abbreviated as -NPD) was vacuum deposited to a thickness of 20 nm to form a hole transport layer. Next, the compound of the present invention was vacuum-deposited to a thickness of 20 nm on the hole transport layer to form a light emission auxiliary layer. After forming the emission auxiliary layer, 5 wt% of CBP as a phosphorescent host material and tris (2-phenylpyridine) iridium (hereinafter abbreviated as Ir (ppy) ₃ ) as an ir metal complex dopant as a phosphorescent dopant material It was added at a concentration to form a light emitting layer by vacuum deposition to a thickness of 30nm. Subsequently, (1,1'-bisphenyl) -4-oleato) bis (2-methyl-8-quinolineoleito) aluminum (hereinafter abbreviated as BAlq) was vacuum-deposited to a thickness of 10 nm as a hole blocking layer. After forming tris (8-quinolinol) aluminum (hereinafter abbreviated as Alq ₃ ) to a thickness of 40 nm with a transport layer, LiF, an alkali metal halide, is deposited to a thickness of 0.2 nm as an electron injection layer, and then Al is 150 nm. An organic light emitting diode was manufactured by using Al as a cathode by evaporating to a thickness of.

Comparative Example 3

An organic light emitting diode was manufactured in the same manner as in Example 6, but the emission auxiliary layer was omitted. That is, an organic light emitting display device was manufactured in the same manner as in Example 6, except that an emission auxiliary layer was not formed.

[Comparative Example 4]

An organic light emitting display device was manufactured in the same manner as in Example 6, except that the Comparative Compound B was used to form the emission auxiliary layer instead of the compound of the present invention.

<Compound B>

The electroluminescent (EL) characteristics of the organic electroluminescent devices manufactured by Example 6, Comparative Example 4 and Comparative Example 5 were measured by applying a forward bias DC voltage to PR-650 of photoresearch company. Same as At this time, the T90 life was measured through the life measurement equipment manufactured by McScience Inc. at 300 cd / m ² reference luminance.

Table 6

As can be seen from the results of Table 6, in the case of forming the light-emitting auxiliary layer formed of the compound according to the present invention, Comparative Example 4 including the light-emitting auxiliary layer formed of Comparative Example 3 and Compound B is not formed It was confirmed that the device characteristics are significantly superior to. That is, the organic electroluminescent device including the light emitting auxiliary layer formed of the compound of the present invention has significantly improved the light emitting efficiency and lifetime while the driving voltage is low. In the light emitting auxiliary layer to which the compound according to the present invention is applied, the T1 energy level is high and the HOMO energy level is deep, thereby lowering the driving voltage of the organic electroluminescent device and significantly improving the luminous efficiency and lifetime.

As described above, when the compound according to the present invention is applied to an organic electroluminescent device, the device exhibits excellent device characteristics. Thus, the compound according to the present invention is not only an organic electroluminescent device (OLED) but also a display device, an organic solar cell, and an organic photoconductor (OPC). ), Organic transistors (organic TFTs), monochromatic or white lighting elements, and the like. In addition, the compound according to the present invention, in addition to the hole transport layer or the light emitting auxiliary layer, The same effect may be obtained even when used in a hole injection layer, a light emitting layer, an electron injection layer, an electron transport layer.

The present invention has been described above by way of example, and those skilled in the art will appreciate that various modifications may be made 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 No. 119 (a) (35 USC § 119 (a)) of the Patent Application No. 10-2012-0075982 filed with Korea on July 12, 2012. 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 (8)

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

               <Formula 1>

   

   Where A =

   

   And condense by sharing one side with two adjacent rings, B =

   

   And * represents a part condensed with an adjacent ring)

   In Chemical Formula 1,

   (1) X is selected from NR ', O, S, CR'R "and SiR'R", and Y is N or CR', wherein R ', R "is hydrogen; C_One~ C₂₀Alkyl group, C_One~ C₂₀Alkoxy group, C_One~ C₂₀Alkylamine groups, C_One~ C₂₀Alkylthiophene groups, C₆~ C₂₀Arylthiophene group, C₂~ C₂₀Alkenyl, C₂~ C₂₀Alkynyl, C₃~ C₂₀Cycloalkyl group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₈~ C₂₀Aryl alkenyl group, silane group, boron group, germanium group and C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of heterocyclic groups₆~ C₆₀Aryl group; Hydrogen, deuterium, halogen, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Arylamine group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₂₀C which is unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group and includes at least one heteroatom of O, N, S, Si and P₂~ C₆₀Heterocyclic group of; And C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₂₀Substituted or unsubstituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene groupC                 _One~ C₅₀An alkyl group; selected from the group consisting of

   (2) R ₁ to R ₆ are each independently hydrogen; heavy hydrogen; Tritium; Halogen group;

   Hydrogen, deuterium, tritium, halogen, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group_One~ C₅₀Alkyl group;Hydrogen, deuterium, tritium, halogen, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Arylamine group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₂₀C which is unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group and includes at least one heteroatom of O, N, S, Si and P₂~ C₆₀Heterocyclic group of; Hydrogen, deuterium, tritium, halogen, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Arylamine group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group₂~ C₂₀Alkenyl group; Hydrogen, deuterium, tritium, halogen, C_One~ C₂₀Alkyl group, C_One~ C₂₀Alkoxy group, C_One~ C₂₀Alkylamine groups, C_One~ C₂₀Alkylthiophene groups, C₆~ C₂₀Arylamine group, C₆~ C₂₀Arylthiophene group, C₂~ C₂₀Alkenyl, C₂~ C₂₀Alkynyl, C₃~ C₂₀Cycloalkyl group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₈~ C₂₀Aryl alkenyl group, silane group, boron group, germanium group and C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of heterocyclic groups₆~ C₆₀Aryl group; And hydrogen, deuterium, tritium, halogen group, amino group, nitrile group, nitro group, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₃~ C₃₀Cycloalkyl group, C₂~ C₃₀Heterocycloalkyl group, C₆~ C₆₀Aryl group and C₂~ C₆₀C unsubstituted or substituted with a substituent selected from the group consisting of heterocyclic groups₆~ C₆₀An arylamine group; selected from the group consisting of remind R_One To R₄May each combine with a neighboring group to form a substituted or unsubstituted alicyclic, aromatic or heterocyclic ring,

   (3) n is an integer of 0 to 2, when n is 2, a plurality of R ₆ may be the same or different from each other, and adjacent R ₆ are bonded to each other to form a substituted or unsubstituted alicyclic, aromatic or heterocyclic ring Can form

   (4) L is nitro, nitrile, halogen, C_One~ C₂₀Alkyl group, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Aryl group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group and an amino group of₆~ C₆₀Arylene group; Hydrogen, deuterium, tritium, halogen, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C_One~ C₅₀Alkyl group, C₂~ C₂₀A fluorenylene group unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group; And Nitro, nitrile, halogen, C_One~ C₂₀Alkyl group, C_One~ C₂₀Alkoxy group C₆~ C₂₀Aryl group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group and an amino group of₃~ C₆₀Heteroarylene group is selected from the group consisting of,

   (5) Ar_One, Ar₂Is hydrogen, deuterium, tritium, halogen, C_One~ C₂₀Alkyl group, C_One~ C₂₀Alkoxy group, C_One~ C₂₀Alkylamine groups, C_One~ C₂₀Alkylthiophene groups, C₆~ C₂₀Arylthiophene group, C₂~ C₂₀Alkenyl, C₂~ C₂₀Alkynyl, C₃~ C₂₀Cycloalkyl group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₈~ C₂₀Aryl alkenyl group, silane group, boron group, germanium group and C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of heterocyclic groups₆~ C₆₀Aryl group; Hydrogen, deuterium, tritium, halogen, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Arylamine group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₂₀C which is unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group and includes at least one heteroatom of O, N, S, Si and P₂~ C₆₀Heterocyclic group of; Hydrogen, deuterium, tritium, halogen, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Arylamine group, C₆~ C₆₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group₂~ C₂₀Alkenyl group; Hydrogen, deuterium, tritium, halogen, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C₂~ C₂₀C unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group_One~ C₅₀Alkyl groups; Hydrogen, deuterium, tritium, halogen group, amino group, nitrile group, nitro group, C_One~ C₂₀Alkyl group, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₃~ C₃₀Cycloalkyl group, C₂~ C₃₀Heterocycloalkyl group, C₆~ C₆₀Aryl group, C₂~ C₆₀C unsubstituted or substituted with a substituent selected from the group consisting of heterocyclic groups₆~ C₆₀Arylamine group; And hydrogen, deuterium, tritium, halogen, C₂~ C₂₀Alkenyl, C_One~ C₂₀Alkoxy group, C₆~ C₂₀Aryl group of C, substituted with deuterium₆~ C₂₀Aryl group, C₇~ C₂₀Arylalkyl group, C₈~ C₂₀Aryl alkenyl group, C_One~ C₅₀Alkyl group, C₂~ C₂₀A fluorene group unsubstituted or substituted with a substituent selected from the group consisting of a heterocyclic group, a nitrile group and an acetylene group, wherein the substituents of the fluorene group may be bonded to each other to form a ring if possible; Is selected from, Ar_OneAnd Ar₂ Each may combine with adjacent groups to form a substituted or unsubstituted alicyclic, aromatic or heterocycle.
2. The method of claim 1,

   B in Chemical Formula 1 is one of the following chemical formulas.

   

   (In the formula, R ', R ", R 5 are each of the formula R', R" are the same and, R _5, * denotes a ring condensed portion adjacent)
3. The method of claim 1,

   Compound which is one of the following compounds.

   

   

   
4. An organic electric device comprising a first electrode sequentially stacked, at least one organic material layer containing the compound of any one of claims 1 to 3, and a second electrode.
5.  The method of claim 4, wherein

   An organic electric device, characterized in that to form the compound to the organic material layer by a solution process.
6. The method of claim 4, wherein

   The organic material layer is an organic electroluminescent device comprising at least one of a hole injection layer, a hole transport layer, a light emitting auxiliary layer, a light emitting layer, an electron transport layer and an electron injection layer.
7. Claim 4 display device comprising the organic electroluminescent element; And

   And a controller for driving the display device.
8. The method of claim 7, wherein

   The organic electroluminescent device is at least one of an organic electroluminescent device (OLED), an organic solar cell, an organic photoconductor (OPC), an organic transistor (organic TFT), and a device for monochrome or white illumination.

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