KR101317511B1 - New compounds and organic electronic device using the same - Google Patents

Abstract

The present invention provides a novel compound and an organic electronic device using the same. The compound according to the present invention can perform hole injection, hole transport, electron injection and transport, and a light emitting material in an organic electronic device including an organic light emitting device, and the organic electronic device according to the present invention can improve efficiency, .

Compound, organic electronic device, organic light emitting device, organic light emitting device material

Description

TECHNICAL FIELD [0001] The present invention relates to a novel compound, and an organic electronic device using the same. BACKGROUND OF THE INVENTION [0002]

The present invention relates to a novel compound and an organic electronic device using the same.

In the present specification, an organic electronic device is an electronic device using an organic semiconductor material, which requires an exchange of holes and / or electrons between the electrode and the organic semiconductor material.

The organic electronic device can be roughly classified into two types according to the operating principle as described below. First, an exciton is formed in an organic material layer by a photon introduced into an element from an external light source. The exciton is separated into an electron and a hole, and the electrons and holes are transferred to different electrodes to be used as a current source Is an electronic device. The second type is an electronic device that injects holes and / or electrons into an organic semiconductor material layer that interfaces with the electrode by applying a voltage or current to two or more electrodes, and operates by injected electrons and holes.

Examples of organic electronic devices include organic light emitting devices, organic solar cells, organic photoconductor (OPC) drums, and organic transistors, all of which are electron / hole injection materials, electron / hole extraction materials, and electron / hole transport materials for driving the devices. Materials or luminescent materials are required. Hereinafter, the organic light emitting device will be described in detail, but in the organic electronic devices, the electron / hole injecting material, the electron / hole extracting material, the electron / hole transporting material, or the light emitting material all have a similar principle.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic layer between them. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between two electrodes in the structure of the organic light emitting device, holes are injected into the anode, electrons are injected into the organic layer, electrons are injected into the organic layer, excitons are formed when injected holes and electrons meet, When it falls to a state, it becomes a light. Such an organic light emitting device is known to have characteristics such as self-emission, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high speed response.

A material used as an organic material layer in an organic light emitting device can be classified into a light emitting material and a charge transporting material such as a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on functions. The luminescent material has blue, green and red luminescent materials and yellow and orange luminescent materials necessary for realizing a better natural color depending on the luminescent color. In addition, in order to increase luminous efficiency through increase in color purity and energy transfer, a host / dopant system may be used as the light emitting material. The principle is that when a small amount of dopant having a smaller energy band gap and a higher luminous efficiency than a host mainly constituting the light emitting layer is mixed with the light emitting layer in a small amount, the excitons generated in the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host is shifted to the wavelength band of the dopant, the desired wavelength light can be obtained depending on the type of the dopant used.

In order to sufficiently exhibit the excellent characteristics of the organic light emitting device, a material constituting the organic material layer in the device such as a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material and an electron injecting material is supported by a stable and efficient material However, the development of a stable and efficient organic material layer material for an organic light emitting device has not yet been sufficiently achieved, and therefore, the development of new materials has been continuously required.

The present invention is to solve the problems of the prior art as described above, an object of the present invention when forming an organic material layer of an organic electronic device is a novel that can exhibit the effects of the efficiency of the device, the driving voltage drop and the stability increase To provide a compound.

Still another object of the present invention is to provide an organic electronic device using the compound.

One aspect of the present invention for achieving the above object provides a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R1 and R2 are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₂ to C ₁₂ alkenyl group, a substituted or unsubstituted A substituted C ₃ to C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₅ to C ₂₀ cycloalkenyl group, a substituted or unsubstituted C ₆ to C ₃₀ arylamino group, a substituted or unsubstituted C ₆ to C ₃₀ Is an aryl group, a substituted or unsubstituted C ₃ to C ₃₀ heteroaryl group having O, N or S as a hetero atom,

Ar ₁ to Ar ₆ are the same as or different from each other, at least one of them is a substituent represented by the following formula (2) or (3), the rest are each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C ₁ ~ C ₃₀ An alkyl group, a substituted or unsubstituted C ₂ to C ₁₂ alkenyl group, a substituted or unsubstituted C ₃ to C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₅ to C ₂₀ cycloalkenyl group, a substituted or unsubstituted C ₆ ~ C ₃₀ arylamino group, substituted or unsubstituted C ₆ ~ C ₃₀ aryl group and substituted or unsubstituted and C ₃ ~ C ₃₀ heteroaryl group having O, N or S in the heteroaryl group Is a substituent selected,

       [Chemical Formula 2] < EMI ID =

In the above Formulas 2 and 3,

n, p, and m are integers from 0 to 4, n and p are not 0 at the same time,

R ₃ is a hydrogen atom, a deuterium atom, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₂ -C ₂₀ alkenyl group, a substituted or unsubstituted C ₃ -C ₂₀ cycloalkyl group , Substituted or unsubstituted C ₅ ~ C ₃₀ cycloalkenyl group, substituted or unsubstituted C ₁ ~ C ₃₀ alkoxy group, substituted or unsubstituted C ₆ ~ C ₂₀ aryloxy group, substituted or unsubstituted C ₁ ~ C ₃₀ Alkylthioxy group, substituted or unsubstituted C ₅ ~ C ₂₀ Arylthioxy group, substituted or unsubstituted C ₁ ~ C ₃₀ Alkylamine group, substituted or unsubstituted C ₅ ~ C ₃₀ Arylamine group, substituted or unsubstituted C ₆ ~ C ₃₀ aryl group, substituted or unsubstituted C ₃ ~ C ₃₀ heteroaryl group having O, N or S as a hetero atom, substituted or unsubstituted boron group Substituted or unsubstituted silane, carbonyl, phosphoryl, amino, nitrile, nitro, hydroxy, halogen, amide and ester groups And when m is an integer of 2 or more, the two or more R ₃ may be the same or different from each other, and may form a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero group with adjacent groups, or form a spiro bond. Can be achieved.

A second aspect of the present invention for achieving the above object provides a method for preparing the compound.

The third aspect of the present invention for achieving the above object provides an organic electronic device comprising the compound.

The novel compounds according to the present invention can be used as organic material layers of organic electronic devices including organic light emitting devices by introducing various alkyl groups, aryl groups, heteroaryl groups, arylamine groups, arylcarbonyl groups, arylphosphoryl groups, and the like. . The organic electronic device including the organic light emitting device using the compound according to the present invention as a material of the organic material layer exhibits excellent characteristics in efficiency, driving voltage, lifetime, and the like.

Hereinafter, the present invention will be described more specifically.

One aspect of the present invention relates to a compound represented by Chemical Formula 1.

In the compound according to the present invention, the substituents of the above formula (1) will be described in more detail as follows.

The alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 12. Specific examples include, but are not limited to, methyl, ethyl, propyl, isopropyl, butyl, t-butyl, pentyl, hexyl and heptyl.

The alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 12. Specific examples thereof include, but are not limited to, an alkenyl group having an aryl group such as a stilbenyl group or a styrenyl group.

The cycloalkyl group preferably has 3 to 12 carbon atoms and does not give steric hindrance. Specific examples thereof include, but are not limited to, a cyclopentyl group, a cyclohexyl group, and the like.

The cycloalkenyl group preferably has 3 to 12 carbon atoms, and more particularly, a cyclic compound having ethenylene in a pentagonal or hexagonal ring, and the like, but is not limited thereto.

The alkoxy group preferably has 1 to 12 carbon atoms, more specifically methoxy, ethoxy, phenyloxy, cyclohexyloxy, naphthyloxy, isopropyloxy, diphenyloxy, and the like, but is not limited thereto. It is not.

The substituted or unsubstituted C ₅ ~ C ₃₀ amine group is independently in the form of -N (Z 1) (Z 2) Z 1 and Z 2 is a substituted unsubstituted C ₁ -C ₅₀ alkyl group, substituted unsubstituted C ₂ -C ₅₀ alkenyl group, substituted unsubstituted C ₅ -C ₅₀ cycloalkyl group, substituted unsubstituted C ₅ -C ₅₀ cycloalkenyl group, substituted unsubstituted C ₅ -C ₅₀ heterocycloalkyl group, substituted unsubstituted C _6- C ₅₀ aryl group, substituted unsubstituted C ₂ -C ₅₀ Heteroaryl group;

In the arylamine group, the aryl group preferably has 5 to 30 carbon atoms, and more specifically, a diphenylamine group, a phenylnaphthylamine group, a phenylbiphenylamine group, a naphthylbiphenylamine group, and a dinaphthylamine group. , Dibiphenylamine group, dianthracenylamine group, 3-methyl-phenylamine group, 4-methyl-naphthylamine group, 2-methyl-biphenylamine group, 9-methyl-anthracenylamine group, ditolyl amine Group, a phenyl tolyl amine group, a triphenylaminophenyl amine group, a phenyl biphenylamino phenyl amine group, a naphthyl phenylaminophenyl biphenylamine group, etc. are mentioned, but it is not limited to this.

The aryl group may be monocyclic or polycyclic, and the number of carbon atoms is not particularly limited, but is preferably 6 to 30. Examples of the monocyclic aryl group include phenyl group, biphenyl group, terphenyl group, stilbene, and the like. Examples of the polycyclic aryl group include naphthyl group, anthracenyl group, phenanthrene group, pyrenyl group, perrylenyl group, and cryo. But may be exemplified, but is not limited thereto.

The heteroaryl group is a cyclic group containing hetero atoms such as O, N or S, and the number of carbon atoms is not particularly limited, but is preferably 3 to 30 carbon atoms. Examples of the heterocyclic group include a carbazole group, a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a pyridazine group, a quinolinyl group, an isoquinoline group , Acridil group and the like, but is not limited thereto.

Examples of the halogen group include, but are not limited to, fluorine, chlorine, bromine, and iodine.

Substituents which may be substituted with Ar ₁ to Ar ₆ , R 1 and R 2 of Formula 1 may include deuterium, a halogen atom, a carbonyl group, an ester group, a phosphoryl group, an imide group, an amino group, a nitro group, a cyano group, a hydroxy group, an alkyl group, Alkoxy group, arylthioxy group, alkylthioxy group, alkylamine group, aralkylamine group, arylamine group, alkenyl group, cycloalkyl group, cycloalkenyl group, silane group, boron group, C ₆ ~ C ₃₀ aryl group, C _And a heteroaryl group of ₃ to C ₃₀ , but are not limited thereto.

In the compound according to the present invention, the compound represented by Chemical Formula 1 may be represented by one of the following Chemical Formulas 4 to 7.

In Formulas 4 to 7, R 1, R ₂ , Ar ₁ , Ar ₂ , Ar ₄ , Ar _5, and Ar ₆ are the same as the descriptions of Formula 1 above.

When the compound represented by Formula 1 is represented by Formula 6, Ar ₆ is represented by Formula 2 or Formula 3, Ar ₄ Is a substituted or unsubstituted C ₁ to C ₂₀ alkyl group, a substituted or unsubstituted C ₅ to C ₃₀ arylamino group, a substituted or unsubstituted C ₃ to C ₅₀ heteroaryl group, a substituted or unsubstituted phenyl group, Or a C ₁₀ to C ₅₀ aryl group substituted with substituted or unsubstituted F to CN.

In Formulas 4 to 7, Ar ₁ , Ar ₂ and Ar ₄ are each independently a substituted or unsubstituted C ₁ ~ C ₂₀ Alkyl group, a substituted or unsubstituted C ₂ ~ C ₂₀ Alkenyl group, a substituted or Unsubstituted C ₅ to C ₃₀ arylamine group, substituted or unsubstituted C ₆ to C ₃₀ aryl group, substituted or unsubstituted C ₃ to C ₃₀ heteroaryl group having O, N or S as a hetero atom , A substituted or unsubstituted boron group, a substituted or unsubstituted silane group, and the like.

Specific examples of the compound represented by the formula (1) include, but are not limited to, the following compounds.

The second aspect of the present invention relates to a method for preparing the compound represented by Chemical Formula 1.

The method for preparing a compound represented by Chemical Formula 1 includes preparing an Chemical Formula 1 by suzuki coupling an arylboronic acid compound or an arylboronate compound with a halogenated aryl compound under a palladium (Pd) catalyst. It is characterized by.

Thomson of the University of Southern California investigated the absorption and phosphorescence of Pt (II) complexes with rectangular planar structure. In particular, in order to make a phosphorescent dopant having a short wavelength, Fluoro atoms were introduced into an aryl group to obtain a blue dopant.

The maximum emission wavelength of ppy is 477 nm, the maximum emission wavelength of 6Fppy is 468 nm, and the maximum emission wavelength of 46 dfppy is 458 nm. The emission wavelength is shifted to the short wavelength region by introduction of F atoms (blue-shift). Accordingly, the present invention is to develop a short wavelength blue light emitting material by using the property of increasing the band gap of the compound under the influence of F atoms. As a result, the compounds represented by Chemical Formula 1 having the compounds represented by Chemical Formula 2 and Chemical Formula 3 as substituents may exhibit a shorter wavelength blue light emitting region than the compound represented by Chemical Formula 1 not containing a Fluoro atom.

The compound represented by Chemical Formula 1 may have properties suitable for use as an organic material layer used in an organic light emitting device by introducing various substituents into the core structure represented by Chemical Formula 1. The compound represented by Chemical Formula 1 may exhibit properties in any layer of the organic light emitting device, but may exhibit the following properties in particular.

Compounds in which substituted or unsubstituted arylamine groups are introduced are suitable as light emitting layer, hole injection and hole transport layer materials, and when heterocyclic ring substituents containing N are introduced, they are suitable as electron injection, electron transport layer and hole blocking layer materials. .

The conjugation length of the compound and the energy band gap are closely related. Specifically, the longer the conjugation length of the compound, the smaller the energy bandgap. As described above, since the core of the compound represented by Chemical Formula 1 includes limited conjugation, it has a property from small to large energy bandgap.

Further, by introducing various substituents into the core structure having the above structure, it is possible to synthesize a compound having the intrinsic characteristics of the substituent introduced. For example, the hole injection layer material and the hole transport layer material used in manufacturing the organic light emitting device have an energy level sufficient to transfer holes along the highest occupied molecular orbital (HOMO), and the low unoccupied molecular orbital (LUMO) from the light emitting layer. It can be a compound that can have an energy level enough to block the electrons coming along. Particularly, the core structure of the present compound exhibits stable characteristics in terms of electrons, which can contribute to improvement of lifetime of the device. The derivatives prepared by introducing the substituents to be used for the light emitting layer and the electron transporting layer material can be manufactured to have appropriate energy band gaps for various arylamine type dopants, aryl type dopants, metal containing dopants and the like.

In addition, by introducing a variety of substituents in the core structure it is possible to finely control the energy band gap, on the other hand to improve the properties at the interface between the organic material and to vary the use of the material.

On the other hand, the compound represented by the formula (1) has a high glass transition temperature (Tg) and is excellent in thermal stability. This increase in thermal stability is an important factor in providing drive stability to the device.

A third aspect of the present invention relates to an organic electronic device comprising the compound represented by the formula (1).

The organic electronic device according to the present invention is an organic electronic device including a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers is the chemical formula It is characterized by including the compound of 1.

The organic electronic device of the present invention may be manufactured by a conventional method and material for manufacturing an organic electronic device, except that at least one organic water layer is formed using the above-described compounds.

The compound of Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method in manufacturing an organic electronic device. Here, the solution coating method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

The organic material layer of the organic electronic device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic electronic device of the present invention may have a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, and the like as an organic material layer. However, the structure of the organic electronic device is not limited to this, and may include a smaller number of organic layers.

Accordingly, in the organic electronic device of the present invention, the organic material layer may include a hole injection layer and a hole transport layer, and the hole injection layer and the hole transport layer may include the compound represented by the above formula (1).

In addition, the organic layer may include a light emitting layer, and the light emitting layer may include a compound represented by the general formula (1).

In the organic layer having such a multi-layer structure, the compound of Formula 1 may be included in a light emitting layer, a layer that simultaneously transports holes and holes, a layer that simultaneously transports holes and light, or a layer that simultaneously transports electrons and emits light.

For example, the structure of the organic light emitting device of the present invention may have a structure as shown in Figs. 1 to 4, but is not limited thereto.

FIG. 1 illustrates a structure of an organic light emitting device in which an anode 102, a light emitting layer 105, and a cathode 107 are sequentially stacked on a substrate 101. In such a structure, the compound of Formula 1 may be included in the light emitting layer 105.

2 illustrates a structure of an organic light emitting device in which an anode 102, a hole injection / hole transporting and light emitting layer 105, an electron transporting layer 106, and a cathode 107 are sequentially stacked on a substrate 101. In such a structure, the compound of Formula 1 may be included in the hole injection / hole transporting and light emitting layer 105.

3 shows a structure of an organic light emitting device in which a substrate 101, an anode 102, a hole injecting layer 103, a hole transporting and emitting layer 105, an electron transporting layer 106, and a cathode 107 are sequentially stacked. . In such a structure, the compound of Formula 1 may be included in the hole injection / hole transporting and light emitting layer 105.

4 shows a structure of an organic light emitting device in which a substrate 101, an anode 102, a hole injecting layer 103, a hole transporting layer 104, an electron transporting and emitting layer 105, and a cathode 107 are sequentially laminated. . In such a structure, the compound of Formula 1 may be included in the electron transporting and light emitting layer 105.

For example, the organic light emitting device according to the present invention uses a metal vapor deposition (PVD) method such as sputtering or e-beam evaporation, and has a metal oxide or a metal oxide or an alloy thereof on a substrate. It can be prepared by depositing an anode to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to such a method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

The organic material layer may have a multi-layer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. The organic material layer may be formed using a variety of polymeric materials by a method such as a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, Layer.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methyl compounds), poly [3,4- (ethylene-1,2-dioxy) compounds] (PEDT), polypyrrole and polyaniline.

The negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto.

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene , An anthraquinone, and a conductive polymer of polyaniline and a poly-compound, but the present invention is not limited thereto.

As the hole transporting material, a material capable of transporting holes from the anode or the hole injection layer to be transferred to the light emitting layer is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

As the electron transporting material, a material capable of transferring electrons from the cathode well into the light emitting layer, which is suitable for electrons, is suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto.

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

The compound according to the present invention may act on a principle similar to that applied to organic light emitting devices in organic electronic devices including organic solar cells, organic photoconductors, organic transistors and the like.

Accordingly, the organic electronic device may be selected from the group consisting of an organic light emitting device, an organic phosphor device, an organic solar cell, an organic photoconductor (OPC), and an organic transistor.

Hereinafter, the method for preparing the compound represented by the formula (1) of the present invention, the method for producing the organic electronic device using the same, and the performance will be described in detail. However, the following examples are for illustrative purposes only, and the scope of the present invention is not limited by the following examples.

The evaluation method in the examples is as follows.

1. Driving voltage: measured using Kethley 236 (source measure unit)

2. Current efficiency: measured using SpectraScan Pr-650

3. Color Coordinates: Measured using SpectraScan Pr-650

The compound represented by formula (1) according to the present invention can be generally prepared by a multistage chemical reaction. That is, some of the intermediate compounds are first prepared, and the compounds of formula (1) are prepared from the intermediate compounds. Exemplary intermediate compounds are compounds such as compounds 1A, 1B, 1C, 2B, 2C, 3A, 3B, 3C, 4A, 4B shown in the following synthesis examples.

Hereinafter, preferred embodiments of the present invention will be described in order to facilitate understanding of the present invention. However, the following examples are intended to illustrate the invention and are not intended to limit the scope of the invention.

< Manufacturing example >

< Manufacturing example  1> Preparation of Compound 1-1-1

9- (naphthalen-5-yl) anthracen-10-yl-10-boronic acid (7.0 g, 20.0 mmol), 1-bromo-4-fluorobenzene (3.4 g, 20.0 mmol) and sodium carbonate (5.0 g, 35.9 mmol) Was suspended in a mixture of tetrahydrofuran (300 mL) and water (100 mL). Tetrakis (triphenylphosphine) palladium (0.4 g, 0.36 mmol) was added to the suspension. The mixture was stirred at reflux for about 6 hours and then cooled to room temperature. The resulting solution was extracted, dried over anhydrous magnesium sulfate, the solvent was distilled off and the solid formed was purified by filtered CH ₂ Cl ₂ / EtOH to prepare compound 1-1-1 (6.8 g, yield 86%). MS: [M + H] ⁺ = 399

< Manufacturing example  2> Preparation of Compound 1-1-5

In Preparation Example of Compound 1-1-1 of Preparation Example 1, instead of 1-bromo-4-fluorobenzene, 1-bromo-2,3,4,5,6-pentafluorobenzene (4.9 g, 20.0 mmol) was added. Compound 1-1-5 (6.3 g, yield 67%) was prepared by reacting in the same manner except using. MS: [M + H] ⁺ = 471

< Manufacturing example  3> Preparation of Compound 1-2-31

In the preparation of Compound 1-1-1 of Preparation Example 1, 9- (1-fluoronaphthalen-4-yl) anthracen instead of 9- (naphthalen-5-yl) anthracen-10-yl-10-boronic acid -10-yl-10-boronic acid (7.3 g, 20.0 mmol) was used, and 1-bromo-2,3,4,5,6-pentafluorobenzene (4.9 g, 20.0 mmol) instead of 1-bromo-4-fluorobenzene Reaction was carried out in the same manner except using) to prepare compound 1-2-31 (8.0 g, 82% yield). MS: [M + H] ⁺ = 489

Preparation Example 4 Preparation of Compound 1-2-9

In the preparation of Compound 1-1-1 of Preparation Example 1, 9- (1-fluoronaphthalen-4-yl) anthracen instead of 9- (naphthalen-5-yl) anthracen-10-yl-10-boronic acid -10-yl-10-boronic acid (7.3 g, 20.0 mmol) was used and the same except 1- (4-bromophenyl) naphthalene (5.7 g, 20.0 mmol) was used instead of 1-bromo-4-fluorobenzene. Reaction was carried out to prepare a compound 1-2-9 (6.9 g, yield 66%). MS: [M + H] &lt; ⁺ &gt; = 525

< Manufacturing example  5> Preparation of Compound 1-2-11

In Preparation Example 1-1 of the compound of Preparation Example 1, 9- (1-fluoronaphthalen-4-yl) anthracen instead of 9- (naphthalen-5-yl) anthracen-10-yl-10-boronic acid -10-yl-10-boronic acid (7.3 g, 20.0 mmol) was used and the same except that 2- (4-bromophenyl) naphthalene (5.7 g, 20.0 mmol) was used instead of 1-bromo-4-fluorobenzene. Reaction was carried out to prepare compound 1-2-11 (6.9 g, 66% yield). MS: [M + H] &lt; ⁺ &gt; = 525

< Manufacturing example  6> Preparation of Compound 1-2-43

In the preparation of Compound 1-1-1 of Preparation Example 1, 9- (1-fluoronaphthalen-4-yl) anthracen instead of 9- (naphthalen-5-yl) anthracen-10-yl-10-boronic acid -10-yl-10-boronic acid (7.3 g, 20.0 mmol) was used, and 1- (4-bromophenyl) -4-fluoronaphthalene (6.0 g, 20.0 mmol) was used instead of 1-bromo-4-fluorobenzene. Except for the reaction in the same manner to give the compound 1-2-43 (8.5 g, yield 78%). MS: [M + H] ⁺ = 543

< Manufacturing example  7> Preparation of Compound 1-2-49

In the preparation of Compound 1-1-1 of Preparation Example 1, 9- (1-fluoronaphthalen-4-yl) anthracen instead of 9- (naphthalen-5-yl) anthracen-10-yl-10-boronic acid -10-yl-10-boronic acid (17.7 g, 44.0 mmol) was used, and 4,4,5,5-tetramethyl-2- (4- (4,4,5) instead of 1-bromo-4-fluorobenzene , 5-tetramethyl-1,3,2-dioxaborolan-2-yl) phenyl) -1,3,2-dioxaborolane (6.6 g, 20.0 mmol) was reacted in the same manner except using the compound 1-2-49 (8.5 g, yield 78%) was prepared. MS: [M + H] ⁺ = 543

< Manufacturing example  8> Preparation of Compound 1-3-11

In Preparation Example of Compound 1-1-1 of Preparation Example 1, instead of 9- (naphthalen-5-yl) anthracen-10-yl-10-boronic acid, 4- (naphthalen-1-yl) phenylboronic acid ( 5.0 g, 20.0 mmol) and 10-bromo-9- (1-fluoronaphthalen-2-yl) anthracene (8.0 g, 20.0 mmol) instead of 1-bromo-4-fluorobenzene The reaction was conducted to prepare compound 1-3-11 (5.1 g, 49% yield). MS: [M + H] &lt; ⁺ &gt; = 525

< Manufacturing example  9> Preparation of Compound 1-2-3

In Preparation Example of Compound 1-1-1 of Preparation Example 1, 9- (phenanthren-10-yl) anthracen-10 instead of 9- (naphthalen-5-yl) anthracen-10-yl-10-boronic acid Reaction was carried out in the same manner except that -yl-10-boronic acid (8.0 g, 20.0 mmol) was used and 1-bromo-4-fluoronaphthalene (4.5 g, 20.0 mmol) was used instead of 1-bromo-4-fluorobenzene. Compound 1-2-3 (8.3 g, yield 91%) was prepared. MS: [M + H] ⁺ = 499

< Manufacturing example  10> Preparation of Compound 1-5-25

In the preparation of Compound 1-1-1 of Preparation Example 1, 1- (phenanthren-9-yl) anthracen-10 instead of 9- (naphthalen-5-yl) anthracen-10-yl-10-boronic acid Reaction was carried out in the same manner except that -yl-10-boronic acid (7.9 g, 20.0 mmol) was used and 5-bromo-2-fluorobenzonitrile (4.0 g, 20.0 mmol) was used instead of 1-bromo-4-fluorobenzene. Compound 1-5-25 (5.6 g, 59% yield) was prepared. MS: [M + H] ⁺ = 474

< Manufacturing example  11> Preparation of Compound 1-1-162

In Preparation Example of Compound 1-1-1 of Preparation Example 1, 4- (9- (naphthalene-5-yl) instead of 9- (naphthalen-5-yl) anthracen-10-yl-10-boronic acid except that anthracen-10-yl) -2-fluorophenyl-1-pinacole boronic acid (10.5 g, 20.0 mmol) was used and 1-bromonaphthalene (4.1 g, 20.0 mmol) was used instead of 1-bromo-4-fluorobenzene. And reacted in the same manner to give compound 1-1-162 (6.3 g, 59% yield). MS: [M + H] &lt; ⁺ &gt; = 525

< Manufacturing example  12> Preparation of Compound 1-1-173

In Preparation Example of Compound 1-1-1 of Preparation Example 1, 4- (naphthalene-5-yl) -fluorophenyl- instead of 9- (naphthalen-5-yl) anthracen-10-yl-10-boronic acid Except for using 1-pinacole boronic acid (7.0 g, 20.0 mmol) and 9- (naphthalene-5-yl) -10-bromoanthracene (7.7 g, 20.0 mmol) instead of 1-bromo-4-fluorobenzene Reaction was carried out in the same manner to obtain Compound 1-1-173 (6.8 g, 65% yield). MS: [M + H] &lt; ⁺ &gt; = 525

< Manufacturing example  13> Preparation of Compound 1-1-177

In Preparation Example 1-1 of the compound of Preparation Example 1, 4- (5-methylthiophen-2-yl)-instead of 9- (naphthalen-5-yl) anthracen-10-yl-10-boronic acid 2-fluorophenyl-1-pinacole boronic acid (6.4 g, 20.0 mmol) was used, and 9- (naphthalene-5-yl) -10-bromoanthracene (7.7 g, 20.0 mmol) was used instead of 1-bromo-4-fluorobenzene. Compound 1-1-177 (6.7 g, yield 68%) was prepared by reacting in the same manner except using. MS: [M + H] ⁺ = 495

< Comparative Example  1-1>

The glass substrate coated with ITO (indium tin oxide) at a thickness of 1,500 kPa was placed in distilled water in which detergent was dissolved and ultrasonically cleaned. At this time, a product of Fischer Co. was used as a detergent, and distilled water filtered secondly as a filter of Millipore Co. was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. The substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

Hexanitrile hexaazatriphenylene was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer. NPB (400 kPa), which is a material for transporting holes, was vacuum deposited thereon, and the host H1 and the dopant D1 compound were vacuum deposited to a thickness of 300 kPa as a light emitting layer.

[Hexanitrile hexaazatriphenylene] [NPB]

Compound E1 was vacuum deposited to a thickness of 200 kPa on the light emitting layer to form an electron injection and transport layer. A cathode was formed by sequentially depositing 12 라이드 thick lithium fluoride (LiF) and 2,000 Å thick aluminum on the electron injection and transport layer. In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the deposition rate of lithium fluoride was 0.2 Å / sec, and the deposition rate of aluminum was 3 to 7 Å / sec.

< Comparative Example  1-2>

The same experiment was conducted except that the compound [H2] was used instead of the compound [H1] in Comparative Example 1-1.

< Comparative Example  1-3>

The same experiment was conducted except that the compound [H3] was used instead of the compound [H1] in Comparative Example 1-1.

< Experimental Example  1-1>

A glass substrate coated with ITO (indium tin oxide) having a thickness of 1,500 Å was placed in distilled water in which detergent was dissolved and ultrasonically cleaned. At this time, a product of Fischer Co. was used as a detergent, and distilled water filtered secondly as a filter of Millipore Co. was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. The substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

Hexanitrile hexaazatriphenylene was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer. NPB (400 kPa), which is a material for transporting holes, was vacuum-deposited, and then compound 1-1-1 prepared in Preparation Example 1 was vacuum-deposited to a light-emitting layer with a compound having a thickness of 300 kPa as a host, and doped with dopant D1. It was. The E1 was vacuum deposited to a thickness of 200 kPa on the light emitting layer to form an electron injection and transport layer. 12 Å thick lithium fluoride (LiF) and 2,000 Å thick aluminum were sequentially deposited on the electron transport layer to form a cathode, thereby manufacturing an organic light emitting device.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7 Å / sec, the lithium fluoride of the cathode was maintained at 0.3 Å / sec, the aluminum was maintained at a deposition rate of 2 Å / sec, the vacuum degree during deposition was 2 × 10 ⁻⁷ to 5 × 10 ⁻⁸ torr was maintained.

< Experimental Example  1-2>

Except for using the compound 1-1-5 instead of compound 1-1-1 in Experimental Example 1-1 and was the same experiment.

< Experimental Example  1-3>

Except for using the compound 1-2-31 instead of compound 1-1-1 in Experimental Example 1-1 and was the same experiment.

< Experimental Example  1-4>

Except for using the compound 1-2-9 instead of compound 1-1-1 in Experimental Example 1-1 and was the same experiment.

< Experimental Example  1-5>

Except for using the compound 1-2-11 instead of compound 1-1-1 in Experimental Example 1-1 was the same experiment.

< Experimental Example  1-6>

Except for using the compound 1-2-43 instead of compound 1-1-1 in Experimental Example 1-1 and was the same experiment.

< Experimental Example  1-7>

Except for using the compound 1-2-49 instead of compound 1-1-1 in Experimental Example 1-1 and was the same experiment.

< Experimental Example  1-8>

Except for using the compound 1-3-11 instead of compound 1-1-1 in Experimental Example 1-1 and was the same experiment.

< Experimental Example  1-9>

Except for using the compound 1-2-3 instead of compound 1-1-1 in Experimental Example 1-1 and was the same experiment.

< Experimental Example  1-10>

Except for using the compound 1-5-25 instead of compound 1-1-1 in Experimental Example 1-1 and was the same experiment.

< Experimental Example  1-11>

Except for using the compound 1-1-162 instead of compound 1-1-1 in Experimental Example 1-1 and was the same experiment.

< Experimental Example  1-12>

Except for using the compound 1-1-173 instead of compound 1-1-1 in Experimental Example 1-1 and was the same experiment.

< Experimental Example  1-13>

Except for using the compound 1-1-177 instead of compound 1-1-1 in Experimental Example 1-1 and was the same experiment.

Experimental results of the organic light emitting device manufactured by using the respective compounds as light emitting layers as in Experimental Examples 1-1 to 1-13 are shown in Table 1 below.

[Table 1]

As can be seen in Table 1, Experimental Examples 1-1 to 1-13 can be used as a blue light emitting layer, and exhibits superior characteristics in terms of voltage or efficiency than Comparative Examples 1 to 3, depending on appropriate substituents or positions of substituents. It was.

1 is an example of an organic light emitting device structure in which an anode 102, a light emitting layer 105, and a cathode 107 are sequentially stacked on a substrate 101.

2 illustrates an organic light emitting device structure in which an anode 102, a hole injection / hole transport and light emitting layer 105, an electron transport layer 106, and a cathode 107 are sequentially stacked on a substrate 101.

3 is an example of an organic light emitting device structure in which a substrate 101, an anode 102, a hole injection layer 103, a hole transport and light emitting layer 105, an electron transport layer 106 and a cathode 107 are sequentially stacked. .

4 is an example of an organic light emitting device structure in which a substrate 101, an anode 102, a hole injection layer 103, a hole transport layer 104, an electron transporting and emitting layer 105, and a cathode 107 are sequentially stacked. .

Claims (10)

A compound represented by any one of the following formulas 4-7:

In Chemical Formulas 4 to 7, R1 and R2 are the same as or different from each other, and each independently a hydrogen atom, a deuterium atom, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted C ₂ to C ₁₂ alkenyl group, a substituted or unsubstituted Of a substituted C ₃ to C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₅ to C ₂₀ cycloalkenyl group, a substituted or unsubstituted C ₆ to C ₃₀ arylamino group, a substituted or unsubstituted C ₆ to C _{30 group} An aryl group, a substituted or unsubstituted C ₃ to C ₃₀ heteroaryl group having O, N or S as a hetero atom, Ar ₁ and Ar ₂ in Formula 4 are different from each other, at least one of them is a substituent represented by the following formula (2) or (3), [Formula 2] [Formula 3]

Ar ₁ and Ar ₆ in Formula 5 are different from each other, at least one is a substituent represented by Formula 2 or Formula 3, In Formula 6 is Ar ₁ or Ar ₆ and Ar ₄ or more different and each is a double one substituent represented by the formula (2) or (3), Ar ₅ and Ar ₆ in Formula 7 are different from each other, at least one of them is a substituent represented by Formula 2 or Formula 3, In the above Chemical Formulas 4 to 7, the remainder not represented by Chemical Formula 2 or Chemical Formula 3 in Ar ₁ to Ar ₆ may each independently represent a hydrogen atom, a deuterium atom, a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, a substituted or unsubstituted group. A substituted C ₂ to C ₁₂ alkenyl group, a substituted or unsubstituted C ₃ to C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₅ to C ₂₀ cycloalkenyl group, a substituted or unsubstituted C ₆ to C ₃₀ An arylamino group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, and a substituent selected from the group consisting of a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group having O, N or S as a hetero atom, In the above Formulas 2 and 3, n, p, and m are integers from 0 to 4, n and p are not 0 at the same time, R ₃ is a hydrogen atom, a deuterium atom, a substituted or unsubstituted C ₁ to C ₂₀ alkyl group, a substituted or unsubstituted C ₂ to C ₂₀ alkenyl group, a substituted or unsubstituted C ₃ to C ₂₀ cycloalkyl group, Substituted or unsubstituted C ₅ to C ₃₀ cycloalkenyl group, substituted or unsubstituted C ₁ to C ₃₀ alkoxy group, substituted or unsubstituted C ₆ to C ₂₀ aryloxy group, substituted or unsubstituted C ₁ to C ₃₀ alkylthioxy group, substituted or unsubstituted C ₅ to C ₂₀ arylthioxy group, substituted or unsubstituted C ₁ to C ₃₀ alkylamine group, substituted or unsubstituted C ₅ to C ₃₀ An arylamine group, a substituted or unsubstituted C ₆ -C ₃₀ aryl group, a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group having O, N or S as a hetero atom, a substituted or unsubstituted boron group, Substituted or unsubstituted silane group, carbonyl group, phosphoryl group, amino group, nitrile group, nitro group, hydroxy group, halogen group, amide group and ester group And when m is an integer of 2 or more, the two or more R ₃ may be the same or different from each other, and may form a condensed ring of an aliphatic, aromatic, aliphatic hetero or aromatic hetero group with adjacent groups, or form a spiro bond. Can be achieved. delete The method according to claim 1, wherein in the compound represented by the formula (6), Ar ₆ is a substituent represented by the formula (2) or formula (3), wherein Ar ₄ is a substituted or unsubstituted C ₁ ~ C ₂₀ Alkyl group, substituted or unsubstituted A substituted C ₅ to C ₃₀ arylamino group, a substituted or unsubstituted C ₃ to C ₅₀ heteroaryl group and a substituted C ₁₀ to C ₅₀ aryl group unsubstituted or substituted with F to CN. The method according to claim 1, Ar ₁ , Ar ₂ and Ar ₄ are each independently a substituted or unsubstituted C ₁ ~ C ₂₀ Alkyl group, a substituted or unsubstituted C ₂ ~ C ₂₀ Alkenyl group, a substituted or unsubstituted C ₅ ~ C ₃₀ arylamine group, substituted or unsubstituted C ₆ ~ C ₃₀ aryl group, substituted or unsubstituted C ₃ ~ C ₃₀ heteroaryl group having O, N or S, hetero or And an unsubstituted boron group and a substituted or unsubstituted silane group. The compound of claim 1, wherein the compound represented by Chemical Formulas 4 to 7 is represented by the following chemical formula:

A method for producing a compound according to any one of claims 1 and 3 to 5, comprising the step of suzuki coupling the arylboronic acid-based or arylboronate-based compound with a halogenated aryl compound under a palladium (Pd) catalyst. An organic electronic device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers is any one of claims 1 and 3 to 5. An organic electronic device comprising a compound represented by the formula (4) to 7 described in claim. The compound of claim 7, wherein the organic material layer comprises at least one layer of a hole injection layer, a hole transport layer, and a layer simultaneously performing hole injection and hole transport, wherein one of the layers is represented by Formulas 4 to 7 An organic electronic device comprising a. The organic electronic device according to claim 7, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes a compound represented by Chemical Formulas 4 to 7. The organic electronic device according to claim 7, wherein the organic material layer includes an electron transport layer, and the electron transport layer comprises a compound represented by Chemical Formulas 4 to 7.

Images