KR20140034892A - Organic light-emitting compound and organic electroluminescent device using the same - Google Patents

Abstract

The present invention relates to a novel cyclic compound in a closed ring structure having excellent hole injection and transfer efficiency and light emitting capacity, and containing one or more carbazol based rings in a molecule; and to an organic electroluminescent device with an improved luminance efficiency, driving voltage and lifetime by containing the cyclic compound in one or more organic layers.

Description

Organic light emitting compound and organic electroluminescent device using the same {ORGANIC LIGHT-EMITTING COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE USING THE SAME}

The present invention relates to a novel organic light emitting compound and an organic electroluminescent device using the same. More particularly, the present invention relates to a novel compound having excellent hole injection and transport ability, And lifetime of the organic electroluminescent device.

A study on organic electroluminescent (EL) devices (hereinafter simply referred to as "organic EL devices") led to blue electroluminescence using anthracene single crystals in 1965 based on observation of organic thin film luminosity of Bernanose in the 1950s, (Tang) and a functional layer of a light emitting layer. In order to produce high efficiency and high number of organic EL devices, the organic EL device has been developed to introduce each characteristic organic material layer in the device, leading to the development of specialized materials used therefor.

In the organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the anode, and electrons are injected into the organic layer from the cathode. When the injected holes and electrons meet, an exciton is formed. When the exciton falls to the ground state, light is emitted. The material used as the organic material layer may be classified into a light emitting material, a hole injecting material, a hole transporting material, an electron transporting material, and an electron injecting material depending on its function.

The light emitting layer forming material of the organic EL device can be classified into blue, green and red light emitting materials depending on the luminescent color. In addition, yellow and orange light emitting materials are also used as light emitting materials for realizing better color. Further, in order to increase the color purity and increase the luminous efficiency through energy transfer, a host / dopant system can be used as a light emitting material. The dopant material can be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. The development of such phosphorescent materials can theoretically improve luminous efficiency up to 4 times compared to fluorescence, and thus, attention has been focused on phosphorescent dopants as well as phosphorescent host materials.

Up to now, hole injecting layer, hole transporting layer. As the hole blocking layer and the electron transporting layer, NPB, BCP and Alq ₃ represented by the following formulas are widely known, and an anthracene derivative as a luminescent material has been reported as a fluorescent dopant / host material. Particularly, phosphorescent materials having great advantages in terms of efficiency improvement among light emitting materials include metal complex compounds containing Ir such as Firpic, Ir (ppy) ₃ , and (acac) Ir (btp) _2, such as blue, green, and red dopant materials. Is being used. So far, CBP has shown excellent properties as a phosphorescent host material.

However, existing materials have advantages in terms of luminescence properties, but the glass transition temperature is low and the thermal stability is very poor, and thus the materials are not satisfactory in terms of lifespan in organic EL devices.

The present invention can be applied to an organic electroluminescent device, and an object of the present invention is to provide a novel organic compound having excellent hole injection, transporting ability, light emitting ability, and the like.

It is another object of the present invention to provide an organic electroluminescent device including the novel organic compound and exhibiting a low driving voltage and a high luminous efficiency and having an improved lifetime.

In order to accomplish the above object, the present invention relates to a carbazole ring system comprising at least one carbazole ring in a molecule; Or one or more carbazole-based rings and one or more linking groups, wherein the at least one carbazole-based ring or the carbazole-based ring and the linking group are bonded to each other to form a closed cyclic structure, and the molecular weight is 500 ≪ / RTI > to < RTI ID = 0.0 > 3000. ≪ / RTI >

Here, the linker may use a conventional linker, i.e., a divalent group of functional groups known in the art.

The present invention also provides an organic electroluminescent device comprising at least one organic material layer interposed between (i) an anode, (ii) a cathode, and (iii) an anode and a cathode, wherein at least one of the one or more organic layers One of the organic electroluminescent devices includes the cyclic compound.

At this time, the compound may be used as a phosphorescent host or a hole transport layer of the light emitting layer.

The compound of the present invention can exhibit excellent heat resistance, hole injection and transport ability, and light emitting ability

Therefore, an organic EL device including the above compound as a phosphorescent / fluorescent host or dopant in a hole injection / transport layer or a light emitting layer can be greatly improved in terms of light emitting performance, driving voltage, lifetime, efficiency, Can be effectively applied.

Hereinafter, the present invention will be described in detail.

<Novel compound>

Conventional biomimetic molecules, such as phthalocyanine or porphyrin derivatives, are typical structures of dyes or pigments. Compounds having such a closed ring-like molecular structure are thermochemical and electrochemical stable. Therefore, they are the most ideal form of the material in a device where an oxidation-reduction reaction is repeated like an OLED.

Thus, the present invention has the above-mentioned molecular structure in the form of a closed loop, and has a higher molecular weight than conventional organic EL device materials (for example, 4,4-dicarbazolybiphenyl (hereinafter referred to as CBP) Lt; RTI ID = 0.0 &gt; and / or &lt; / RTI &gt;

The novel compounds according to the present invention comprise at least one carbazole ring in the molecule; Or one or more carbazole-based rings and at least one linking group, and the at least one carbazole-based ring or the carbazole-based ring and the linking group are bonded to each other to form a closed cyclic structure. Due to such a molecular structure, stability can be shown thermochemically and electrochemically.

Further, the cyclic compound has a wide band gap (sky blue to red) by controlling the energy level by introducing various substituents into one molecular structure. As a result, it is possible to improve the phosphorescence characteristics of the device and improve the electron and / or hole transporting ability, luminous efficiency, driving voltage, lifetime characteristics, and the like. And the like.

On the other hand, since the molecular weight of the compound is significantly increased, the glass transition temperature is improved, and thus, it can have higher thermal stability than conventional CBP. Accordingly, the organic electroluminescent device including the compound of the present invention can greatly improve durability and lifetime characteristics. In particular, when the number of the carbazole groups forming the closed ring structure is large, the molecular weight is significantly increased and the closed ring structure is stabilized, so that the thermal stability of the compound can be enhanced.

In addition, when the compound of the present invention is used as a hole injecting / transporting layer of an organic electroluminescence (EL) device, a blue, green and / or red phosphorescent host material or a fluorescent host material, . Therefore, the compounds according to the present invention can greatly contribute to improvement of the performance and lifetime of the organic EL device.

The novel cyclic compound according to the present invention can be further compounded by any one of the compounds represented by the following general formulas (1) to (5).

Where

Ar ₁ to Ar ₄ are the same or different and each independently represents hydrogen, a substituted or unsubstituted C ₁ to C ₄₀ alkyl group, a substituted or unsubstituted C ₂ to C ₄₀ alkenyl group, a substituted or unsubstituted C ₂ ~ C ₄₀ of the alkynyl group, a substituted or unsubstituted C ₃ ~ C ₄₀ cycloalkyl group, a substituted or unsubstituted C of ₃ ~ C ₄₀ heterocycloalkyl group, a substituted or unsubstituted C ₆ ~ C ₆₀ unsubstituted aryl A substituted or unsubstituted C ₁ -C ₄₀ alkyloxy group, a substituted or unsubstituted C ₆ -C ₆₀ aryloxy group, a substituted or unsubstituted heteroaryl group having 5 to 60 ring atoms, An unsubstituted C ₁ to C ₄₀ alkylsilyl group, a substituted or unsubstituted C ₆ to C ₆₀ arylsilyl group, and a substituted or unsubstituted C ₆ to C ₆₀ arylamine group,

L ₁ to L ₄ Are the same as or different from each other, and each independently a substituted or unsubstituted C ₁ to C ₄₀ alkylene group, a substituted or unsubstituted C ₃ to C ₄₀ cycloalkylene group, a substituted or unsubstituted C ₃ to C ₄₀ Heterocycloalkylene group, substituted or unsubstituted C ₆ ~ C ₆₀ arylene group, substituted or unsubstituted heteroarylene group having 5 to 60 nuclear atoms, substituted or unsubstituted C ₁ ~ C ₄₀ oxyalkylene group , A substituted or unsubstituted C ₁ ~ C ₄₀ silylalkylene group and a substituted or unsubstituted C ₆ ~ C ₆₀ arylamine group,

X is Ar ₁ or a single bond, and wherein if is a single bond connected to a direct bond and Ar _1,

Wherein _{Ar 1 ~ Ar 4, L 1} ~ at L _4, substituents described the term "substituted or unsubstituted", more specifically, C ₁ ~ alkenyl group of the C ₄₀ alkyl group, C ₂ ~ C ₄₀ of, C ₂ ~ for C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, C ₃ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₆₀ aryl group, the number of nuclear atoms of 5 to 60 of the heteroaryl group, C ₁ ~ C ₄₀ C ₆ -C ₆₀ aryloxy groups, C ₁ -C ₄₀ alkylsilyl groups, C ₆ -C ₆₀ arylsilyl groups, C ₆ -C ₆₀ arylamine groups, C ₁ -C ₄₀ alkyl groups, A C ₃ to C ₄₀ cycloalkylene group, a C ₃ to C ₄₀ heterocycloalkylene group, a C ₆ to C ₆₀ arylene group, a heteroarylene group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ The C ₁ to C ₄₀ silylalkylene groups are each independently selected from the group consisting of deuterium, halogen, cyano, C ₁ to C ₄₀ alkyl, C ₂ to C ₄₀ alkenyl, C ₂ to C ₄₀ alkenyl, A C ₆ to C ₄₀ aryl group, a heteroaryl group having 5 to 40 nuclear atoms, a C ₆ to C ₄₀ aryl group, The aryloxy group, C ₁ ~ C ₄₀ of the alkyloxy group, C ₆ ~ C ₄₀ aryl amine group, C ₆ ~ C ₄₀ aryl group, C of ₃ ~ C ₄₀ cycloalkyl group, C of ₃ ~ C ₄₀ heteroaryl A C ₁ to C ₄₀ alkylsilyl group, a C ₆ to C ₆₀ arylsilyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, a C ₆ to C ₆₀ aryl phosphine group may be substituted with one or more substituents selected from C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ C ₆₀ aryl group consisting of amine groups of the.

In the compounds represented by formulas (1) to (5) according to the present invention, when considering the triplet energy level, Ar ₁ to Ar ₄ are the same or different and each independently represents a substituted or unsubstituted C6 to C60 aryl Substituted or unsubstituted heteroaryl group having 5 to 60 nuclear atoms. In one example, the C ₆ ~ C ₄₀ aryl group or a nuclear atoms groups are heteroaryl of 5 to 60, phenyl, naphthyl, indene, anthracene, phenanthrene, pyrene, triphenylene, pyridine, pyrimidine, pyrazine, tri- And examples thereof include azine, quinoline, isoquinoline, quinoxaline, fluorene, carbazole, dibenzothiophene, dibenzofuran, acridine, indole, benzofuran, benzothiophene, benzimidazole, benzothiazole, It can be Lin.

Also L ₁ to L ₄ Are divalent functional groups, the same as or different from each other, each independently represent a substituted or unsubstituted C6-C60 arylene group, a substituted or unsubstituted heteroarylene group having 5 to 60 nuclear atoms, and It is preferably selected from substituted or unsubstituted C ₆ -C ₆₀ arylamine groups. More preferably L ₁ to L ₄ May be selected from phenylene, pyridinylene, pyrimidylene, pyrazinylene, triazinylene, and each phenylene, pyridinylene group, pyrimidylene, pyrazinylene, triazinylene is one or more identical or Or substituted with different aforementioned substituents.

In the above Ar ₁ to Ar ₄ , L ₁ to L ₄ , A C6 ~ C60 aryl group, the number of nuclear atoms of 5 to 60 heteroaryl group, a group arylamine of C6 ~ C60 aryl group, a number of nuclear atoms of 5 to 60 heteroaryl group, a C ₆ ~ C ₆₀ each independently represents deuterium , a halogen, a nitrile group, a nitro group, a cyano group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, an alkoxy group of _{C 1 ~ C 40, C 1} ~ C 40 of the amino group, C ₃ ~ C _A C ₃ to C ₄₀ heterocycloalkyl group, a C ₆ to C ₄₀ aryl group, a heteroaryl group having 5 to 60 nuclear atoms, a C ₁ to C ₄₀ alkyloxy group, a C ₆ to C ₆₀ A C ₁ to C ₄₀ alkylsilyl group, a C ₆ to C ₆₀ arylsilyl group, a C ₁ to C ₄₀ alkylboron group, a C ₆ to C ₆₀ arylboron group, a C ₆ to C ₆₀ An aryl phosphine group of C ₆ to C _60, an aryl phosphine oxide group of C ₆ to C ₆₀ , and an arylamine group of C ₆ to C ₆₀ , or may be unsubstituted.

As used herein, "unsubstituted alkyl" refers to straight or branched chain saturated hydrocarbons having 1 to 40 carbon atoms, including but not limited to methyl, ethyl, propyl, isobutyl, sec- - Amyl, hexyl and the like.

"Unsubstituted aryl" means an aromatic moiety having from 6 to 60 carbon atoms, either alone or in combination with at least two rings. Where two or more rings may be attached to each other in a simple attached or condensed form.

"Unsubstituted heteroaryl" means a monoheterocyclic or polyheterocyclic aromatic moiety having 5 to 60 nuclear atoms in which at least one carbon, preferably one to three carbons, of the ring is replaced by N, O , S, or Se. In this case, two or more rings may be attached to each other in a form of simple attachment or condensation, and further, it may be interpreted as including a condensed form with an aryl group.

Further, "condensed rings" means condensed aliphatic rings, condensed aromatic rings, condensed heteroaliphatic rings, condensed heteroaromatic rings, or a combination thereof.

According to the present invention described above, the compounds represented by the formulas (1) to (5) can be further specified by the following illustrated formulas. However, the compounds represented by the general formulas (1) to (5) of the present invention are not limited by the following examples.

According to the present invention, the compounds represented by the general formulas (1) to (5) can be synthesized according to a general synthetic method. Detailed synthesis of the compound of the present invention will be described in detail in Synthesis Examples to be described later. However, it is not limited by the following synthesis examples.

<Organic Field  Light emitting element>

According to another aspect of the present invention, there is provided an organic electroluminescent device comprising a compound represented by any of Formulas 1 to 5 according to the present invention.

More specifically, the organic electroluminescent device according to the present invention comprises at least one organic layer interposed between (i) an anode, (ii) a cathode, and (iii) an anode and a cathode, One of them is characterized by containing one or more compounds represented by the above Chemical Formulas (1) to (5).

Here, the organic compound layer containing the compound of the present invention may be at least one of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. In this case, the organic EL device may improve luminous efficiency, brightness, power efficiency, thermal stability, and device life.

In particular, according to the present invention, the compounds represented by the general formulas (1) to (5) can be used as a phosphorescent host or a fluorescent host or a dopant material of the light emitting layer. Preferably, the compound represented by Formula 1 may be included in the organic light emitting device as a blue, green, and / or red phosphorescent host or hole transport material.

As a non-limiting example of the organic electroluminescent device structure according to the present invention, a substrate, an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and a cathode may be sequentially stacked. At this time, at least one of the hole injection layer, the hole transporting layer and the light emitting layer may contain at least one compound represented by the above Chemical Formulas 1 to 5. Further, the compound of the present invention can be used as a phosphorescent host or a hole transporting material of the light emitting layer. An electron injection layer may be disposed on the electron transport layer.

In addition, as described above, the organic EL device according to the present invention may not only have a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked, but an insulating layer or an adhesive layer may be inserted at an interface between an electrode and an organic material layer.

In the organic electroluminescent device according to the present invention, the organic material layer including the compound represented by Formula 1 may be formed by a vacuum deposition method or a solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer.

The organic electroluminescent device according to the present invention can be formed by using materials and methods known in the art, except that one or more of the organic material layers are formed so as to include the compounds represented by the general formulas (1) to (5) An organic layer and an electrode.

For example, a silicon wafer, quartz or glass plate, a metal plate, a plastic film or a sheet can be used as the substrate.

Examples of the positive electrode material 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 polythiophene, poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDT), polypyrrole and polyaniline; Or carbon black, but are not limited thereto.

Examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin or lead or alloys thereof; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

The hole injecting layer, the hole transporting layer, the electron injecting layer and the electron transporting layer are not particularly limited, and conventional materials known in the art can be used.

Hereinafter, the present invention will be described in detail with reference to the following examples. However, the following examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[ Synthetic example  One] Macrocycle Preparation of -I

Step 1) Compound One Manufacturing

1 equiv. (20 g, 40.49 mmol), 3-bromo-3-methylbenzoic acid A mixed solution of 9-phenylcarbazole, 2 eq (26 g, 81 mmol), K ₂ CO ₃ 33.5 g, toluene 800 ml and water 200 ml was added to a 2 L 2-neck round bottom flask and stirred for 30 minutes at room temperature It was added to give put _{Pd (PPh 3) 4 (1.4} g, 1.21 mmol) and then to the mixture was refluxed for 24 hours. After the reaction was completed, the reaction mixture was extracted with methylene chloride, added with MgSO ₄ and filtered. After removing the solvent of the obtained organic layer, it was purified by column chromatography to obtain intermediate compound 1 (24.80 g, yield 82%).

GC-Mass (calculated: 725.88 g / mol, measured: 725 g / mol)

Step 2) Preparation of Compound 2

The compound 1 (20.0 g, 27.55 mmol) obtained above was dissolved in 300 ml of DMF under a nitrogen stream, 5.40 g (30.31 mol) of N-bromosuccinimide was added thereto, stirred at 60 ° C for 8 hours, . The reaction mixture was extracted with ethyl acetate and water, and the obtained organic layer was filtered with MgSO ₄ . The solvent was removed by distillation under reduced pressure and then purified by column chromatography to obtain a yellow intermediate compound 2 (15.58 g, yield 64%).

GC-Mass (calculated: 883.67 g / mol, measured: 883 g / mol)

Step 3) Macrocycle - I  of  Produce

Compound obtained in the above 2 (15.0 g, 16.98 mmol) and 3,6-bis (4,4,5,5-tetramethyl- 1,3,2-dioxaborolan-2-yl) -9-phenylcarbazole 8.15g (16.98 mmol ), 14.0 g of anhydrous K ₂ CO ₃ , 800 ml of toluene and 200 ml of water was added to a 2-liter 2-neck round bottom flask, stirred at room temperature for 30 minutes, and further treated with Pd (PPh ₃ ) ₄ g, 0.52 mmol) and refluxed for 24 hours. After the reaction was completed, the reaction mixture was extracted with methylene chloride, added with MgSO ₄ and filtered. The solvent of the obtained organic layer was removed, and then purified by column chromatography to obtain Macrocycle- I (4.42 g, 27% yield) as a target compound.

GC-Mass (calculated: 965.15 g / mol, measured: 965 g / mol)

[ Synthetic example  2] Macrocycle -II

(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9-phenylcarbazole (10.0 g, 20.19 mmol) and 4- (3,5- -phenyl) -2,6-diphenyl-pyrimidine A mixture of 9.41 g (20.19 mmol) of K ₂ CO _3, 16.7 g of K ₂ CO ₃ , 800 ml of toluene and 200 ml of water was placed in a 2-liter 2-neck round bottom flask, to put the Pd (PPh ₃₎ with stirring and then added ₄ (70 mg, 0.61 mmol) at room temperature and refluxed for 18 hours. After the reaction was completed, the reaction mixture was extracted with methylene chloride, added with MgSO ₄ and filtered. The solvent of the obtained organic layer was removed, and the residue was purified by column chromatography to obtain the target compound Macrocycle-II (4.93 g, yield 22.3%).

GC-Mass (calculated: 1095.29 g / mol, measured: 1095 g / mol)

[ Synthetic example  3] Macrocycle -III

Step 1) Compound 3 Manufacturing

20 g (23.86 mmol) of 2,8-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) _{23.86 mmol), K 2 CO 3} 19.8 g, toluene 800 ml, and a mixed solution of water 200 ml of the following additional stirring at room temperature for 30 minutes to put a 2-neck round bottom flask of 2L Pd (PPh _{3) 4} ( 0.83 g, 0.72 mmol) and refluxed for 24 hours. After the reaction was completed, the reaction mixture was extracted with methylene chloride, added with MgSO ₄ and filtered. The solvent of the obtained organic layer was removed and then purified by column chromatography to obtain intermediate compound 3 (2.14 g, yield 18.5%).

GC-Mass (calculated: 484.55 g / mol, measured: 484 g / mol)

Step 2) Macrocycle Preparation of -III

Compound 3 (2.0 g, 4.13 mmol) and 2.72 g (8.26 mmol) of 1,4-diiodobenzene, 3.42 g of anhydrous K ₂ CO ₃ , Cu powder 52 mg (0.83 mmol) and Na ₂ SO ₄ 1.2 g (8.26 mmol) was added to 50 ml of nitrobenzene and refluxed for 24 hours. After the reaction was completed, nitrobenzene was removed, and the mixture was extracted with methylene chloride, and then filtered through MgSO ₄ to remove moisture. The solvent of the obtained organic layer was distilled off under reduced pressure, and then purified by column chromatography to obtain Macrocycle- III (1.22 g, yield 53%) as a target compound.

GC-Mass (calculated: 558.63 g / mol, measured: 558 g / mol)

[ Synthetic example  4] Macrocycle -IV production

Step 1) Compound 4 of  Produce

9,9'-diphenyl-6,6'-bis- (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9H, 9'H-3,3 (27.16 mmol) of 6'-dibromo-9H, 9'H-3,3'-bicarbazolyl, 22.5 g of K ₂ CO ₃ , 800 ml of toluene and 200 ml of water (PPh ₃ ) ₄ (0.94 g, 0.81 mmol) was added thereto, followed by refluxing for 24 hours. The resulting mixture was stirred at room temperature for 30 minutes. After the reaction was completed, the reaction mixture was extracted with methylene chloride, added with MgSO ₄ and filtered. The solvent of the obtained organic layer was removed and then purified by column chromatography to obtain an intermediate compound 4 (4.11 g, yield 18.6%).

GC-Mass (calculated: 812.95 g / mol, measured: 812 g / mol)

Step 2) Macrocycle -IV production

Compound 4 (4.0 g, 4.92 mmol) obtained above, 3.05 g (9.84 mmol) of 2-bromo-4,6-diphenylpyridine, 4.08 g of anhydrous K ₂ CO ₃ , 63 mg (0.98 mmol) of Cu powder, and Na ₂ SO ₄ 1.4 g (9.84 mmol) was added to 50 ml of nitrobenzene and refluxed for 24 hours. After the reaction was completed, nitrobenzene was removed, and the mixture was extracted with methylene chloride, and then filtered through MgSO ₄ to remove moisture. The solvent of the obtained organic layer was distilled off under reduced pressure, and then purified by column chromatography to obtain Macrocycle- IV (3.32 g, yield 53%) as a target compound.

GC-Mass (calculated: 1,271.51 g / mol, measured: 1,271 g / mol)

[ Synthetic example  5] Macrocycle Manufacturing of -V

Since the Macrocycle-Ⅱ manufacturing Macrocycle-V compound is also produced with the, the Macrocycle -V compound of the aimed compound by further column chromatography Isolated and purified. (1.15 g, 2.6% yield)

GC-Mass (theory: 2,190.59 g / mol, measured: 2,190 g / mol)

[ Example  1 to 5] organic EL  Fabrication of devices (1)

The compounds Macrocycle-I to Macrocycle-V synthesized in Synthesis Examples 1 to 5 were subjected to high purity sublimation purification by a known method, and then an organic EL device was fabricated according to the following procedure.

First, a glass substrate coated with ITO (Indium Tin Oxide) with a thickness of 1500 Å was washed with distilled water ultrasonic waves. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, dried and transferred to a UV OZONE cleaner (Power Sonic 405, Hoshin Tech), the substrate was cleaned using UV for 5 minutes, The substrate was transferred.

On this ITO transparent electrode, m-MTDATA (60 nm) / TCTA (80 nm) / Macrocycle-I to Macrocycle-V The respective compounds of + 10% Ir (ppy) stacked in _{3 (300nm) / BCP (10} nm) / Alq 3 (30 nm) / LiF (1 nm) / Al (200 nm) in order to prepare a organic EL device .

The structures of m-MTDATA, TCTA, Ir (ppy) ₃ , CBP and BCP are as follows.

[ Comparative Example  1] Organic EL  Device fabrication

A green organic EL device was fabricated in the same manner as in Example 1, except that CBP was used instead of the compound Macrocycle-I as a luminescent host material in forming the light emitting layer.

[ Evaluation example  One]

The driving voltage, current efficiency and emission peak at current densities of 10 mA / cm 2 were measured for each of the organic EL devices manufactured in Example 1-5 and Comparative Example 1, and the results are shown in Table 1 below.

Host Driving voltage
(V) EL peak
(nm) Current efficiency
(cd / A) Example 1 Macrocycle-I 6.44 519 40.5 Example 2 Macrocycle-II 6.60 518 41.3 Example 3 Macrocycle-III 6.65 520 42.2 Example 4 Macrocycle-Ⅳ 6.55 520 41.0 Example 5 Macrocycle-V 6.50 521 41.5 Comparative Example 1 CBP 6.93 516 38.2

As shown in Table 1, the organic EL device of Example 1-5 using the compound (Macrocycle-I to Macrocycle-V) according to the present invention as the light emitting layer was compared with the organic EL device of Comparative Example 1 using the conventional CBP It can be seen that it shows superior performance in terms of efficiency and driving voltage.

[ Example  6-7] Organic EL  Fabrication of devices (2)

The compounds Macrocycle-I and Macrocycle-III synthesized in Synthesis Examples 1 and 3 were subjected to high purity sublimation purification by a conventionally known method, and then an organic EL device was fabricated according to the following procedure.

First, a glass substrate coated with ITO (Indium Tin Oxide) with a thickness of 1500 Å was washed with distilled water ultrasonic waves. After the distilled water was washed, the substrate was ultrasonically washed with a solvent such as isopropyl alcohol, acetone, or methanol, dried and transferred to a UV OZONE cleaner (Power Sonic 405, Hoshin Tech), the substrate was cleaned using UV for 5 minutes, The substrate was transferred.

DS-205 (Doosan) was thermally vacuum deposited on the prepared ITO transparent electrode to a thickness of 800 Å to form a hole injecting layer, and Macrocycle-I or Macrocycle-III Each of them was vacuum deposited at a thickness of 150 ANGSTROM to form a hole transport layer.

Doped with 5% of DS-405 (Doosan) as a dopant and vacuum-deposited to a thickness of 300 Å to form a light emitting layer. An electron transport layer was formed by vacuum depositing Alq3, which is an electron transport material, on the light emitting layer to a thickness of 250 kPa. Thereafter, LiF, which is an electron injection material, was deposited to a thickness of 10 kW to form an electron injection layer, and aluminum was vacuum deposited to a thickness of 2000 kW thereon to form a cathode to fabricate an organic EL device.

The structures of ADN and NPB are as follows.

[ Comparative Example  2] Organic EL  Device fabrication

An organic EL device was fabricated in the same manner as in Example 6, except that NPB was used instead of the compound Macrocycle-I as a hole transport material in the formation of the light emitting layer.

[ Evaluation example  2]

The driving voltage, current efficiency and emission peak at current densities of 10 mA / cm 2 were measured for each of the organic EL devices manufactured in Example 6-7 and Comparative Example 2, and the results are shown in Table 2 below.

Hole transport material Driving voltage
(V) EL peak
(nm) Current efficiency
(cd / A) Example 6 Macrocycle-I 4.50 _ 6.6 Example 7 Macrocycle-III 4.92 _ 6.8 Comparative Example 2 NPB 5.60 _ 4.8

As shown in Table 2 above, the organic EL device of Example 6-7 using the compound (Macrocycle-I, Macrocycle-III) according to the present invention as a hole transporting layer of an organic EL device had a comparative example 2 shows superior performance in terms of efficiency and driving voltage.

Claims (9)

At least one carbazole ring in the molecule; Or one or more carbazole-based rings and one or more linking groups, wherein the at least one carbazole-based ring or the carbazole-based ring and the linking group are bonded to each other to form a closed cyclic structure, and the molecular weight is 500 To &lt; RTI ID = 0.0 &gt; 3000,
A cyclic compound, characterized in that represented by any one of the following formulas (1) to (3):
[Chemical Formula 1]

(2)

(3)

In this formula,
Ar ₁ to Ar ₄ are the same as or different from each other, and each independently hydrogen, a substituted or unsubstituted C ₁ to C ₄₀ alkyl group, a substituted or unsubstituted C ₂ to C ₄₀ alkenyl group, a substituted or unsubstituted C ₂ -C ₄₀ alkynyl group, substituted or unsubstituted C ₃ -C ₄₀ cycloalkyl group, substituted or unsubstituted C ₃ -C ₄₀ heterocycloalkyl group, substituted or unsubstituted C ₆ -C ₆₀ aryl Groups, substituted or unsubstituted heteroaryl groups having 5 to 60 nuclear atoms, substituted or unsubstituted C ₁ to C ₄₀ alkyloxy groups, substituted or unsubstituted C ₆ to C ₆₀ aryloxy groups, substituted or An unsubstituted C ₁ to C ₄₀ alkylsilyl group, a substituted or unsubstituted C ₆ to C ₆₀ arylsilyl group, and a substituted or unsubstituted C ₆ to C ₆₀ arylamine group,
L ₁ to L ₄ Are the same as or different from each other, and each independently a substituted or unsubstituted C ₁ to C ₄₀ alkylene group, a substituted or unsubstituted C ₃ to C ₄₀ cycloalkylene group, a substituted or unsubstituted C ₃ to C ₄₀ Heterocycloalkylene group, substituted or unsubstituted C ₆ ~ C ₆₀ arylene group, substituted or unsubstituted heteroarylene group having 5 to 60 nuclear atoms, substituted or unsubstituted C ₁ ~ C ₄₀ oxyalkylene group , A substituted or unsubstituted C ₁ ~ C ₄₀ silylalkylene group, and a substituted or unsubstituted C ₆ ~ C ₆₀ arylamine group,
X is Ar ₁ or a single bond, and wherein if is a single bond connected to a direct bond and Ar _1,
Wherein the C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ alkenyl group, C ₂ to C ₄₀ alkynyl group, C ₃ to C ₄₀ cycloalkyl group, C ₃ to C ₄₀ heterocycloalkyl group, C ₆ Aryl group of ~ C ₆₀ , heteroaryl group of 5 to 60 nuclear atoms, alkyloxy group of C ₁ ~ C ₄₀ , aryloxy group of C ₆ ~ C ₆₀ , alkylsilyl group of C ₁ ~ C ₄₀ , C ₆ Aryl silyl group of ~ C ₆₀ , C ₆ ~ C ₆₀ arylamine group, C ₁ ~ C ₄₀ alkylene group, C ₃ ~ C ₄₀ cycloalkylene group, C ₃ ~ C ₄₀ heterocycloalkylene group, C ₆ ~ C ₆₀ aryl group, a nuclear atoms groups are silyl alkylene of 5 to 60 heteroaryl group, a C ₁ ~ C ₄₀ of the oxyalkylene group, C ₁ ~ C ₄₀ of each independently deuterium, halogen, cyano, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₆ ~ C ₄₀ aryl group, nuclear atoms aryl of from 5 to 40 heteroaryl group, C ₆ ~ C ₄₀ Aryloxy group, C ₁ to C ₄₀ alkyloxy group, C ₆ to C ₄₀ arylamine group, C ₆ to C ₄₀ arylalkyl group , C ₃ ~ C ₄₀ cycloalkyl group, C ₃ ~ C ₄₀ heterocycloalkyl group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, aryl of C ₆ ~ C ₆₀ boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C aryl phosphine oxide groups of _60, and a C ₆ ~ C at least one selected from ₆₀ the group consisting of an aryl amine of the substituents Cyclic compound, characterized in that substituted by. According to claim 1, Ar ₁ to Ar ₄ are the same as or different from each other, each independently selected from the group consisting of a C ₆ ~ C ₆₀ aryl group, a heteroaryl group of 5 to 60 nuclear atoms,
The C ₆ ~ C ₆₀ aryl group, the heteroaryl group of 5 to 60 nuclear atoms are each independently deuterium, halogen, nitrile group, nitro group, cyano group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₁ ~ C ₄₀ of the amino group, C ₃ ~ C ₄₀ cycloalkyl group, C ₃ ~ C ₄₀ of the heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group, a nuclear atom Heteroaryl group of 5 to 60, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ group of an alkyl boron, C ₆ ~ C group ₆₀ arylboronic of, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ arylamine group of C ₆₀ of A cyclic compound, which is unsubstituted or substituted with one or more selected from the group consisting of. According to claim 1, wherein L ₁ to L ₄ Are the same as or different from each other, and each independently a substituted or unsubstituted C6-C60 arylene group, a substituted or unsubstituted heteroarylene group having 5 to 60 nuclear atoms, and a substituted or unsubstituted C ₆ to C ₆₀ Is selected from the group consisting of arylamine groups,
The C ₆ to C ₆₀ arylene group, the heteroarylene group having 5 to 60 nuclear atoms, and the C ₆ to C ₆₀ arylamine group are each independently deuterium, halogen, nitrile group, nitro group, cyano group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₁ ~ C ₄₀ alkoxy group, C ₁ ~ C ₄₀ amino group, C ₃ ~ C ₄₀ cycloalkyl group, C ₃ ~ C ₄₀ heterocycloalkyl group, C ₆ ~ C ₄₀ aryl group, nuclear atom 5 to 60 heteroaryl group, C ₁ ~ C ₄₀ alkyloxy group, C ₆ ~ C ₆₀ aryloxy group, C ₁ ~ C ₄₀ alkylsilyl group, C ₆ ~ C ₆₀ arylsilyl group, C ₁ ~ C ₄₀ alkyl boron group, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide A cyclic compound, which is unsubstituted or substituted with one or more selected from the group consisting of a group and a C ₆ -C ₆₀ arylamine group. The compound of claim 1, wherein the compound represented by Chemical Formula 1 is selected from the group of compounds represented by the following chemical formulas.

The compound of claim 1, wherein the compound represented by Chemical Formula 2 is selected from the group of compounds represented by the following chemical formulas.

The compound of claim 1, wherein the compound represented by Chemical Formula 3 is selected from the group of compounds represented by the following chemical formulas:

An organic electroluminescent device comprising: (i) a cathode, (ii) a cathode, and (iii) one or more organic layers sandwiched between the anode and the cathode,
At least one of the said one or more organic compound layers contains the cyclic compound of any one of Claims 1-6, The organic electroluminescent element characterized by the above-mentioned. The organic electroluminescent device according to claim 7, wherein the organic material layer is selected from the group consisting of a hole injection layer, a hole transport layer and a light emitting layer. The organic electroluminescent device according to claim 7, wherein the cyclic compound is used as a phosphorescent host or a hole transport layer of the light emitting layer.