KR20180055688A - Compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a compound represented by chemical formula 1 and an organic light emitting device comprising the same. The compound according to at least one embodiment can improve efficiency, driving voltage and/or lifetime properties of the organic light emitting device.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a compound and an organic light-

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound and an organic light emitting device including the same. This specification claims the benefit of Korean Patent Application No. 10-2016-0153292, filed on November 17, 2016, to the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

The organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic light emitting device having such a structure, electrons and holes injected from the two electrodes couple to each other in the organic thin film and form a pair, which then extinguishes and emits light. The organic thin film may be composed of a single layer or a multilayer, if necessary.

The material of the organic thin film may have a light emitting function as needed. For example, as the organic thin film material, a compound capable of forming a light emitting layer by itself may be used, or a compound capable of serving as a host or a dopant of a host-dopant light emitting layer may be used. In addition, as the material of the organic thin film, a compound capable of performing a role such as hole injection, hole transport, electron blocking, hole blocking, electron transport or electron injection may be used.

In order to improve the performance, life or efficiency of an organic light emitting device, development of materials for organic thin films is continuously required.

International Patent Application Publication No. 2003-012890

In this specification, compounds and organic light emitting devices containing them are described.

An embodiment of the present invention provides a compound represented by the following formula (1).

[Chemical Formula 1]

In formula (1)

And at least one of X1 to X3 is N, the rest are CR _5,

Y is S or O,

Ar ₁ and R ₁ to R ₅ are the same or different and each independently hydrogen; heavy hydrogen; A halogen group; Cyano; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

L is a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,

a is an integer of 0 to 5, b, c and d are each an integer of 0 to 7,

When a to d are two or more, the substituents in parentheses are the same or different from each other.

In addition, one embodiment of the present disclosure includes a first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers includes the compound of Formula 1.

The compound described in this specification can be used as a material of an organic layer of an organic light emitting device. The compound according to at least one embodiment can improve the efficiency, lower driving voltage and / or lifetime characteristics in the organic light emitting device.

Fig. 1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3 and a cathode 4. Fig.
2 shows an example of an organic light emitting element comprising a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 3, an electron transporting layer 7 and a cathode 4 It is.
3 is the MS spectrum of Compound 1. Fig.
4 is the MS spectrum of compound 2. Fig.
5 is an MS spectrum of Compound 3. Fig.
Fig. 6 is the MS spectrum of Compound 4. Fig.
7 is the MS spectrum of Compound 5. Fig.

Hereinafter, the present invention will be described in more detail.

An embodiment of the present invention provides a compound represented by the above formula (1).

The compound represented by the formula (1) is a compound in which the benzene ring of one carbazole and the N of the other carbazole are directly bonded to each other and, when they are bonded directly, the HOMO is bonded to the two carbazoles The stability against holes is enhanced. Therefore, when the compound is applied to an organic light emitting device, the lifetime is increased.

Illustrative examples of such substituents are set forth below, but are not limited thereto.

As used herein, the term " substituted or unsubstituted " A halogen group; A nitrile group; A nitro group; An amino group; An alkyl group; A cycloalkyl group; An alkenyl group; An aryl group; And a heterocyclic group, or a substituted or unsubstituted one in which at least two of the above-exemplified substituents are connected to each other. For example, "a substituent to which at least two substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to one embodiment, the alkyl group has 1 to 20 carbon atoms. According to another embodiment, the alkyl group has 1 to 10 carbon atoms. According to another embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert- But are not limited to, pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl and the like.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to one embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

In this specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms. According to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specific examples include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to one embodiment, the aryl group has 6 to 30 carbon atoms. According to one embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, a terphenyl group or the like as the monocyclic aryl group, but is not limited thereto. Examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group.

,

,

및

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

And

And the like. However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a hetero ring group containing at least one of O, N, S, Si and Se as a hetero atom, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furane group, a furyl group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, A pyridazinyl group, a pyrazinopyrazinyl group, an isoquinoline group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, A benzothiazole group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, a phenanthroline group, a thiazolyl group, a thiazolyl group, a thiazolyl group, An isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

In the present specification, the heterocyclic group may be monocyclic or polycyclic, and may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and examples of the heterocyclic group may be selected.

In the present specification, the description of the aryl group described above can be applied, except that the arylene group is a divalent group.

In one embodiment of the present invention, the compound represented by the formula (1) is represented by any one of the following formulas (2) to (10).

(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the general formulas (2) to (10), Ar 1, X 1 to X 3, Y, R ₁ to R ₄ , L and a to d are as defined in the above formula (1).

In one embodiment of the present invention, the compound represented by the formula (1) is represented by any one of the following formulas (11) to (14).

(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

In the general formula 11 to 14, Ar1, X1 to X3, Y, R ₁ to R _4, the definition of L and a to d are the same as defined in the general formula (1).

In one embodiment of the present disclosure, X1 is N.

In one embodiment of the present disclosure, X2 is N.

In one embodiment of the present disclosure, X3 is N.

In one embodiment of the present specification, at least two of X1 to X3 are N, and the remainder is CH.

In one embodiment of the present disclosure, X1 to X3 are all N.

In one embodiment of the present disclosure, L is a direct bond; Or a substituted or unsubstituted arylene group.

In one embodiment of the present disclosure, L is a direct bond; Or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In one embodiment of the present disclosure, L is a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene group; A substituted or unsubstituted naphthalene group; A substituted or unsubstituted pyridyl group; A substituted or unsubstituted pyrimidylene group; A substituted or unsubstituted furanyl group; A substituted or unsubstituted thiophenylene group; A substituted or unsubstituted imidazolylene group; A substituted or unsubstituted benzothiophenylene group; A substituted or unsubstituted benzofuranyl group; A substituted or unsubstituted benzothiazolyl group; Or a substituted or unsubstituted benzoxazolylene group.

In one embodiment of the present disclosure, L is a direct bond; A phenylene group; Biphenyllylene groups; A naphthalene group; A pyridyl group; A pyrimidylene group; A furanylene group; Thiophenylene group; An imidazolylene group; Benzothiophenylene groups; Benzofuranyl groups; A benzothiazolyl group; Or a benzoxazolylene group.

In one embodiment of the present specification, L is a direct bond or a phenylene group.

이다. In one embodiment of the present disclosure, L is a direct bond; or

to be.

In one embodiment of the present specification, L is a direct bond.

In one embodiment of the present specification, Ar1 is a substituted or unsubstituted aryl group.

In one embodiment of the present specification, Ar1 represents a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted anthracene group; A substituted or unsubstituted phenanthrene group; Or a substituted or unsubstituted triphenylene group.

In one embodiment of the present specification, Ar1 represents a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted terphenyl group.

In one embodiment of the present specification, Ar1 represents a phenyl group; A biphenyl group; Or a terphenyl group.

In one embodiment of the present invention, Ar1 is a phenyl group.

In one embodiment of the present invention, the compound represented by Formula 1 is selected from the following structural formulas.

The compound according to one embodiment of the present application can be produced by a production method described below.

For example, the compound of Formula 1 can be prepared as shown in Reaction Scheme 1 below. Substituent groups may be attached by methods known in the art, and the type, position or number of substituent groups may be varied according to techniques known in the art.

[Reaction Scheme 1]

The present invention also provides an organic light emitting device comprising the above-described compound.

In one embodiment of the present application, the first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers includes the compound.

When a member is referred to herein as being "on " another member, it includes not only a member in contact with another member but also another member between the two members.

Whenever a component is referred to as "comprising ", it is understood that it may include other components as well, without departing from the other components unless specifically stated otherwise.

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

In one embodiment of the present application, the thickness of the organic material layer including the compound is 1 ANGSTROM to 1000 ANGSTROM, more preferably 1 ANGSTROM to 500 ANGSTROM.

In one embodiment of the present application, the organic layer includes a light emitting layer, and the light emitting layer includes the compound.

In one embodiment of the present application, the organic layer includes a light emitting layer, and the light emitting layer contains the compound as a host material.

In one embodiment of the present application, the organic layer includes a light emitting layer, the light emitting layer includes the compound, and further includes a dopant compound.

In one embodiment of the present application, the organic layer includes a light emitting layer, the light emitting layer includes the compound, and further includes a phosphorescent dopant compound.

In one embodiment of the present application, the organic layer includes a light emitting layer, the light emitting layer includes the compound, and further includes an iridium complex.

In one embodiment of the present application, the organic layer includes a light emitting layer, and the light emitting layer contains the compound and the dopant compound in a weight ratio of 100: 1 to 5: 5.

In one embodiment of the present application, the organic layer includes a light emitting layer, and the light emitting layer contains a dopant compound in a weight ratio of 5% to 20% with respect to the compound.

In one embodiment of the present application, the organic layer includes a hole injection layer or a hole transport layer, and the hole injection layer or the hole transport layer includes the compound.

In one embodiment of the present application, the organic material layer includes an electron transporting layer or an electron injecting layer, and the electron transporting layer or the electron injecting layer includes the above compound.

In one embodiment of the present application, the organic layer includes an electron blocking layer or a hole blocking layer, and the electron blocking layer or the hole blocking layer includes the compound.

In one embodiment of the present application, the organic light emitting device includes a first electrode; A second electrode facing the first electrode; And a light emitting layer provided between the first electrode and the second electrode; At least one of the two or more organic layers includes two or more organic layers disposed between the light emitting layer and the first electrode or between the light emitting layer and the second electrode.

In one embodiment of the present application, the two or more organic layers may be selected from the group consisting of an electron transport layer, an electron injection layer, a layer that simultaneously transports electrons and electrons, and a hole blocking layer.

In one embodiment of the present application, the organic material layer includes two or more electron transporting layers, and at least one of the two or more electron transporting layers includes the above compound. Specifically, in one embodiment of the present specification, the compound may be contained in one of the two or more electron transporting layers, and may be included in each of two or more electron transporting layers.

In the embodiment of the present application, when the compound is contained in each of the two or more electron transporting layers, the materials other than the above compounds may be the same or different from each other.

In one embodiment of the present application, the organic layer further includes a hole injection layer or a hole transport layer containing a compound containing an arylamino group, a carbazolyl group or a benzocarbazolyl group in addition to the organic compound layer containing the compound.

In another embodiment, the organic light emitting device may be a normal type organic light emitting device in which an anode, at least one organic layer, and a cathode are sequentially stacked on a substrate.

 In another embodiment, the organic light emitting device may be an inverted type organic light emitting device in which a cathode, at least one organic compound layer, and an anode are sequentially stacked on a substrate.

For example, the structure of an organic light emitting device according to one embodiment of the present application is illustrated in Figs. 1 and 2. Fig.

1 shows a structure of an organic light emitting device in which a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially laminated. In such a structure, the compound may be included in the light emitting layer (3).

2 shows an organic light emitting device in which a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 3, an electron transporting layer 7 and a cathode 4 are sequentially laminated Structure is illustrated. In such a structure, the compound may be contained in at least one of the hole injecting layer 5, the hole transporting layer 6, the light emitting layer 3, and the electron transporting layer 7.

In such a structure, the compound may be contained in at least one of the hole injecting layer, the hole transporting layer, the light emitting layer, and the electron transporting layer.

The organic light emitting device of the present application may be manufactured by materials and methods known in the art, except that one or more of the organic layers include the compound of the present application, i.e., the compound.

When the organic light emitting diode includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

 The organic light emitting device of the present application can be produced by materials and methods known in the art, except that one or more of the organic layers include the above compound, that is, the compound represented by the above formula (1).

For example, the organic light emitting device of the present application can be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as a sputtering method or an e-beam evaporation method, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate to form a positive electrode Forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer and an electron transporting layer thereon, and depositing a material usable as a cathode thereon. In addition to such a method, an organic light emitting device can be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

In addition, the compound of Formula 1 may be formed into an organic material layer by a solution coating method as well as a vacuum evaporation method in the production of an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating and the like, but is not limited thereto.

In addition to such a method, an organic light emitting device may be fabricated by sequentially depositing an organic material layer and a cathode material on a substrate from a cathode material (International Patent Application Publication No. 2003/012890). However, the manufacturing method is not limited thereto.

In one embodiment of the present application, the first electrode is an anode and the second electrode is a cathode.

In another embodiment, the first electrode is a cathode and the second electrode is a cathode.

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-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), 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; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

The hole injecting layer is a layer for injecting holes from an electrode. The hole injecting material has a hole injecting effect, and has a hole injecting effect on the light emitting layer or a light emitting material. A compound which prevents the migration of excitons to the electron injecting layer or the electron injecting material and is also excellent in the thin film forming ability is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be 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 porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

The hole transport layer is a layer that transports holes from the hole injection layer to the light emitting layer. The hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer. The material 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.

The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic compound. Specific examples of the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds. Examples of heterocycle-containing compounds include compounds, dibenzofuran derivatives, ladder furan compounds , Pyrimidine derivatives, and the like, but are not limited thereto.

The electron transporting layer is a layer that receives electrons from the electron injecting layer and transports electrons to the light emitting layer. The electron transporting material is a material capable of transferring electrons from the cathode well to the light emitting layer. 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 electron transporting layer can be used with any desired cathode material as used according to the prior art. In particular, an example of a suitable cathode material is a conventional material with a low work function followed by an aluminum layer or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer for injecting electrons from the electrode. The electron injection layer has the ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron injection effect with respect to the light emitting layer or the light emitting material. A compound which prevents migration to a layer and is excellent in a thin film forming ability is preferable. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A complex compound and a nitrogen-containing five-membered ring derivative, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, But is not limited thereto.

The hole blocking layer prevents holes from reaching the cathode, and may be formed under the same conditions as those of the hole injecting layer. Specific examples thereof include, but are not limited to, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes and the like.

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

The preparation of the compound represented by Formula 1 and the organic light emitting device comprising the same will be described in detail in the following examples. However, the following examples are intended to illustrate the present specification, and the scope of the present specification is not limited thereto.

< Manufacturing example >

PREPARATION EXAMPLE 1 Preparation of Compound 1

1) Preparation of Compound 1-1

3-chlorobenzoic acid (20 g, 128 mmol) was added to thionyl chloride (200 mL), and the mixture was refluxed with stirring for 2 hours. After cooling to room temperature, the resulting solid was distilled and washed with diethyl ether and dried to obtain Compound 1-1. (20.3 g, 91% yield)

2) Preparation of Compound 1-2

After the addition of a 2.0 M solution of dimethylamine (74.8 mL, 150 mmol) and triethylamine (37.9 mL, 272 mmol) into 500 mL of diethyl ether, 24 g, 138 mmol) was slowly added dropwise thereto, followed by stirring for 30 minutes. The resulting solid was filtered, and the filtrate was distilled to prepare Compound 1-2. (19.8 g, 83% yield)

3) Preparation of compound 1-3

N'-cyanobenzimidamide (16.8 g, 115 mmol) and Compound 1-2 (21 g, 115 mmol) and phosphorus oxychloride (12 mL, 128 mmol) Was added to 500 mL of acetonitrile, and the mixture was refluxed with stirring for 1 hour. After cooling to room temperature, the resulting solid was filtered, washed with water and ethanol, and dried to give Compound 1-3. (27.6 g, 80% yield)

4) Preparation of compounds 1-4

Dibenzo [b, d] furan-4-ylboronic acid (15.5 g, 73.2 mmol) was dissolved in tetrahydrofuran , And potassium carbonate (19.0 g, 139 mmol) was dissolved in 50 mL of water and added to the mixture. After nitrogen charging, tetrakis (triphenylphosphine) palladium (0.8 g, 1 mol%) was added to the suspension. Under nitrogen, the mixture was stirred at reflux for about 6 hours. After cooling to room temperature, the resulting solid was filtered. The filtered solid was dissolved in chloroform and washed twice with water. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, concentrated under reduced pressure, and ethanol was added while stirring in a small amount of chloroform. This was filtered to give white solid compound 1-4. (26.6 g, yield 88%).

5) Preparation of compound 1-5

(9H-carbazol-3-yl) boronic acid (9.2 g, 43.6 mmol) was reacted with 1,4-dioxane ( 150 mL) and additional potassium phosphate (17.6 g, 83 mmol) and water (50 mL). 0.7 g (1.2 mmol) of dibenzylidene acetone palladium and 0.7 g (2.5 mmol) of tricyclohexylphosphine were added under reflux and stirring, and the mixture was stirred under reflux for 12 hours. When the reaction was completed, the mixture was cooled to room temperature, and the water layer was separated. The filtrate was concentrated under reduced pressure. The residue was dissolved in chloroform, and the organic layer was separated by washing with water. The separated organic layer was dried over anhydrous magnesium sulfate and filtered. Compound 1-5 was prepared by recrystallization under reflux by adding ethyl acetate while concentrating. (17.1 g, yield 73%).

6) Preparation of compound 1

The compound 1-5 (14 g, 24.8 mmol) and 2-bromo-9-phenyl-9H-carbazole (8.0 g, 24.8 mmol) were dispersed in 100 mL of xylene , And sodium tertiary-butoxide (4.8 g, 50 mmol) was added thereto and warmed. Bis (tritiated-butylphosphine) palladium (0.13 g, 1 mol%) was added under reflux for reaction for 6 hours. After completion of the reaction, the temperature was lowered to room temperature and the resulting solid was filtered. The pale yellow solid was dissolved in chloroform, and magnesium sulfate and acidic white clay were added thereto, followed by stirring, followed by filtration and distillation under reduced pressure. Recrystallization was performed using chloroform and ethyl acetate to prepare a white solid compound 1 . (15 g, yield 75%, MS: [M + H] &lt; ⁺ &gt; = 806)

The MS spectrum of Compound 1 is shown in Fig.

PREPARATION EXAMPLE 2 Preparation of Compound 2

1) Preparation of Compound 2-1

The same procedures as in the synthesis of the compound 1-3 of Preparation Example 1 were carried out except that 2-chlorobenzoic acid was used in place of 3-chlorobenzoic acid to obtain the desired compound 2-1 .

2) Preparation of compound 2-2

The compound 2-1 (20 g, 66 mmol) and dibenzo [b, d] furan-2-ylboronic acid (14 g, 66 mmol) The objective compound 2-2 was prepared in the same manner as in the preparation example 1-4, (23.8 g, yield 83%).

3) Preparation of compound 2-3

Using the compound 2-2 (22 g, 51 mmol) and (2-nitrophenyl) boronic acid (8.9 g, 53 mmol), the same procedure To obtain the target compound 2-3 (20 g, yield 76%).

4) Preparation of compound 2-4

Triethylphosphite (P (OEt) ₃ ) (7.7 g, 45.6 mmol) was added to compound 2-3 (20 g, 38 mmol), and the mixture was warmed and stirred. When the reaction was completed, the remaining triethyl phosphite was removed by distillation in vacuo, and the mixture was cooled to room temperature and stirred. The resulting solid was filtered through addition of hexane and ethyl acetate, and the filtered solid was washed with hexane. The solid was dissolved again in chloroform and washed twice with water. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The compound was recrystallized from ethanol and ethyl acetate to give compound 2-4 (15.2 g, yield 81%).

5) Preparation of Compound 2

Compound 9 was obtained by the same procedure as described in the synthesis of Compound 1 using Compound 2-4 (15 g, 28.8 mmol) and 2-bromo-9-phenyl-9H-carbazole (9.28 g, 28.8 mmol) Compound 2 was prepared in the same manner as in Production Example. (14.7 g, yield 70%, MS: [M + H] &lt; ⁺ &gt; = 730)

The MS spectrum of the compound 2 is shown in Fig.

PREPARATION EXAMPLE 3 Preparation of Compound 3

1) Preparation of compound 3-1

The same procedures as in the synthesis of the compound 1-3 of Preparation Example 1 were carried out except that 4-chlorobenzoic acid was used in place of 3-chlorobenzoic acid to obtain the desired compound 3-1 .

 2) Preparation of compound 3-2

Dibenzo [b, d] thiophen-3-ylboronic acid (20 g, 87 mmol) was used instead of the compound 3-1 (25 g, 73 mmol) The objective compound 3-2 was prepared (30.8 g, yield: 83%).

3) Preparation of compound 3-3

Using the compound 3-2 (30 g, 67 mmol) and (2-nitrophenyl) boronic acid (11.7 g, 70 mmol), the same procedure To obtain the target compound 3-3 (29 g, yield 80%).

4) Preparation of compound 3-4

Compound 3-4 (15.0 g, yield 80%) was prepared using Compound 3-3 (20 g, 37 mmol) in the same manner as in Preparation Example 2-4.

5) Preparation of Compound 3

9.58 g (30 mmol) of Compound 1 (15 g, 30 mmol) and 2-bromo-9-phenyl-9H- Compound 3 was prepared in the same manner as in Production Example. (17.0 g, yield 77%, MS: [M + H] &lt; ⁺ &gt; = 746)

The MS spectrum of the compound 3 is shown in Fig.

Preparation Example 4 Preparation of Compound 4

1) Preparation of compound 4-1

The compound 2-1 (30 g, 99 mmol) and dibenzo [b, d] furan-1-ylboronic acid (21 g, 99 mmol) The objective compound 4-1 was prepared in the same manner as in the preparation example 1-4, (34.9 g, yield 81%).

2) Preparation of compound 4-2

Using the compound 4-1 (30 g, 69 mmol) and (2-nitrophenyl) boronic acid (11.5 g, 69 mmol), the same procedure To obtain the target compound 4-2 (29 g, yield 80%).

3) Preparation of compound 4-3

Compound 4-2 (20 g, 38 mmol) was used in the same manner as the preparation example of compound 2-4 to prepare compound 4-3 (14.4 g, yield 77%).

4) Preparation of Compound 4

Compound 11 was obtained by using Compound 4-3 (17 g, 34.8 mmol) and 4-bromo-9-phenyl-9H-carbazole (11.2 g, 34.8 mmol) Compound 4 was prepared in the same manner as in Production Example. (17.8 g, yield 70%, MS: [M + H] &lt; ⁺ &gt; = 730)

The MS spectrum of the compound 4 is shown in Fig.

PREPARATION EXAMPLE 5 Preparation of Compound 5

1) Preparation of compound 5-1

A mixture of 2,4-dichloro-6-phenylpyrimidine (25 g, 111 mmol) and dibenzo [b, d] furan-1-ylboronic acid ] furan-1-ylboronic acid (24 g, 111 mmol), the target compound 5-1 was prepared (34.9 g, yield 88%).

2) Preparation of compound 5-2

Using compound 5-1 (25 g, 70 mmol) and (9H-carbazol-3-yl) boronic acid (15.5 g, 73.6 mmol) 5, the target compound 5-2 was prepared (29 g, yield 80%).

3) Preparation of Compound 5

Compound 5-2 (20 g, 41 mmol) and 3-bromo-9-phenyl-9H-carbazole (13.2 g, 43 mmol) Compound 5 was prepared in the same manner as in Production Example. (19.3 g, yield 76%, MS: [M + H] &lt; ⁺ &gt; = 729)

The MS spectrum of the compound 5 is shown in Fig.

< Example >

Example  One

A thin glass substrate coated with ITO (indium tin oxide) at a thickness of 1,300 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, a Fischer Co. product was used as a detergent, and distilled water, which was filtered with 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. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

The following HI-1 compound was thermally vacuum deposited on the ITO transparent electrode prepared above to a thickness of 50 Å to form a hole injection layer.

The HT-1 compound was thermally vacuum-deposited on the hole injection layer to a thickness of 250 Å to form a hole transport layer, and an HT-2 compound was vacuum deposited on the HT-1 deposition layer to a thickness of 50 Å to form an electron blocking layer.

Subsequently, the phosphorescent dopant GD-1 was vacuum deposited on the HT-2 deposited film at a weight ratio of 90% to the phosphorescent host at a weight ratio of 10% to deposit the light emitting layer with a thickness of 300 Å.

An ET-1 material was vacuum deposited on the light-emitting layer to a thickness of 250 ANGSTROM and an ET-2 material was co-deposited with a 2% weight ratio Li to a thickness of 100 ANGSTROM to form an electron transport layer and an electron injection layer. Aluminum was deposited on the electron injecting layer to a thickness of 1000 to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.7 Å / sec, the deposition rate of aluminum was maintained at 2 Å / sec, and the vacuum degree during deposition was maintained at 1 × 10 ^-7 to 5 × 10 ^-8 torr Respectively.

Example  2 to Example  5

The organic light emitting devices of Examples 2 to 5 were fabricated in the same manner as in Example 1, except that the phosphorescent host material and the dopant content in the light emitting layer were changed as shown in Table 1 below.

< Comparative Example >

Comparative Example  1 to Comparative Example  4

The organic light emitting devices of Comparative Examples 1 to 4 were fabricated in the same manner as in Example 1, except that the phosphorescent host material and the dopant content in the light emitting layer were changed as shown in Table 1 below. Here, the host material compounds A to D used in the comparative example are as follows.

< Experimental Example >

The currents were applied to the organic light emitting devices fabricated in Examples 1 to 5 and Comparative Examples 1 to 4 to measure voltage, efficiency, color coordinates, and lifetime. The results are shown in Table 1 below. In this case, T95 is the optical density of 20mA / cm ² Is the time required for the luminance to be reduced to 95% when the initial luminance is 100%.

division Host: dopant
(Thickness, A) dopant content Voltage (V)
(@ 10 mA / cm ² ) efficiency (%)
(@ 10 mA / cm ² ) Color coordinates
(x, y) Life (T ₉₅ , h)
(@ 20 mA / cm ² ) Example 1 Compound 1: GD-1
(300) 10% 2.94 64.4 (0.318, 0.641) 28.6 Example 2 Compound 2: GD-1
(300) 13% 3.09 67.2 (0.322, 0.630) 32.6 Example 3 Compound 3: GD-1
(400) 12% 2.95 68.2 (0.341, 0.620) 25.0 Example 4 Compound 4: GD-1
(400) 12% 3.06 69.0 (0.340, 0.621) 23.1 Example 5 Compound 5: GD-1
(300) 7% 3.10 68.5 (0.319, 0.6131) 25.6 Comparative Example 1 Compound A: GD-1
(300) 10% 3.22 65.4 (0.318, 0.632) 14.6 Comparative Example 2 Compound B: GD-1
(300) 10% 3.05 63.6 (0.323, 0.629) 19.1 Comparative Example 3 Compound C: GD-1
(400) 10% 3.25 65.3 (0.345, 0.616) 13.4 Comparative Example 4 Compound D: GD-1
(300) 13% 3.33 63.1 (0.334, 0.625) 11.4

1: substrate
2: anode
3: light emitting layer
4: cathode
5: Hole injection layer
6: hole transport layer
7: Electron transport layer

Claims (11)

A compound represented by the following formula (1):
[Chemical Formula 1]

In formula (1)
And at least one of X1 to X3 is N, the rest are CR _5,
Y is S or O,
Ar ₁ and R ₁ to R ₅ are the same or different and each independently hydrogen; heavy hydrogen; A halogen group; Cyano; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
L is a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,
a is an integer of 0 to 5, b, c and d are each an integer of 0 to 7,
When a to d are two or more, the substituents in parentheses are the same or different from each other. The compound of claim 1, wherein the compound represented by Formula 1 is represented by any one of the following Formulas 2 to 10:
(2)

(3)

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

(7)

[Chemical Formula 8]

[Chemical Formula 9]

[Chemical formula 10]

In the general formulas (2) to (10), Ar 1, X 1 to X 3, Y, R ₁ to R ₄ , L and a to d are as defined in the above formula (1). The compound of claim 1, wherein the compound represented by Formula 1 is represented by any one of the following Formulas 11 to 14:
(11)

[Chemical Formula 12]

[Chemical Formula 13]

[Chemical Formula 14]

In the general formula 11 to 14, Ar1, X1 to X3, Y, R ₁ to R _4, the definition of L and a to d are the same as defined in the general formula (1). 2. The compound according to claim 1, wherein X1 to X3 are all N. 2. The compound of claim 1, wherein L is a direct bond; A phenylene group; Biphenyllylene groups; A naphthalene group; A pyridyl group; A pyrimidylene group; A furanylene group; Thiophenylene group; An imidazolylene group; Benzothiophenylene groups; Benzofuranyl groups; A benzothiazolyl group; Or a benzooxazolylene group. 2. The compound according to claim 1, wherein L is a direct bond or a phenylene group. 2. The compound according to claim 1, wherein Ar1 is a substituted or unsubstituted phenyl group. The compound according to claim 1, wherein the compound represented by Formula 1 is selected from the following structural formulas:

A first electrode; A second electrode facing the first electrode; And at least one organic layer disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes a compound according to any one of claims 1 to 8, device. The organic light emitting device according to claim 9, wherein the organic layer includes a light emitting layer, and the light emitting layer comprises the compound. [Claim 11] The organic light emitting device according to claim 9, wherein the organic layer includes an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer comprises the compound.

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