KR102032953B1 - Novel hetero-cyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a novel compound and an organic light emitting device using the same.

Description

Novel hetero-cyclic compound and organic light emitting device comprising the same

The present invention relates to a novel compound and an organic light emitting device comprising the same.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, excellent brightness, driving voltage and response speed characteristics, many studies have been conducted.

The organic light emitting device generally has a structure including an anode and a cathode and an organic material layer between the anode and the cathode. The organic material layer is often made of a multi-layered structure composed of different materials to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and the electrons meet each other. When it falls back to the ground, it glows.

There is a continuous demand for the development of new materials for organic materials used in such organic light emitting devices.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to a novel compound and an organic light emitting device comprising the same.

The present invention provides a compound represented by Formula 1:

[Formula 1]

In Chemical Formula 1,

X ₁ is O or S,

X ₂ is O, S, or N (Ar ₃ ),

Y ₁ to Y ₃ are each independently N or CR ₅ , at least one of Y ₁ to Y ₃ is N,

L ₁ and L ₂ are each independently a bond; Substituted or unsubstituted C _6-60 arylene; Or C _2-60 heteroarylene containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted O, N, Si, and S,

Ar ₁ to Ar ₃ are each independently, substituted or unsubstituted C _6-60 aryl; Or C 2 _-60 heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,

R ₁ to R ₅ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Amino; Substituted or unsubstituted C _1-60 alkyl; C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Or a C _2-60 heterocyclic group containing one or more hetero atoms selected from the group consisting of substituted or unsubstituted N, O and S,

a1, a2 and b1 to b4 are each independently an integer of 0 to 3.

In addition, the present invention is a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include the compound represented by Chemical Formula 1. .

The compound represented by Chemical Formula 1 may be used as a material of the organic material layer of the organic light emitting device, and may improve efficiency, low driving voltage, and / or lifetime characteristics in the organic light emitting device. In particular, the compound represented by Chemical Formula 1 may be used as a hole injection, hole transport, hole injection and transport, light emission, electron transport, or electron injection material.

FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. As shown in FIG.
FIG. 2 shows an example of an organic light emitting element consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4 It is.

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

는 다른 치환기에 연결되는 결합을 의미하고, 단일 결합은 L₁ 및 L₂로 표시되는 부분에 별도의 원자가 존재하지 않은 경우를 의미한다. In this specification,

Means a bond connected to another substituent, and a single bond means a case where no separate atom is present in a moiety represented by L ₁ and L ₂ .

As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Cyano group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; An alkyl group; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Alkylamine group; Aralkyl amine groups; Heteroarylamine group; Arylamine group; Aryl phosphine group; Or substituted or unsubstituted with one or more substituents selected from the group consisting of heterocyclic groups including one or more of N, O and S atoms, or two or more substituents of the above-described substituents connected or substituted. . For example, "a substituent to which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are linked.

Although carbon number of a carbonyl group in this specification is not specifically limited, It is preferable that it is C1-C40. Specifically, it may be a compound having a structure as follows, but is not limited thereto.

In the present specification, the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In this specification, although carbon number of an imide group is not specifically limited, It is preferable that it is C1-C25. Specifically, it may be a compound having a structure as follows, but is not limited thereto.

In the present specification, specifically, the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like. However, the present invention is not limited thereto.

In the present specification, the boron group specifically includes, but is not limited to, trimethylboron group, triethylboron group, t-butyldimethylboron group, triphenylboron group, phenylboron group, and the like.

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary 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-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present specification, the alkenyl group may be linear or branched chain, the carbon number is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary 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, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 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 an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, but may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto. The polycyclic aryl group may be naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. When the fluorenyl group is substituted,

And so on. However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing one or more of O, N, Si, and S as a dissimilar element, and the carbon number is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heterocyclic groups include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole group, Acridyl group, pyridazine group, pyrazinyl group, quinolinyl group, quinazoline group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinoline group , Indole group, carbazole group, benzoxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group (phenanthroline), thiazolyl group, Isooxazolyl group, oxdiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group and the like, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, and arylamine group is the same as the example of the aryl group described above. In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group is the same as the example of the alkyl group described above. In the present specification, the heteroaryl of the heteroarylamine may be applied to the description of the aforementioned heterocyclic group. In the present specification, the alkenyl group in the aralkenyl group is the same as the example of the alkenyl group described above. In the present specification, the description of the aryl group described above may be applied except that the arylene is a divalent group. In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the aforementioned aryl group or cycloalkyl group may be applied except that two substituents are formed by bonding. In the present specification, the heterocyclic group is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied except that two substituents are formed by bonding.

On the other hand, the present invention provides a compound represented by the formula (1).

In Chemical Formula 1,

X ₁ may be O and X ₂ may be N (Ar ₃ ).

Also,

Y ₁ is N, Y ₂ and Y ₃ are CR _5, or

Y ₂ is N, Y ₁ and Y ₃ are CR _5, or

Y ₁ and Y ₂ are N, Y ₃ is CR _5, or

Y ₁ and Y ₃ are N, Y ₂ is CR _5, or or

Y ₁ , Y ₂ and Y ₃ may be N.

E.g,

Y ₁ is N, Y ₂ and Y ₃ are CH,

Y ₂ is N, Y ₁ and Y ₃ are CH, or

Y ₁ and Y ₂ are N, Y ₃ is CH, or

Y ₁ and Y ₃ are N, Y ₂ is CH, or or

Y ₁ , Y ₂ and Y ₃ may be N.

In addition, L ₁ and L ₂ may each independently be a bond, a substituted or unsubstituted phenylene, a substituted or unsubstituted biphenylene, or a substituted or unsubstituted naphthylene. In this case, a1 and a2 may be each independently 0 or 1.

For example, L ₁ and L ₂ may each independently be a bond, or any one selected from the group consisting of:

.

.

For example, L ₁ and L ₂ can be a bond.

In addition, Ar ₁ to Ar ₃ may each independently be any one selected from the group consisting of:

In the above,

Z ₁ to Z ₄ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Amino; Substituted or unsubstituted C _1-20 alkyl; Substituted or unsubstituted C _1-20 haloalkyl; Substituted or unsubstituted C _6-20 aryl; Or a C _2-20 heterocyclic group containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,

c1 and c2 are each independently an integer of 0-3.

Here, Z ₁ and Z ₂ are each independently hydrogen; heavy hydrogen; Cyano; Phenyl; Biphenyl; Pyridinyl; Or pyridinylphenyl, Z ₃ and Z ₄ may be methyl.

For example, Ar ₁ and Ar ₂ may each independently be any one selected from the group consisting of:

In addition, Ar ₃ may be any one selected from the group consisting of:

.

.

R ₁ to R ₅ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Amino; methyl; Or phenyl, b1 and b4 may each independently be 0 or 1.

For example, R ₁ to R ₅ may be hydrogen.

In this case, a1 represents the number of L ₁ , and when a1 is 2 or more, two or more L ₁ may be identical to or different from each other. Description of a2, b1 to b4, c1 and c2 can be understood with reference to the description of a1 and the structure of the formula.

In addition, the compound may be represented by the following Formula 1-1:

[Formula 1-1]

In Chemical Formula 1-1,

Description of X ₁ , X ₂ , Y ₁ to Y ₃ and Ar ₁ to Ar ₃ are the same as defined in Chemical Formula 1.

In addition, the compound may be any one selected from the group consisting of the following compounds:

The compound represented by Formula 1 is a 6-membered heterocyclic group containing at least one N atom and a dibenzofuran / dibenzothiophene / carbazolyl group connected to a specific position of dibenzofuran or dibenzothiophene core By having a structure, the organic light emitting device using the same may have high efficiency, low driving voltage, high brightness, long life, and the like.

On the other hand, the compound represented by the formula (1-1) can be prepared by a manufacturing method such as Scheme 1 below. The manufacturing method may be more specific in the production examples to be described later.

Scheme 1

In Reaction Scheme 1, X ₁ , X ₂ , Y ₁ to Y ₃ and Ar ₁ to Ar ₃ , the description of the same as defined in Formula 1 above, Z each independently represent a halogen.

The compound represented by Formula 1 may be prepared by appropriately replacing the starting material in accordance with the structure of the compound to be prepared with reference to Scheme 1.

On the other hand, the present invention provides an organic light emitting device comprising the compound represented by the formula (1). In one embodiment, the present invention is a first electrode; A second electrode provided to face the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include the compound represented by Chemical Formula 1. .

The organic material layer of the organic light emitting 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 light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

The organic material layer may include a hole injection layer, a hole transport layer, or a layer for simultaneously injecting and transporting holes, and the hole injection layer, a hole transport layer, or a layer for simultaneously injecting holes and transporting holes may be represented by Chemical Formula 1 above. It may include a compound represented.

In addition, the organic material layer may include a light emitting layer, and the light emitting layer may include a compound represented by Chemical Formula 1.

In addition, the electron transport layer, the electron injection layer, or may include a layer for simultaneously transporting electrons and electron injection, the electron transport layer, the electron injection layer, or a layer for the simultaneous transport and electron injection is represented by the formula (1) It may include a compound.

In addition, the organic material layer may include a light emitting layer and an electron transport layer, and the electron transport layer may include a compound represented by Chemical Formula 1.

In addition to the organic layer, the organic light emitting device may include an electron blocking layer (EBL) positioned between the hole transport layer and the light emitting layer and / or a hole blocking layer disposed between the light emitting layer and the electron transport layer. layer: HBL) may be further included. In such a structure, the compound represented by Formula 1 may be included in one or more layers of the electron blocking layer and the hole blocking layer. The electron blocking layer and the hole blocking layer may each be an organic material layer adjacent to the emission layer.

In this case, the compound represented by Chemical Formula 1 may be included in the emission layer, the electron transport layer, or the hole blocking layer.

The organic material layer of the organic light emitting 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 light emitting device of the present invention further includes a hole injection layer and a hole transport layer between the first electrode and the light emitting layer, an electron transport layer and an electron injection layer between the light emitting layer and the second electrode, in addition to the light emitting layer as an organic layer. It may have a structure to. However, the structure of the organic light emitting device is not limited thereto, and may include fewer or more organic layers.

In addition, the organic light emitting device according to the present invention may be an organic light emitting device having a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. In addition, the organic light emitting device according to the present invention may be an organic light emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. For example, the structure of an organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 and 2.

FIG. 1 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. As shown in FIG. In such a structure, the compound represented by Formula 1 may be included in the light emitting layer.

FIG. 2 shows an example of an organic light emitting element consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4 It is. In such a structure, the compound represented by Chemical Formula 1 may be included in one or more layers of the hole injection layer, the hole transport layer, the light emitting layer and the electron transport layer.

The organic light emitting device according to the present invention may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer includes the compound represented by Chemical Formula 1. In addition, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on the substrate to form an anode. In addition, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer may be formed thereon, and then, a material that may be used as a cathode may be deposited thereon. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, the compound represented by Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method in the manufacture of the organic light emitting device. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.

In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material on a substrate from a cathode material (WO 2003/012890). However, the manufacturing method is not limited thereto.

In one example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode, the second electrode is an anode.

As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific 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), indium zinc oxide (IZO); Combinations of oxides with metals such as ZnO: Al or SNO ₂ : Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, and the like, but are not limited thereto.

It is preferable that the cathode material is 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.

The hole injection layer is a layer for injecting holes from the electrode, and has a capability of transporting holes to the hole injection material, and has a hole injection effect at the anode, an excellent hole injection effect to the light emitting layer or the light emitting material, and is produced in the light emitting layer The compound which prevents the excitons from moving to the electron injection layer or the electron injection material, and is excellent in thin film formation ability is preferable. Preferably, the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based Organic materials, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light emitting layer. As a hole transport material, 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 thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq ₃ ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; 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 as described above. The host material may further include a condensed aromatic ring derivative or a hetero ring-containing compound in addition to the compound represented by Formula 1 above. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and the heterocyclic containing compounds include carbazole derivatives, dibenzofuran derivatives and ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Dopant materials include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic amine derivatives include condensed aromatic ring derivatives having a substituted or unsubstituted arylamino group, and include pyrene, anthracene, chrysene, and periplanthene having an arylamino group, and a styrylamine compound may be substituted or unsubstituted. At least one arylvinyl group is substituted with the arylamine, and one or two or more substituents selected from the group consisting of aryl group, silyl group, alkyl group, cycloalkyl group and arylamino group are substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the light emitting layer. The electron transporting material is a material that can inject electrons well from the cathode and transfer them to the light emitting layer. Suitable. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The electron transport layer can be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by an aluminum or silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, followed by aluminum layers or silver layers in each case.

The electron injection layer is a layer for injecting electrons from an electrode, has an ability of transporting electrons, has an electron injection effect from the cathode, an excellent electron injection effect to the light emitting layer or the light emitting material, and the hole injection of excitons generated in the light emitting layer The compound which prevents the movement to a layer and is excellent in thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the derivatives thereof, metal Complex compounds, nitrogen-containing five-membered ring derivatives, and the like, 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-hydroxyquinolinato) manganese, Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtolato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtolato) gallium, It is not limited to this.

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

In addition, the compound represented by Formula 1 may be included in an organic solar cell or an organic transistor in addition to the organic light emitting device.

The invention is explained in more detail in the following examples. However, the following examples are merely to illustrate the invention, but the content of the present invention is not limited by the following examples.

Preparation Example 1 Compound Synthesis of Intermediates A1 to A3

(1) Preparation of Intermediate A1

1000 mL of 2-hydrodobenzene-1,3-diol (100 g, 0.42 mol) and (3-chloro-2-fluorophenyl) boronic acid (81.3 g, 0.47 mol) in a 2000 mL round-bottom flask under nitrogen atmosphere After dissolving in water, an aqueous solution of potassium carbonate (175 g, 1.27 mol) dissolved in 500 ml of water was added, Bis (tri- tert- butylphosphine) palladium (0) (2.17 g, 4.23 mmol) was added thereto, and the mixture was heated and stirred for 1 hour. The temperature was lowered to room temperature, the water layer was separated and removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, recrystallized with hexane and dried to prepare the intermediate A1 (80.2 g, yield 79%, MS: [M + H). ] ⁺ = 239).

(2) Preparation of Intermediate A2

Intermediate A1 (80.2 g, 0.33 mol) and potassium carbonate (139 g, 1.01 mol) were dissolved in 400 mL of N-methyl-2-pyrrolidone and heated and stirred for 1 hour. Lower the temperature to room temperature and filter by reverse precipitation in water. After completely dissolved in dichloromentane, washed with water, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, recrystallized with ethanol and dried to prepare the intermediate A2 (53.2 g, yield 72%, MS: [M + H] ⁺ = 219).

(3) Preparation of Intermediate A3

Dissolve intermediate A2 (53.2 g, 0.23 mol) in 75 mL of acetonitrile, dissolve calcium carbonate (47.3 g, 0.34 mol) in 100 mL of water, and add nonafluorobutanesulfonyl fluoride (45.2 mL, 0.25 mol) at 0 ° C for 25 minutes. Slowly drop it off. Then stirred at room temperature for 3 hours. Upon completion of the reaction, the mixture was filtered, completely dissolved in dichloromentane, washed with water, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, recrystallized with ethanol and dried to prepare the intermediate A3 (83.3 g, yield 73%, MS: [ M + H] ⁺ = 501).

Preparation Example 2-1 Compound Synthesis of Intermediate B1

(1) Preparation of Intermediate B-1

Intermediate A4 (20.0 g, 0.04 mol) and (9-phenyl-9H-carbazol-3-yl) boronic acid (11.5 g, 0.04 mmol) were dissolved in 250 mL of tetrahydrofuran and potassium carbonate (16.6) dissolved in 60 ml of water. g, 0.12 mol) was added, tetrakis- (triphenylphosphine) palladium (0.2 g, 0.40 mmol) was added thereto, followed by heating and stirring for 9 hours. The temperature was lowered to room temperature, the water layer was separated and removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with a tetrahydrofuran and ethyl acetate mixed solution and dried to prepare the intermediate B-1 (15.1 g, Yield 85%, MS: [M + H] ⁺ = 444).

(2) Preparation of Intermediate B1

Intermediate B-1 (15.1 g, 0.03 mol), 4,4,5,5-tetramethyl- [1, 3, 2] -dioxaboralane (9.5 g, 0.04 mol), Pd (dba) ₂ (0.59 g, 1.02 mmol ), PCy ₃ (0.57 g, 2.04 mmol) and KOAc (10.01 g, 0.10 mol) were added to 150 mL of dioxane and stirred at reflux for 7 hours. The temperature was lowered to room temperature and the solvent was concentrated under reduced pressure. The concentrate was completely dissolved in CHCl ₃ , washed with water, and the solution was dissolved under reduced pressure, and then purified by column chromatography. Intermediate B1 was obtained (16.8 g, yield 92%, MS: [M + H] ⁺ = 536).

Preparation Example 2-2: Compound Synthesis of Intermediate B2

Intermediate B2 was prepared by the same method as the method for preparing Intermediate B1, except that (9-phenyl-9H-carbazol-2-yl) boronic acid was used instead of (9-phenyl-9H-carbazol-3-yl) boronic acid. It was.

Preparation Example 2-3 Compound Synthesis of Intermediate B3

Intermediate B3 was prepared by the same method as the method for preparing intermediate B1, except that (9-phenyl-9H-carbazol-4-yl) boronic acid was used instead of (9-phenyl-9H-carbazol-3-yl) boronic acid. It was.

Preparation Example 2-4 Compound Synthesis of Intermediate B4

Intermediate B4 was prepared in the same manner as the preparation of intermediate B1, except that dibenzo [b, d] furan-2-ylboronic acid was used instead of (9-phenyl-9H-carbazol-3-yl) boronic acid.

Preparation Example 2-5 Compound Synthesis of Intermediate B5

Intermediate B5 was prepared by the same method as the preparation of intermediate B1, except that dibenzo [b, d] furan-4-ylboronic acid was used instead of (9-phenyl-9H-carbazol-3-yl) boronic acid.

Preparation Example 2-6 Compound Synthesis of Intermediate B6

Intermediate B6 was prepared by the same method as the method of preparing intermediate B1, except that dibenzo [b, d] furan-3-ylboronic acid was used instead of (9-phenyl-9H-carbazol-3-yl) boronic acid.

Preparation Example 2-7 Compound Synthesis of Intermediate B7

Intermediate B7 was prepared by the same method as the method of preparing intermediate B1, except that dibenzo [b, d] furan-1-ylboronic acid was used instead of (9-phenyl-9H-carbazol-3-yl) boronic acid.

Preparation Example 2-8 Compound Synthesis of Intermediate B8

Intermediate B8 was prepared by the same method as the method of preparing intermediate B1, except that dibenzo [b, d] thiophen-3-ylboronic acid was used instead of (9-phenyl-9H-carbazol-3-yl) boronic acid.

Preparation Example 3-1 Synthesis of Compound 1

Dissolve intermediate B1 (10.0 g, 0.019 mol) and 2-chloro-4,6-diphenyl-1,3,5-triazine (4.99 g, 00.19 mol) in 120 mL of tetrahydrofuran in a nitrogen atmosphere, and then in 60 ml of water. Dissolved potassium carbonate (5.2 g, 0.04 mol) was added, tetrakis- (triphenylphosphine) palladium (0.7 g, 0.56 mmol) was added thereto, and the mixture was heated and stirred for 17 hours. The temperature was lowered to room temperature and filtered. After dissolving with chloroform and washing with water, water is removed with MgSO ₄ and solvent is removed. Subsequently, Compound 1 was prepared by recrystallization using a tetrahydrofuran and ethyl acetate mixed solution. (9.5 g, yield 79%, MS: [M + H] ⁺ = 641)

Preparation Example 3-2: Synthesis of Compound 2

2-([1,1'-biphenyl] -3-yl) -4-chloro-6-phenyl-1,3,5-triazine instead of 2-chloro-4,6-diphenyl-1,3,5-triazine Compound 2 was prepared by the same method as the method of preparing compound 1, except for using. (Yield 70%, MS: [M + H] ⁺ = 717)

Preparation Example 3-3: Synthesis of Compound 3

2-chloro-4- (dibenzo [b, d] furan-4-yl) -6-phenyl-1,3,5-triazine instead of 2-chloro-4,6-diphenyl-1,3,5-triazine Compound 3 was prepared by the same method as the method of preparing compound 1, except that it was used. (Yield 72%, MS: [M + H] ⁺ = 731)

Preparation Example 3-4: Synthesis of Compound 4

Compound 4 was prepared by the same method as the method of preparing compound 1, except that 2-chloro-4,6-diphenylpyrimidine was used instead of 2-chloro-4,6-diphenyl-1,3,5-triazine. (Yield 68%, MS: [M + H] ⁺ = 640)

Preparation Example 3-5 Synthesis of Compound 5

Compound 5 was prepared by the same method as the method of preparing compound 1, except that intermediate B2 was used instead of intermediate B1. (Yield 70%, MS: [M + H] ⁺ = 641)

Preparation Example 3-6: Synthesis of Compound 6

Except that intermediate B2 and 2- (3-bromophenyl) -4,6-diphenyl-1,3,5-triazine are used instead of intermediate B1 and 2-chloro-4,6-diphenyl-1,3,5-triazine Compound 6 was prepared by the same method as the method of preparing compound 1. (Yield 74%, MS: [M + H] ⁺ = 717).

Preparation Example 3-7 Synthesis of Compound 7

Compound 7 was prepared in the same manner as in the preparation of Compound 1, except that Intermediate B2 and 4-chloro-2,6-diphenylpyrimidine were used instead of Intermediate B1 and 2-chloro-4,6-diphenyl-1,3,5-triazine. Was prepared. (Yield 68%, MS: M + H) ⁺ = 640)

Preparation Example 3-8: Synthesis of Compound 8

Intermediate B2 and 2-([1,1'-biphenyl] -2-yl) -4-chloro-6-phenyl-1 instead of Intermediate B1 and 2-chloro-4,6-diphenyl-1,3,5-triazine Compound 8 was prepared by the same method as the method of preparing compound 1, except that 3,5-triazine was used. (Yield 66%, MS: [M + H] ⁺ = 717)

Preparation Example 3-9: Synthesis of Compound 9

Compound 9 was prepared by the same method as the method of preparing compound 1, except that intermediate B3 was used instead of intermediate B1. (Yield 69%, MS: [M + H] ⁺ = 641)

Preparation Example 3-10: Synthesis of Compound 10

Intermediate B3 and 3- (4-([1,1'-biphenyl] -4-yl) -6-chloro-1, instead of intermediate B1 and 2-chloro-4,6-diphenyl-1,3,5-triazine Compound 10 was prepared by the same method as the method of preparing compound 1, except that 3,5-triazin-2-yl) benzene-1-ylium was used. (Yield 73%, MS: [M + H] ⁺ = 717)

Preparation Example 3-11 Synthesis of Compound 11

Compound 11 was prepared in the same manner as for preparing Compound 1, except that Intermediate B4 was used instead of Intermediate B1. (Yield 67%, MS: [M + H] ⁺ = 566)

Preparation Example 3-12 Synthesis of Compound 12

Intermediate B1 and 2-([1,1'-biphenyl] -3-yl) -4-chloro-6-phenyl-1 instead of Intermediate B1 and 2-chloro-4,6-diphenyl-1,3,5-triazine Compound 12 was prepared by the same method as the method of preparing compound 1, except that 3,5-triazine was used. (Yield 70%, MS: [M + H] ⁺ = 642)

Preparation Example 3-13: Synthesis of Compound 13

Compound 13 was prepared by the same method as the method of preparing compound 1, except that intermediate B5 was used instead of intermediate B1. (Yield 69%, MS: [M + H] ⁺ = 566)

Preparation Example 3-14: Synthesis of Compound 14

Except for using Intermediate B5 and 2- (4-bromophenyl) -4,6-diphenyl-1,3,5-triazine in place of Intermediate B1 and 2-chloro-4,6-diphenyl-1,3,5-triazine Compound 14 was prepared by the same method as the method of preparing compound 1. (Yield 72%, MS: [M + H] ⁺ = 642)

Preparation Example 3-15: Synthesis of Compound 15

Intermediate B1 and 4- (4-chloro-6-phenyl-1,3,5-triazin-2-yl) benzonitrile instead of intermediate B1 and 2-chloro-4,6-diphenyl-1,3,5-triazine Compound 15 was prepared by the same method as the method of preparing compound 1, except that. (Yield 73%, MS: [M + H] ⁺ = 591)

Preparation Example 3-16 Synthesis of Compound 16

Intermediates B6 and 2,4-di ([1,1'-biphenyl] -4-yl) -6-chloro-1, instead of intermediate B1 and 2-chloro-4,6-diphenyl-1,3,5-triazine Compound 16 was prepared by the same method as the method of preparing compound 1, except that 3,5-triazine was used. (Yield 74%, MS: [M + H] ⁺ = 718)

Preparation Example 3-17: Synthesis of Compound 17

Compound 17 was prepared in the same manner as in the preparation of Compound 1, except that Intermediate B7 and 2-chloro-4,6-diphenylpyridine were used instead of Intermediate B1 and 2-chloro-4,6-diphenyl-1,3,5-triazine. Was prepared. (Yield 67%, MS: [M + H] ⁺ = 564).

Preparation Example 3-18 Synthesis of Compound 18

Intermediate B7 and 2-([1,1'-biphenyl] -4-yl) -4-chloro-6-phenyl-1 instead of Intermediate B1 and 2-chloro-4,6-diphenyl-1,3,5-triazine Compound 18 was prepared by the same method as the method of preparing compound 1, except that 3,5-triazine was used. (Yield 69%, MS: [M + H] ⁺ = 642)

Preparation Example 3-19: Synthesis of Compound 19

Intermediate B8 and 2-chloro-4- (dibenzo [b, d] furan-3-yl) -6-phenyl-1, instead of intermediate B1 and 2-chloro-4,6-diphenyl-1,3,5-triazine Compound 19 was prepared by the same method as the method of preparing compound 1, except that 3,5-triazine was used. (Yield 70%, MS: [M + H] ⁺ = 672)

Preparation Example 3-20 Synthesis of Compound 20

Intermediate B8 and 4-([1,1'-biphenyl] -4-yl) -2-chloro-6-phenylpyrimidine instead of intermediate B1 and 2-chloro-4,6-diphenyl-1,3,5-triazine Compound 20 was prepared by the same method as the method of preparing compound 1, except that. (Yield 71%, MS: [M + H] ⁺ = 657)

Example 1

A glass substrate coated with a thin film of ITO (indium tin oxide) having a thickness of 1,300 mm 3 was placed in distilled water in which detergent was dissolved and ultrasonically cleaned. In this case, Fischer Co. product was used as a detergent, and distilled water filtered secondly as a filter of Millipore Co. product was used as distilled water. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After washing the distilled water, ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol, dried and transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.

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

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

Subsequently, Compound 1 and phosphorescent dopant YGD-1 were co-deposited on the HT-2 deposited film to form a light emitting layer having a thickness of 400 kHz. In this case, the content of the phosphorescent dopant YGD-1 in the total light emitting layer is 12% by weight.

An ET-1 compound was vacuum deposited on the emission layer to form a electron transport layer by vacuum deposition, and an electron injection layer was formed by co-depositing the ET-2 compound and Li at a weight ratio of 98: 2 on the electron transport layer. . Aluminum was deposited to a thickness of 1000 Å on the electron injection layer to form a cathode.

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

Examples 2 to 10

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 1 in Example 1 was used instead of Compound 1. In Table 1 below, H 2 means the following compound. In this case, when a mixture of two compounds is used as the host material, the parenthesis means the weight ratio between the compounds.

Comparative Examples 1 to 3

An organic light-emitting device was manufactured in the same manner as in Example 1, except that Compound 1 in Example 1 was used instead of Compound 1. In Table 1, C1 and C2 mean the following compounds, respectively. In this case, when a mixture of two compounds is used as the host material, the parenthesis means the weight ratio between the compounds.

Applying a current of 10mA / cm ² to the organic light emitting device of Examples 1 to 10 and Comparative Examples 1 to 3 to measure the voltage and efficiency, and applying a current of 20mA / cm ² to measure the lifetime, respectively It is shown in Table 1 below. T95 means the time taken for the luminance to decrease to 95% from the initial luminance.

Host substance Voltage
(V, @ 10mA / cm ² ) efficiency
(cd / A, @ 10mA / cm ² ) Color coordinates
(x, y) life span
(T95, h,
@ 20mA / cm ² ) Example 1 Compound 1 3.7 73 0.45, 0.52 52 Example 2 Compound 4 3.9 70 0.44, 0.53 42 Example 3 Compound 6 3.8 75 0.44, 0.52 44 Example 4 Compound 14 3.8 74 0.45, 0.53 47 Example 5 Compound 17 3.9 73 0.45, 0.52 51 Example 6 Compound 2: h2
(50:50) 4.1 84 0.45, 0.52 96 Example 7 Compound 5: h2
(50:50) 4.0 81 0.45, 0.53 97 Example 8 Compound 12: H2
(50:50) 4.0 85 0.44, 0.52 92 Example 9 Compound 18: H2
(50:50) 4.1 75 0.46, 0.53 95 Example 10 Compound 20: H2
(50:50) 4.0 79 0.45, 0.52 91 Comparative Example 1 C1: H2
(50:50) 4.6 72 0.45, 0.51 80 Comparative Example 2 C1 3.9 60 0.45, 0.53 10 Comparative Example 3 C2 3.0 60 0.46, 0.53 40

According to Table 1, it was confirmed that the organic light emitting device of Examples 1 to 10 has a higher efficiency than the organic light emitting device of Comparative Examples 1 to 3 each containing C1 and C2 as a host material.

In particular, it was confirmed that the difference in efficiency and life according to the position of the substituent substituted in the dibenzofuran, specifically, the host material of Examples 1 to 10 where the substituents are substituted at positions 1 and 6 of the dibenzofuran Compared with C1 of Comparative Examples 1 and 2, in which substituents are substituted at positions 2 and 4 of dibenzofuran, the device exhibits elemental strengths in terms of the balance between the electrons and the electrons entering the light emitting layer from adjacent layers, and the efficiency and lifespan are remarkable. Confirmed that it is high.

1: substrate 2: anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: light emitting layer 8: electron transport layer

Claims (14)

Compound represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
X ₁ is O, or S,
X ₂ is O, or S,
Y ₁ to Y ₃ are each independently N or CR ₅ , at least one of Y ₁ to Y ₃ is N,
L ₁ and L ₂ are each independently a bond; C _6-60 arylene; Or C _2-60 heteroarylene containing one or more heteroatoms selected from the group consisting of O, N, Si and S,
Ar ₁ and Ar ₂ are each independently C _6-60 aryl unsubstituted or substituted with a cyano group; Or C 2 _-60 heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of N, O and S,
R ₁ to R ₅ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Amino; C _1-60 alkyl; C _1-60 haloalkyl; C _1-60 alkoxy; C _1-60 haloalkoxy; C _3-60 cycloalkyl; C _2-60 alkenyl; C _6-60 aryl; C _6-60 aryloxy; Or a C _2-60 heterocyclic group including one or more heteroatoms selected from the group consisting of N, O and S,
a1, a2 and b1 to b4 are each independently an integer of 0 to 3;
The method of claim 1,
X ₁ is O.
The method of claim 1,
Y ₁ is N, Y ₂ and Y ₃ are CH,
Y ₂ is N, Y ₁ and Y ₃ are CH, or
Y ₁ and Y ₂ are N, Y ₃ is CH, or
Y ₁ and Y ₃ are N, Y ₂ is CH, or or
Y ₁ , Y ₂ and Y ₃ are N, compound.
The method of claim 1,
L ₁ and L ₂ are each independently a bond, or any one selected from the group consisting of:

.
The method of claim 1,
Ar ₁ and Ar ₂ are each independently any one selected from the group consisting of:

In the above,
Z ₁ to Z ₄ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Amino; C _1-20 alkyl; C _1-20 haloalkyl; C _6-20 aryl; Or a C _2-20 heterocyclic group containing at least one heteroatom selected from the group consisting of N, O and S,
c1 and c2 are each independently an integer of 0-3.
The method of claim 5,
Ar ₁ and Ar ₂ are each independently any one selected from the group consisting of:

delete The method of claim 1,
R ₁ to R ₅ are hydrogen.
The method of claim 1,
The compound is represented by Formula 1-1, a compound:
[Formula 1-1]

In Chemical Formula 1-1,
Description of X ₁ , X ₂ , Y ₁ to Y ₃ , Ar ₁ and Ar ₂ is as defined in claim 1.
The method of claim 1,
The compound is any one selected from the group consisting of the following compounds:

A first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers is any one of claims 1 to 6 and 8 to 10. An organic light emitting device comprising the compound according to one claim.
The method of claim 11,
The organic material layer containing the compound is a hole injection layer; Hole transport layer; Or an organic light emitting device which is a layer for simultaneously injecting holes and transporting holes.
The method of claim 11,
The organic material layer containing the compound is an electron injection layer; Electron transport layer; Or an organic light emitting element, which is a layer for simultaneously performing electron injection and electron transport.
The method of claim 11,
The organic material layer containing the compound is a light emitting layer, an organic light emitting device.

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