KR102230060B1 - Novel 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 including the same.

Description

Novel 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, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy by using an organic material. An organic light-emitting device using the organic light-emitting phenomenon has a wide viewing angle, excellent contrast, and fast response time, and has excellent luminance, driving voltage, and response speed characteristics, and thus many studies are being conducted.

An 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 multilayer structure made of different materials in order to increase the efficiency and stability of the organic light emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an organic light emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. When it falls back to the ground, it glows.

Development of new materials for organic materials used in organic light emitting devices as described above is continuously required.

Korean Patent Publication No. 10-2000-0051826

The present invention relates to a novel organic light-emitting material and an organic light-emitting device including the same.

The present invention provides a compound represented by the following formula (1):

[Formula 1]

In Formula 1,

Y is O or S,

L is a single bond; Substituted or unsubstituted C _6-60 arylene; _{Or substituted or unsubstituted C 6-60} heteroarylene including any one or more selected from the group consisting of N, O and S,

X ₁ , X ₂ and X ₃ are each independently N or CH, provided that at least two of _{X 1} , X ₂ , and X _{3 are N,}

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 6-60} heteroaryl including any one or more selected from the group consisting of N, O and S.

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 at least one of the organic material layers includes a compound represented by Formula 1 do.

The compound represented by Chemical Formula 1 may be used as a material for an organic material layer of an 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 Formula 1 may be used as a hole injection, hole transport, hole injection and transport, electron blocking, light emission, hole blocking, electron transport, or electron injection material.

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.
2 is a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (7), a light emitting layer (3), an electron transport layer (9), an electron injection layer (10). And an example of an organic light-emitting device comprising the cathode 4 is shown.
3 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, a hole blocking layer 8, an electron transport layer 9 and a cathode 4 It shows an example of an organic light-emitting device.

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

The present invention provides a compound represented by Chemical Formula 1.

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

Means a bond connected to another substituent.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; Or it means substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more of N, O, and S atoms, or substituted or unsubstituted with two or more substituents connected among the above exemplified substituents. . For example, "a substituent to which two or more substituents are connected" 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 connected.

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the ester group may be substituted with a C1-C25 linear, branched or cyclic alkyl group or an aryl group having 6 to 25 carbon atoms in the oxygen of the ester group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

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

In the present specification, the boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, and a phenyl boron group, but is not limited thereto.

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, and the number of carbon atoms 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 are not limited thereto.

In the present specification, the alkenyl group may be a linear or branched chain, and the number of carbon atoms 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 an exemplary 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 is preferably 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 phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a 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,

Can be, etc. However, it is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group containing at least one of O, N, Si, and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but it is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group 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, 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, isoxazolyl group, thiiadia There are a zolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, the aryl group among 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 aforementioned alkyl group. In the present specification, for heteroaryl among heteroarylamines, the description of the aforementioned heterocyclic group may be applied. In the present specification, the alkenyl group of 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 aryl group or cycloalkyl group described above may be applied except that the hydrocarbon ring is formed by bonding of two substituents. In the present specification, the heterocycle is not a monovalent group, and the description of the aforementioned heterocyclic group may be applied, except that two substituents are bonded to each other and formed.

Preferably, L is a single bond, phenylene, biphenylene, carbazolylene, dibenzofuranylene, or dibenzothiophenylene.

Preferably, X ₁ , X ₂ and X ₃ are all N.

Preferably, at least one of _{Ar 1} and Ar _{2 is substituted or unsubstituted C 6-60} aryl.

Preferably, at least one of _{Ar 1} and Ar _{2 is substituted or unsubstituted C 6-20} aryl.

More preferably, Ar ₁ and Ar ₂ are each independently, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl , Carbazolyl, carbazolyl substituted with phenyl, phenyl substituted with dibenzofuranyl, or phenyl substituted with dibenzothiophenyl.

More preferably, Ar ₁ and Ar ₂ are each independently, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, 9,9-dimethyl-9H-fluorenyl, dibenzo Furanyl, dibenzothiophenyl, carbazolyl, 9-phenyl-9H-carbazolyl, phenyl substituted with dibenzofuranyl, or phenyl substituted with dibenzothiophenyl.

More preferably _{, at least one of Ar 1} and Ar ₂ is phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, or dimethylfluorenyl.

The compound may be represented by any one of the following Formulas 1-1 to 1-3:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3,

Description of Y, L, X ₁ , X _2, X ₃ , Ar ₁ and Ar ₂ are as defined in Chemical Formula 1.

Representative examples of the compound represented by Formula 1 are as follows:

The compound represented by Formula 1 may be prepared by the same method as in Scheme 1 below, for example, and other compounds may be prepared similarly.

[Scheme 1]

In Reaction Scheme 1, Y, L, X ₁ , X _2, X ₃ , Ar ₁ and Ar ₂ are as defined in Formula 1, Z is halogen, and preferably Z is chloro or bromo.

Scheme 1 is an amine substitution reaction, preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the amine substitution reaction may be changed as known in the art. The manufacturing method may be more specific in the manufacturing examples to be described later.

In addition, the present invention provides an organic light-emitting device including the compound represented by Formula 1 above. For example, the present invention provides 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 at least one of the organic material layers includes a compound represented by Formula 1 do.

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.

In addition, the organic material layer may include an emission layer, and the emission layer includes a compound represented by Formula 1 above. In particular, the compound according to the present invention can be used as a host of a light emitting layer.

In addition, the organic material layer may include an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer may include a compound represented by Formula 1 above.

In addition, the electron transport layer, the electron injection layer, or a layer that simultaneously transports electrons and injects electrons may include a compound represented by Formula 1 above.

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

In addition, the organic light-emitting device according to the present invention may be a normal type organic light-emitting device 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 inverted type organic light-emitting device 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.

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. In such a structure, the compound represented by Formula 1 may be included in the emission layer.

2 shows a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), an electron blocking layer (7), a light emitting layer (3), an electron transport layer (9), an electron injection layer (10). And an example of an organic light-emitting device comprising the cathode 4 is shown. In such a structure, the compound represented by Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the electron blocking layer, the light emitting layer, the electron transport layer, and the electron injection layer.

3 is a substrate (1), an anode (2), a hole injection layer (5), a hole transport layer (6), a light emitting layer (3), a hole blocking layer (8), consisting of an electron transport layer (9) and a cathode (4). It shows an example of an organic light-emitting device. In such a structure, the compound represented by Formula 1 may be included in one or more of the hole injection layer, the hole transport layer, the light emitting layer, the hole blocking 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 of the organic material layers 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, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, the anode is formed by depositing a metal or a conductive metal oxide or an alloy thereof on the substrate. And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, it can be prepared by depositing a material that can be used as a cathode thereon. In addition to this 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 Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

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

For example, the first electrode is an anode, the second electrode is a cathode, or the first electrode is a cathode, and the second electrode is an anode.

As the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the cathode material include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO:Al or SnO _{2 :Sb;} Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as 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; There are multilayered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

The hole injection layer is a layer that injects holes from the electrode, and has the ability to transport holes as a hole injection material, so that it has a hole injection effect at the anode, an excellent hole injection effect for the light emitting layer or the light emitting material, and is generated from the light emitting layer. A compound that prevents the movement of excitons to the electron injection layer or the electron injection material and has excellent ability to form a thin film is preferable. It is preferable that the HOMO (highest occupied molecular orbital) 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 hole injection materials include metal porphyrin, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, 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, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer and having high mobility for holes This is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer including a conjugated portion and a non-conjugated portion, but are not limited thereto.

The electron blocking layer is a layer interposed between the hole transport layer and the light emitting layer in order to prevent electrons injected from the cathode from passing over to the hole transport layer without being recombined in the light emitting layer, and is also referred to as an electron suppressing layer. The electron blocking layer is preferably a material having less electron affinity than the electron transport layer.

As the light-emitting material, a material capable of emitting light in a visible light 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 against fluorescence or phosphorescence is preferable. Specific examples of 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzthiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The emission layer may include a host material and a dopant material. Host materials include condensed aromatic ring derivatives or heterocyclic-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto. Preferably, the compound represented by Formula 1 may be included as a host material for the emission layer.

Dopant materials include aromatic amine derivatives, strylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specifically, the aromatic amine derivative is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene and the like having an arylamino group, and the styrylamine compound is substituted or unsubstituted As a compound in which at least one arylvinyl group is substituted on the arylamine, 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, there are styrylamine, styryldiamine, styryltriamine, and styryltetraamine, but are not limited thereto. In addition, examples of the metal complex include, but are not limited to, an iridium complex and a platinum complex.

The hole blocking layer is a layer between the electron transport layer and the light emitting layer to prevent holes injected from the anode from being recombined in the light emitting layer and passing to the electron transport layer, and is also referred to as a hole suppressing layer. A material having high ionization energy is preferable for the hole blocking layer.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports electrons to the emission layer.As an electron transport material, a material capable of receiving electrons from the cathode and transferring them to the emission layer is suitable. Do. Specific examples include 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 transport layer can be used with any desired cathode material as used according to the prior art. In particular, examples of suitable cathode materials are conventional materials that have a low work function and are followed by an aluminum layer or a silver layer. Specifically, they are cesium, barium, calcium, ytterbium, and samarium, and in each case an aluminum layer or a silver layer follows.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect for the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer A compound that prevents migration to the layer and is excellent in thin film forming ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and their derivatives, metals Complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include lithium 8-hydroxyquinolinato, 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-naphtholato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtholato)gallium, etc. 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 preparation of the compound represented by Formula 1 and the organic light-emitting device including the same will be described in detail in the following examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

The preparation of the compound represented by Formula 1 and the organic light-emitting device including the same will be described in detail in the following examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

Preparation Example 1: Preparation of Compound 1

(9H-carbazol-2-yl)boronic acid (30 g, 142 mmol), 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3, 5-triazine (48.7 g, 142 mmol) was dissolved in 600 mL of tetrahydrofuran. Potassium carbonate (K ₂ CO ₃ ) 2 M solution (250 mL), tetrakis (triphenylphosphine) palladium (0) (0.73 g, 1.42 mmol) was added and refluxed for 7 hours. After the reaction was completed, the reaction was cooled to room temperature, the water layer was separated and removed, dried over anhydrous magnesium sulfate, and concentrated under reduced pressure. The mixture was recrystallized using chloroform and ethanol to obtain compound a1 (58.3 g, yield: 86%; MS: [ M+H] ⁺ = 475) was obtained.

Then, in a nitrogen atmosphere, compound a1 (15 g, 32 mmol), 2-chloro-benzothiazole (5.4 g, 32 mmol), and potassium phosphate (23.0 g, 94 mmol) were added to 150 ml of dimethylformamide and stirred and refluxed. I did. After the reaction for 2 hours, the temperature was lowered to room temperature and filtered. After the filtrate was extracted with toluene and water, the organic layer was dried over magnesium sulfate. Thereafter, the organic layer was distilled under reduced pressure and recrystallized using a mixed solution of tetrahydrofuran and ethyl acetate. The resulting solid was filtered and dried to prepare compound 1 (12.1 g, yield: 63%).

MS: [M+H] ⁺ = 608

Preparation Example 2: Preparation of Compound 2

2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine instead of 2-([1,1'-biphenyl]-4- Il)-4-chloro-6-phenyl-1,3,5-triazine (48.7 g, 142 mmol) was used in the same manner as the method of preparing compound a1 in Preparation Example 1, and compound b1 (60.1 g, yield: 89%, MS: [M+H] ⁺ =475) was prepared.

Compound 2 (13.1 g, yield: 70%) was prepared in the same manner as in Preparation Example 1 except for using Compound b1 and 2-chloro-benzoxazole instead of Compound a1 and 2-chloro-benzothiazole. Was prepared.

MS: [M+H] ⁺ = 592

Preparation Example 3: Preparation of compound 3

2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine instead of 2-(3'-bromo-[1,1'- Biphenyl]-3-yl)-4,6-diphenyl-1,3,5-triazine (32.9 g, 71 mmol) was used, except that compound c1 (22.0 g, yield: 56%, MS: [M+H] ⁺ = 551) was prepared.

Compound 3 (10.8 g, yield: 50%) was prepared in the same manner as in Preparation Example 1, except that compound c1 was used instead of compound a1.

MS: [M+H] ⁺ = 684

Preparation Example 4: Preparation of compound 4

(9H-carbazol-2-yl)boronic acid and 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine instead of (9H- Except that carbazol-4-yl) boronic acid and 2-chloro-4-(dibenzothiophen-4-yl)-6-phenyl-1,3,5-triazine (26.6 g, 71 mmol) were used. Compound d1 (30.3 g, yield: 84.5%, MS: [M+H] ⁺ = 505) was prepared in the same manner as the method for preparing compound a1.

Compound 4 (10.4 g, yield: 53%) was prepared in the same manner as in Preparation Example 1 except for using Compound d1 and 2-chloro-benzoxazole instead of Compound a1 and 2-chloro-benzothiazole. Was prepared.

MS: [M+H] ⁺ = 622

Preparation Example 5: Preparation of compound 5

2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine instead of 2-chloro-4-(dibenzofuran-3-yl) Compound e1 (24.7 g, yield: 71%; MS: [M +H] ⁺ =489) was prepared.

Compound 5 (11.1 g, yield: 56%) was prepared in the same manner as in Preparation Example 1, except that compound e1 was used instead of compound a1.

MS: [M+H] ⁺ = 622

Preparation Example 6: Preparation of compound 6

(9H-carbazol-2-yl)boronic acid and 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine instead of (9H- Except that carbazol-3-yl) boronic acid and 9-(4-chloro-6-phenyl-1,3,5-triazine-2-yl)-9H-carbazole (25.3 g, 71 mmol) were used. Compound f1 (21.7 g, yield: 63%, MS: [M+H] ⁺ = 488) was prepared in the same manner as the method for preparing compound a1.

Compound 6 (10.9 g, yield: 56%) was prepared in the same manner as in Preparation Example 1, except that compound f1 was used instead of compound a1.

MS: [M+H] ⁺ = 621

Preparation Example 7: Preparation of compound 7

(9H-carbazol-2-yl)boronic acid and 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine instead of (9H- Compound a1 was used except that carbazol-4-yl) boronic acid and 2-chloro-4-phenyl-6-(triphenylene-2)-1,3,5-triazine (29.7 g, 71 mmol) were used. Compound g1 (27.2 g, yield: 70%, MS: [M+H] ⁺ =549) was prepared in the same manner as the preparation method.

Compound 7 (13.9 g, yield: 66%) was prepared in the same manner as in Preparation Example 1 except for using compound g1 and 2-chloro-benzoxazole instead of compound a1 and 2-chloro-benzothiazole. Was prepared.

MS:[M+H] ⁺ = 666

Preparation Example 8: Preparation of compound 8

(9H-carbazol-2-yl)boronic acid and 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine instead of (9H- Carbazol-4-yl) boronic acid and 2-chloro-4,6-diphenyl-1,3,5-triazine (19.0 g, 71 mmol) was used in the same manner as the method of preparing compound a1. Compound h1 (18.4 g, yield: 65%, MS: [M+H] ⁺ = 399) was prepared.

Compound h1 (18.4 g, 46 mmol), 3-chloro-9H-carbazole (9.31 g, 46 mmol), bis (tri-tert-butylphosphine) palladium (0) (Bis (tri-tert- butylphosphine) palladium(0)) (0.24 g, 0.46 mmol) and sodium tert-butoxide (6.66 g, 0.69 mol) were added to 350 ml of xylene and heated and stirred for 10 hours. After lowering the temperature to room temperature and filtering to remove salts, xylene was concentrated under reduced pressure, followed by column with a mixed solution of tetrahydrofuran and hexane, and the compound h2 (19.6 g, yield: 75%; MS: [M+H] ⁺ = 564 ) Was prepared.

Compound 8 (14.2 g, yield: 59%) was prepared in the same manner as in Preparation Example 1, except that compound h2 was used instead of compound a1.

MS: [M+H] ⁺ = 697

Preparation Example 9: Preparation of compound 9

Instead of (9H-carbazol-2-yl)boronic acid and 2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine (8- Same as the method for preparing compound a1, except that chlorodibenzofuran-1-yl) boronic acid and 2-chloro-4,6-diphenyl-1,3,5-triazine (16.3 g, 61 mmol) were used. Compound i1 (16.8 g, yield: 64%, MS: [M+H] ⁺ = 434) was prepared by the method.

Compound i1 (16.8 g, 39 mmol), (9H-carbazol-3-yl) boronic acid (8.17 g, 39 mmol), bis(tri-tert-butylphosphine)palladium(0)(Bis( Tri-tert-butylphosphine) palladium (0)) (0.20 g, 0.39 mmol) was added to 200 ml of dioxane, potassium phosphate (28.1 g, 116 mmol) was dissolved in 100 ml of water, and heated and stirred for 12 hours. After lowering the temperature to room temperature and filtering to remove the salt, xylene was concentrated under reduced pressure, followed by column with a mixed solution of tetrahydrofuran and hexane, and the compound i2 (14.1 g, yield: 64%, MS: [M+H] ⁺ = 565) Got it.

Compound 9 (9.9 g, yield: 57%) was prepared in the same manner as in Preparation Example 1, except that compound i2 was used instead of compound a1.

MS: [M+H] ⁺ = 698

Preparation Example 10: Preparation of Compound 10

4-(4-chloro-6-phenyl-1,3,5-triazin-2-yl)-9-phenyl-9H-carbazole (15 g, 35 mmol), (3-chlorophenyl) boronic acid ( 5.42 g, 35 mmol) was dissolved in 200 mL of tetrahydrofuran. Potassium carbonate (K ₂ CO ₃ ) 2 M solution (100 mL), tetrakis (triphenylphosphine) palladium (0) (0.18 g, 0.35 mmol) was added and refluxed for 3 hours. After the reaction was completed, the mixture was cooled to room temperature, the water layer was separated and removed, dried over anhydrous magnesium sulfate, and then concentrated under reduced pressure. The mixture was recrystallized using chloroform and ethanol, and compound j1 (12.9 g, yield: 73%, MS: [ M+H] ⁺ = 509) was obtained.

Compound j1 (12.9 g, 25 mmol), (9H-carbazol-3-yl) boronic acid (5.40 g, 25 mmol), bis (tri-tert-butylphosphine) palladium (0) (Bis( tri-tert-butylphosphine) palladium(0)) (0.13 g, 0.25 mmol) was added to 200 ml of dioxane, potassium phosphate (18.4 g, 76 mmol) was dissolved in 100 ml of water, and heated and stirred for 13 hours. After lowering the temperature to room temperature and filtering to remove salts, xylene was concentrated under reduced pressure and columned with a mixed solution of tetrahydrofuran and hexane, and the compound j2 (18.0 g, yield: 69%, MS: [M+H] ⁺ = 640) Got it.

Compound 10 (14.6 g, yield: 59%) was prepared in the same manner as in Preparation Example 1, except that compound j2 was used instead of compound a1.

MS: [M+H] ⁺ = 773

Preparation Example 11: Preparation of compound 11

Compound k1 (17.5 g, yield: 81%) by the same method as the method of preparing compound a1, except that (9H-carbazol-3-yl) boronic acid was used instead of (9H-carbazol-2-yl) boronic acid. , MS: [M+H] ⁺ = 475) was prepared.

^{Compound k2 (14.0 g, yield: 59%, MS: [M+H] +} = 640) was prepared in the same manner as the method of preparing compound h2 of Preparation Example 8, except that compound k1 was used instead of compound h1.

Compound 11 (9.7 g, yield: 59%) was prepared in the same manner as in Preparation Example 1 except for using compound k2 and 2-chloro-benzoxazole instead of compound a1 and 2-chloro-benzothiazole. Was prepared.

MS: [M+H] ⁺ = 757

Preparation Example 12: Preparation of compound 12

2-([1,1'-biphenyl]-3-yl)-4-chloro-6-phenyl-1,3,5-triazine instead of 2-chloro-4-(4-chlorophenyl)-6- ^{Compound l1 (22.4 g, yield: 73%, MS: [M+H] +} = 433 in the same manner as the method of preparing a1 of Compound Preparation Example 1 except that phenyl-1,3,5-triazine was used. ) Was prepared.

^{Compound l2 (20.6 g, yield: 70%, MS: [M+H] +} = 565) was prepared in the same manner as in the method of preparing compound i2 of Preparation Example 9, except that compound l1 was used instead of compound i1.

Compound 12 (10.2 g, yield: 56%) was prepared in the same manner as in Preparation Example 1 except for using Compound l2 and 2-chloro-benzoxazole instead of Compound a1 and 2-chlorobenzothiazole I did.

MS: [M+H] ⁺ = 682

Example 1

A glass substrate coated with a thin film of ITO (indium tin oxide) to a thickness of 1,300 Å was placed in distilled water dissolved in a detergent and washed with ultrasonic waves. At this time, a Fischer Co. product was used as a detergent, and distilled water secondarily filtered with a filter manufactured by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

On the ITO transparent electrode prepared as described above, the following hexanitrile hexaazatriphenylene (HAT) was thermally vacuum deposited to a thickness of 50 Å to form a hole injection layer. Hole-transporting material 4-4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB; compound HT-1) was thermally vacuum deposited to a thickness of 250 Å on the hole. A transport layer was formed, and compound HT-2 was vacuum-deposited to a thickness of 50 Å on the HT-1 deposition film to form an electron blocking layer. Subsequently, as a host on the HT-2 deposition film, the compound 1 prepared in Preparation Example 1, the following compound H-1, and the phosphorescent dopant compound GD-1 were co-deposited at a weight ratio of 44:44:12 to form a light emitting layer having a thickness of 400 Å. Formed. Compound ET-1 was vacuum-deposited on the emission layer to a thickness of 250 Å, and compound ET-2 was further co-deposited with Li at a weight ratio of 2% to a thickness of 100 Å to form an electron transport layer and an electron injection layer. A cathode was formed by depositing aluminum to a thickness of 1000 Å on the electron injection layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 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 ~ 5 × 10 ^-8 torr. Thus, an organic light emitting device was manufactured.

Examples 2 to 7

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the compound shown in Table 1 below was used as a phosphorescent host when forming the light emitting layer in Example 1.

Comparative Example 1 and Comparative Example 2

The organic light emitting diodes of Comparative Example 1 and Comparative Example 2 were manufactured using the same method as in Example 1, except that the compound of Table 1 was used instead of Compound 1 as a host when forming the emission layer. Compounds C1 and C2 in Table 1 are as follows.

Experimental Example 1

By applying a current to the organic light emitting device prepared in Examples 1 to 7, Comparative Examples 1 and 2, voltage, efficiency, color coordinates, and lifetime were measured, and the results are shown in Table 1 below. T95 refers to the time it takes for the luminance to decrease to 95% from the initial luminance.

compound Voltage(V)
(@10mA/cm ² ) Efficiency (Cd/A)
(@10mA/cm ² ) Color coordinates
(x,y) Life (hr)
(LT ₉₅ at 50mA/cm ² ) Example 1 Compound 1 3.7 80 0.45, 0.53 134 Example 2 Compound 3 3.9 79 0.46, 0.53 120 Example 3 Compound 4 3.7 77 0.45, 0.52 130 Example 4 Compound 6 4.0 84 0.45, 0.53 125 Example 5 Compound 8 3.8 81 0.46, 0.52 115 Example 6 Compound 9 3.7 80 0.46, 0.52 135 Example 7 Compound 12 3.9 78 0.45, 0.53 120 Comparative Example 1 Compound C1 3.6 68 0.45, 0.54 91 Comparative Example 2 Compound C2 4.4 65 0.46, 0.53 75

As shown in Table 1, in the case of an organic light-emitting device manufactured using the compound according to the present invention as a host of the light-emitting layer, compared to the organic light-emitting device of Comparative Example, it exhibits excellent performance in terms of driving voltage, current efficiency, and lifespan. You can look at it.

In particular, it was confirmed that the organic light-emitting device according to the embodiment has a long life characteristic by increasing its life by about 25-45% compared to the organic light-emitting device according to Comparative Example 1 using compound C1, which is a commonly used phosphorescent host material. Could. In addition, compared to Comparative Example 2 having the compound C2 substituted with only the triazine substituent as a phosphorescent host, it has a high-efficiency characteristic of up to 30%, and in terms of lifespan, the lifespan increased from 50% to 80%.

Example 8

On the ITO transparent electrode prepared as in Example 1, the following hexanitrile hexaazatriphenylene (HAT) was thermally vacuum deposited to a thickness of 500 Å to form a hole injection layer. Compound HT-1 was thermally vacuum deposited to a thickness of 800 Å on the hole injection layer, and compound HT-3 was sequentially vacuum-deposited to a thickness of 500 Å to form a hole transport layer. Subsequently, as a host on the hole transport layer, the compound 1 prepared in Preparation Example 1, the following compound H-2, and the phosphorescent dopant compound GD-2 were co-deposited at a weight ratio of 47:47:6 to form a light emitting layer having a thickness of 350 Å. . Compound ET-3 was vacuum-deposited on the emission layer to a thickness of 50 Å to form a hole blocking layer, and compound ET-4 and LiQ (Lithium Quinolate) were vacuum-deposited on the hole blocking layer at a weight ratio of 1:1 to 250 Å. The electron transport layer of was formed. Lithium fluoride (LiF) having a thickness of 10 Å was sequentially deposited on the electron transport layer, and aluminum was deposited thereon to a thickness of 1000 Å to form a negative electrode.

In the above process, the deposition rate of organic materials was maintained at 0.4 ~ 0.7 Å/sec, the deposition rate of lithium fluoride at the cathode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec. ^-7 ~ 5 × 10 ^-8 torr was maintained.

Examples 9-14

Organic light-emitting devices of Examples 9 to 14 were fabricated in the same manner as in Example 8, except that the compound of Table 2 was used instead of Compound 1 as a host when forming the emission layer.

Comparative Example 3 and Comparative Example 4

The organic light emitting diodes of Comparative Example 3 and Comparative Example 4 were manufactured using the same method as in Example 8, except that the compound of Table 2 was used instead of Compound 1 as a host when forming the emission layer. Compounds C1 and C3 in Table 2 are as follows.

Experimental Example 2

By applying a current to the organic light emitting device prepared in Examples 8 to 14, Comparative Examples 3 and 4, voltage, efficiency and lifetime were measured, and the results are shown in Table 2 below. T95 refers to the time it takes for the luminance to decrease to 95% from the initial luminance.

compound Voltage(V)
(@10mA/cm ² ) Efficiency (Cd/A)
(@10mA/cm ² ) Color coordinates
(x,y) Life (hr)
(LT ₉₅ at 50mA/cm ² ) Example 8 Compound 1 3.8 80 0.45, 0.54 90 Example 9 Compound 2 3.7 75 0.46, 0.52 85 Example 10 Compound 5 3.7 78 0.45, 0.52 80 Example 11 Compound 6 3.9 80 0.46, 0.54 76 Example 12 Compound 7 3.8 77 0.46, 0.54 85 Example 13 Compound 10 3.7 78 0.45, 0.54 90 Example 14 Compound 11 3.7 76 0.45, 0.52 79 Comparative Example 3 Compound C1 4.2 55 0.35, 0.61 55 Comparative Example 4 Compound C3 4.5 50 0.35, 0.62 25

As can be seen in Table 2, when the compound of the present invention is used as a light emitting layer material, when compared with the case of using the material of Comparative Example, similar to Examples 1 to 7 above, it is observed that the compound of the present invention exhibits excellent properties in terms of efficiency and lifespan. can see.

In addition, when comparing Example 8 and Example 9, it can be seen that the substitution position is the same, but the characteristics differ in terms of efficiency depending on the type of substituent. Comparing Comparative Example 4 and Example 14, a triazine substituent was included. It can be seen that the voltage of the organic light-emitting device including the Example compound is about 20% low and has high efficiency characteristics.

As described above, it was confirmed that the compounds of the present invention exhibited superior characteristics in terms of driving voltage, efficiency, and life according to the position of the substituent and the type of the substituent compared to the comparative compounds.

1: substrate 2: anode
3: light-emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: electron block 8: hole block
9: electron transport layer 10: electron injection layer

Claims (8)

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

In Chemical Formula 1,
Y is O or S,
L is a single bond, phenylene, biphenylene, dibenzofuranylene, or dibenzothiophenylene,
X ₁ , X ₂ and X ₃ are each independently N or CH, provided that at least two of _{X 1} , X ₂ and X _{3 are N,}
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 6-60} heteroaryl including any one or more selected from the group consisting of N, O and S.
delete The method of claim 1,
X ₁ , X ₂ and X ₃ are all N,
compound.
The method of claim 1,
At least one of Ar ₁ and Ar ₂ is substituted or unsubstituted C _6-60 aryl,
compound.
The method of claim 1,
Ar ₁ and Ar ₂ are each independently, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, dimethylfluorenyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, phenyl Carbazolyl substituted with, phenyl substituted with dibenzofuranyl, or phenyl substituted with dibenzothiophenyl,
compound.
The method of claim 1,
The compound is represented by any one of the following formulas 1-1 to 1-3,
compound:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3,
Descriptions of Y, L, X ₁ , X _2, X _3, Ar ₁ and Ar ₂ are as defined in claim 1.
Any one selected from the group consisting of,
compound:

.
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 at least one of the organic material layers is defined in any one of claims 1 and 3 to 7. Containing the compound according to,
Organic light emitting device.

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