KR20210027978A - 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 comprising the same. The compound represented by chemical formula 1 described above can be used as a material for an organic layer of the organic light emitting device, and thus can improve efficiency, lower driving voltage, and/or improve lifespan characteristics in the organic light emitting device.

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 multi-layered structure composed 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,

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

R ₁ to R ₄ are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-60 alkyl; Or substituted or unsubstituted C _6-60 aryl, provided that at least one of _{R 1} to R _{4 is substituted or unsubstituted C 6-60} aryl.

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 .

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, electron suppression, light emission, electron transport, or electron injection material.

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

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.

또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

or

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 heteroaryl 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, a phenyl boron group, and the like, 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 heteroaryl group is a heteroaryl group including one or more of O, N, Si, and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but it is preferably 2 to 60 carbon atoms. According to an exemplary embodiment, the heteroaryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the heteroaryl group has 6 to 20 carbon atoms. Examples of the heteroaryl 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 heteroaryl 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 heteroaryl 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 heteroaryl is not a monovalent group, and the description of the heteroaryl group described above may be applied except that the heteroaryl group is formed by bonding of two substituents.

Preferably, Formula 1 may be represented by any one of the following Formulas 1-1 to 1-4:

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formula 1-1 to Formula 1-4,

Description of Ar ₁ , Ar ₂ and R ₁ to R ₄ are as defined in Formula 1.

Preferably, Ar ₁ and Ar ₂ are each independently substituted or unsubstituted C _6-30 aryl; _{Or it may be a substituted or unsubstituted C 2-30} heteroaryl including any one or more selected from the group consisting of N, O and S,

More preferably, Ar ₁ and Ar ₂ are each independently, phenyl, biphenylyl, terphenylyl, biphenylyl substituted with five deuterium, naphthyl, naphthyl phenyl, dimethylfluorenyl, diphenylflu Orenyl, triphenylenyl, phenanthrenyl phenyl, naphthyl biphenylyl, phenyl dimethylfluorenyl, dibenzofuranyl, or dibenzothiophenyl,

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

Preferably, R ₁ to R ₄ are each independently hydrogen, substituted or unsubstituted C _1-10 alkyl, or substituted or unsubstituted C _6-20 aryl, provided that at least one of _{R 1} to R _{4 is substituted} Or it may be an _{unsubstituted C 6-20 aryl,}

More preferably, R ₁ to R ₄ are each independently hydrogen, phenyl, biphenylyl, naphthyl, phenanthrenyl, or phenyl substituted with one tertbutyl, and at least one of _{R 1} to R _{4 is phenyl} , Biphenylyl, naphthyl, phenanthrenyl, or may be phenyl substituted with one tertbutyl,

Most preferably, R ₁ to R ₄ may each independently be hydrogen, or any one selected from the group consisting of, and _{at least one of R 1} to R ₄ is one selected from the group consisting of Can be:

Preferably _{, one of R 1} to R ₄ is phenyl, biphenylyl, naphthyl, phenanthrenyl, or phenyl substituted with one tertbutyl, and the rest may be hydrogen,

More preferably _{, one of R 1} to R ₄ may be any one selected from the group consisting of, and the rest may be hydrogen:

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, Ar ₁ , Ar ₂ and R ₁ to R ₄ are as defined in Formula 1, X is halogen, and preferably X is chloro or bromo.

Reaction Scheme 1 is a Suzuki coupling reaction, preferably carried out in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling 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, an electron suppression layer, a light emitting layer, a hole blocking 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 material layers.

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

In addition, the organic material layer may include a hole transport layer, a hole injection layer, a layer for simultaneous hole transport and hole injection, and an electron suppression layer, and the hole transport layer, a hole injection layer, a layer for simultaneously transporting and injecting holes, Alternatively, the electron suppressing layer may include the compound represented by Formula 1.

In addition, the organic material layer may include a hole transport layer, a hole injection layer, an electron suppression layer, an emission layer, a hole blocking layer, an electron transport layer and an electron injection layer, and the hole transport layer, a hole injection layer, an electron suppression layer, an emission layer, a hole The blocking layer, the electron transport layer, or the electron injection layer may include the 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, an electron suppressing layer 3, a light-emitting layer 4, and a cathode 5. In such a structure, the compound represented by Formula 1 may be included in the electron suppressing layer or the emission layer.

2 shows a substrate (1), an anode (2), a hole injection layer (6), a hole transport layer (7), an electron suppression layer (3), a light emitting layer (4), a hole blocking layer (8), an electron transport layer (9). , An example of an organic light-emitting device comprising an electron injection layer 10 and a cathode 4 is shown. In such a structure, the compound represented by Formula 1 may be included in the hole injection layer, the hole transport layer, the electron suppression layer, or the emission 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 multi-layered 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-suppression layer is a layer between the hole-transport layer and the light-emitting layer 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-blocking layer. The electron-suppressing layer is preferably a material having less electron affinity than the electron transport layer. Preferably, the compound represented by Formula 1 may be included as a material of the electron suppressing 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.

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 injecting electrons from the cathode and transferring them to the emission layer, and a material having high mobility for electrons 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, perylene tetracarboxylic acid, preorenylidene methane, anthrone, etc. Complex compounds and nitrogen-containing 5-membered ring derivatives, 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-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.

Hereinafter, it will be described in more detail to aid the understanding of the present invention. However, the following examples are merely illustrative of the present invention, and the contents of the present invention are not limited by the following examples.

Preparation Example 1: Preparation of compound 1-1

Compound 9-(2-bromophenyl)-2-phenyl-9H-carbazole (6.52 g, 16.42 mmol) and compound a-1 (7.97 g, 18.07 mmol) in a 500 ml round bottom flask in a nitrogen atmosphere and 240 ml of tetrahydrofuran. After completely dissolved in 2M potassium carbonate aqueous solution (120 ml) was added, tetrakis-(triphenylphosphine) palladium (0.57g, 0.49 mmol) was added, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with ethyl acetate 270 ml to prepare compound 1-1 (7.26 g, yield: 62%).

MS[M+H] ⁺ = 715

Preparation Example 2: Preparation of compound 1-2

Compound 9-(2-bromophenyl)-3-phenyl-9H-carbazole (6.28 g, 15.82 mmol) and compound a-2 (8.37 g, 17.40 mmol) in a 500 ml round bottom flask in a nitrogen atmosphere and 240 ml of tetrahydrofuran. After completely dissolved in 2M potassium carbonate aqueous solution (120 ml) was added, tetrakis-(triphenylphosphine) palladium (0.55 g, 0.47 mmol) was added, followed by heating and stirring for 2 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 320 ml of ethyl acetate to prepare compound 1-2 (8.34 g, yield: 70%).

MS[M+H] ⁺ = 755

Preparation Example 3: Preparation of compound 1-3

In a nitrogen atmosphere, add compound 9-(2-bromophenyl)-4-phenyl-9H-carbazole (6.38g, 16.07 mmol) and compound a-3 (9.58g, 17.68 mmol) to 240 ml of tetrahydrofuran in a 500 ml round bottom flask. After completely dissolved in 2M potassium carbonate aqueous solution (120 ml) was added, tetrakis-(triphenylphosphine) palladium (0.56g, 0.48 mmol) was added, followed by heating and stirring for 6 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 210 ml of ethyl acetate to prepare compound 1-3 (7.16 g, yield: 55%).

MS[M+H] ⁺ = 816

Preparation Example 4: Preparation of compound 1-4

In a nitrogen atmosphere, add compound 9-(2-bromophenyl)-1-phenyl-9H-carbazole (5.96g, 15.01 mmol) and compound a-4 (9.78g, 16.51 mmol) to 240 ml of tetrahydrofuran in a 500 ml round bottom flask. After completely dissolved in 2M potassium carbonate aqueous solution (120 ml) was added, tetrakis-(triphenylphosphine) palladium (0.52g, 0.45 mmol) was added, followed by heating and stirring for 7 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 420 ml of ethyl acetate to prepare compound 1-4 (9.32 g, yield: 72%).

MS[M+H] ⁺ = 866

Preparation Example 5: Preparation of compound 1-5

Compound 9-(2-bromophenyl)-2-phenyl-9H-carbazole (6.63 g, 16.70 mmol) and compound a-5 (9.75 g, 18.37 mmol) in a 500 ml round bottom flask in a nitrogen atmosphere and 240 ml of tetrahydrofuran. After completely dissolved in 2M potassium carbonate aqueous solution (120 ml) was added, tetrakis-(triphenylphosphine) palladium (0.58g, 0.50 mmol) was added, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 240 ml of ethyl acetate to prepare compound 1-5 (7.76 g, yield: 58%).

MS[M+H] ⁺ = 805

Preparation Example 6: Preparation of compound 1-6

Compound 9-(2-bromophenyl)-3-phenyl-9H-carbazole (7.11 g, 17.91 mmol) and compound a-6 (8.57 g, 19.70 mmol) in a 500 ml round bottom flask in a nitrogen atmosphere and 240 ml of tetrahydrofuran After completely dissolved in 2M potassium carbonate aqueous solution (120 ml) was added, tetrakis-(triphenylphosphine) palladium (0.62 g, 0.54 mmol) was added, followed by heating and stirring for 7 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 240 ml of ethyl acetate to prepare compound 1-6 (6.92 g, yield: 53%).

MS[M+H] ⁺ = 729

Preparation Example 7: Preparation of compound 1-7

In a nitrogen atmosphere, add compound 9-(2-bromophenyl)-3-phenyl-9H-carbazole (7.53 g, 18.97 mmol) and compound a-7 (8.78 g, 20.86 mmol) to 240 ml of tetrahydrofuran in a 500 ml round bottom flask. After completely dissolved in 2M potassium carbonate aqueous solution (120 ml) was added, tetrakis-(triphenylphosphine) palladium (0.66 g, 0.57 mmol) was added, followed by heating and stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 250 ml of ethyl acetate to prepare compound 1-7 (8.53 g, yield: 63%).

MS[M+H] ⁺ = 715

Preparation Example 8: Preparation of compound 1-8

Compound 9-(2-bromophenyl)-3-phenyl-9H-carbazole (6.89 g, 17.36 mmol) and compound a-8 (8.61 g, 19.09 mmol) in a 500 ml round-bottom flask in a nitrogen atmosphere were added to 240 ml of tetrahydrofuran. After completely dissolved in 2M potassium carbonate aqueous solution (120 ml) was added, tetrakis-(triphenylphosphine) palladium (0.60 g, 0.52 mmol) was added, followed by heating and stirring for 6 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 310 ml of ethyl acetate to prepare compound 1-8 (5.97 g, yield: 46%).

MS[M+H] ⁺ = 745

Preparation Example 9: Preparation of compound 1-9

In a nitrogen atmosphere, add compound 9-(2-bromophenyl)-3-phenyl-9H-carbazole (7.06 g, 17.78 mmol) and compound a-9 (10.35 g, 19.56 mmol) to 240 ml of tetrahydrofuran in a 500 ml round bottom flask. After completely dissolved in 2M potassium carbonate aqueous solution (120 ml) was added, tetrakis-(triphenylphosphine) palladium (0.62 g, 0.53 mmol) was added, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 250 ml of ethyl acetate to prepare compound 1-9 (9.23 g, yield: 65%).

MS[M+H] ⁺ = 804

Preparation Example 10: Preparation of Compound 1-10

Compound 9-(2-bromophenyl)-3-(naphthalen-1-yl)-9H-carbazole (8.26 g, 18.48 mmol), compound a-10 (8.96 g, 20.33 mmol) in a 500 ml round bottom flask in a nitrogen atmosphere Was completely dissolved in 240 ml of tetrahydrofuran, 2M aqueous potassium carbonate solution (120 ml) was added, tetrakis-(triphenylphosphine) palladium (0.64 g, 0.55 mmol) was added, followed by heating and stirring for 4 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 320 ml of ethyl acetate to prepare compound 1-10 (7.55 g, yield: 53%).

MS[M+H] ⁺ = 765

Preparation Example 11: Preparation of compound 1-11

Compound 9-(2-bromophenyl)-3-(naphthalen-2-yl)-9H-carbazole (7.77 g, 17.38 mmol), compound a-11 (9.22 g, 19.12 mmol) in a 500 ml round bottom flask in a nitrogen atmosphere Was completely dissolved in 240 ml of tetrahydrofuran, 2M aqueous potassium carbonate solution (120 ml) was added, tetrakis-(triphenylphosphine) palladium (0.60 g, 0.52 mmol) was added, followed by heating and stirring for 2 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with ethyl acetate 260 ml to prepare compound 1-11 (6.85 g, yield: 49%).

MS[M+H] ⁺ = 806

Preparation Example 12: Preparation of compound 1-12

Compound 2-([1,1'-biphenyl]-4-yl)-9-(2-bromophenyl)-9H-carbazole (6.96 g, 14.68 mmol), compound a-12 in a 500 ml round bottom flask in a nitrogen atmosphere (7.51g, 16.15 mmol) was completely dissolved in 240 ml of tetrahydrofuran, 2M aqueous potassium carbonate solution (120 ml) was added, tetrakis-(triphenylphosphine) palladium (0.51g, 0.44 mmol) was added, and 5 Heated and stirred for hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with ethyl acetate 270 ml to prepare compound 1-12 (5.73 g, yield: 48%).

MS[M+H] ⁺ = 816

Preparation Example 13: Preparation of compound 1-13

Compound 9-(2-bromophenyl)-2-phenyl-9H-carbazole (6.87 g, 14.49 mmol) and compound a-13 (5.58 g, 15.94 mmol) in a 500 ml round bottom flask in a nitrogen atmosphere and 240 ml of tetrahydrofuran. After completely dissolved in 2M potassium carbonate aqueous solution (120 ml) was added, tetrakis-(triphenylphosphine) palladium (0.50g, 0.43 mmol) was added, followed by heating and stirring for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with ethyl acetate 260 ml to prepare compound 1-13 (7.44 g, yield: 72%).

MS[M+H] ⁺ = 715

Example 1-1

A glass substrate coated with a thin film of ITO (indium tin oxide) to a thickness of 1,000 Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. At this time, a product made by Fischer Co. 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.

A hole injection layer was formed by thermally vacuum depositing a compound of the following compound HI1 and the following compound HI2 to a thickness of 100 Å in a ratio of 98:2 (molar ratio) on the prepared anode ITO transparent electrode. The following compound HT1 (1150 Å) was vacuum deposited on the hole injection layer to form a hole transport layer. Subsequently, the previously prepared Compound 1 with a film thickness of 50 Å was vacuum deposited on the hole transport layer to form an electron suppressing layer. Subsequently, the following compound BH and the following compound BD were vacuum-deposited at a weight ratio of 25:1 to form a light emitting layer on the electron inhibiting layer with a film thickness of 200 Å. A hole blocking layer was formed by vacuum depositing the following compound HB1 with a film thickness of 50 Å on the emission layer. Subsequently, the following compound ET1 and the following compound LiQ were vacuum-deposited at a weight ratio of 1:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 310 Å. Lithium fluoride (LiF) at a thickness of 12 Å and aluminum at a thickness of 1,000 Å were sequentially deposited on the electron injection and transport layer 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, and the vacuum degree during deposition was 2×10 ^-7 By maintaining ~ 5x10 ^-6 torr, an organic light emitting device was manufactured.

Examples 1-2 to 1-13

An organic light-emitting device was manufactured in the same manner as in Example 1-1, except that the compound shown in Table 1 was used instead of the compound of Preparation Example 1.

Comparative Examples 1-1 to 1-4

An organic light-emitting device was manufactured in the same manner as in Example 1-1, except that the compound shown in Table 1 was used instead of the compound of Preparation Example 1. Compounds EB2, EB3, EB4 and EB5 used in Table 1 are as follows.

Experimental example

^{When a current of 10 mA/cm 2} was applied to the organic light emitting device prepared in the above Examples and Comparative Examples, 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 from the initial luminance (1600 nit) to 95%.

compound
(Electronic suppression layer) Voltage
(V@10mA/cm ² ) efficiency
(cd/A@10mA/cm ² ) Color coordinates
(x,y) T95
(hr@10mA/cm ² ) Example 1-1 Compound 1 4.22 6.84 (0.147, 0.043) 295 Example 1-2 Compound 2 4.23 6.80 (0.146, 0.044) 280 Example 1-3 Compound 3 4.31 6.71 (0.147, 0.045) 275 Example 1-4 Compound 4 4.35 6.72 (0.146, 0.043) 270 Example 1-5 Compound 5 4.57 6.65 (0.147, 0.044) 265 Example 1-6 Compound 6 4.56 6.60 (0.145, 0.045) 260 Example 1-7 Compound 7 4.23 6.82 (0.147, 0.046) 270 Example 1-8 Compound 8 4.54 6.63 (0.146, 0.044) 255 Example 1-9 Compound 9 4.23 6.87 (0.145, 0.044) 250 Example 1-10 Compound 10 4.43 6.64 (0.147, 0.043) 260 Example 1-11 Compound 11 4.43 6.63 (0.147, 0.045) 265 Example 1-12 Compound 12 4.43 6.60 (0.145, 0.044) 260 Example 1-13 Compound 13 4.43 6.61 (0.145, 0.045) 310 Comparative Example 1-1 Compound EB2 5.32 5.79 (0.146, 0.044) 85 Comparative Example 1-2 Compound EB3 4.86 6.03 (0.146, 0.043) 130 Comparative Example 1-3 Compound EB4 5.12 5.92 (0.145, 0.042) 65 Comparative Example 1-4 Compound EB5 4.79 6.15 (0.144, 0.042) 175

As shown in Table 1, the organic light-emitting device using the compound of the present invention as an electron suppressing layer exhibited excellent characteristics in terms of efficiency, driving voltage, and stability of the organic light-emitting device.

In Examples 1-1 to 1-13, the carbazole core and the amine substituent are each substituted at a specific position in the biphenylylene linker, and the carbazole core is low voltage when a material containing an aryl substituent is used as the electron suppressing layer. It can be seen that it shows high efficiency and long life.

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

Claims (7)

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

In Formula 1,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; _{Or substituted or unsubstituted C 2-60} heteroaryl including any one or more selected from the group consisting of N, O and S,
R ₁ to R ₄ are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C _1-60 alkyl; Or substituted or unsubstituted C _6-60 aryl, provided that at least one of _{R 1} to R _{4 is substituted or unsubstituted C 6-60} aryl.
The method of claim 1,
Formula 1 is represented by any one of the following Formulas 1-1 to 1-4,
compound:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formula 1-1 to Formula 1-4,
Description of Ar ₁ , Ar ₂ and R ₁ to R ₄ are as defined in claim 1.
The method of claim 1,
Ar ₁ and Ar ₂ are each independently, phenyl, biphenylyl, terphenylyl, biphenylyl substituted with five deuterium, naphthyl, naphthyl phenyl, dimethylfluorenyl, diphenylfluorenyl, triphenyl Renyl, phenanthrenyl phenyl, naphthyl biphenylyl, phenyl dimethylfluorenyl, dibenzofuranyl, or dibenzothiophenyl,
compound.
The method of claim 1,
Ar ₁ and Ar ₂ are each independently, any one selected from the group consisting of,
compound:

.
The method of claim 1,
R ₁ to R ₄ are each independently hydrogen, phenyl, biphenylyl, naphthyl, phenanthrenyl, or phenyl substituted with one tertbutyl, and _{at least one of R 1} to R ₄ is phenyl, biphenylyl, Naphthyl, phenanthrenyl, or phenyl substituted with one tertbutyl,
compound.
The method of claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of the following,
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 includes the compound according to any one of claims 1 to 6 doing,
Organic light emitting device.

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