KR20200110508A - 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 using the same. In the compound represented by a formula 1 of the present invention, L1 and L2 are each independently a single bonded or substituted or unsubstituted C_6-60 arylene.

Description

Novel compound and organic light emitting device using the same

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

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy 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.

The organic light emitting device generally has a structure including an anode and a cathode, and an organic material layer between the anode and the cathode. The organic material layer is often made of a multi-layered structure composed of different materials 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. It glows when it falls back to the ground.

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 compound 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,

L ₁ and L ₂ are each independently a single bond; Or a substituted or unsubstituted C _6-60 arylene,

Ar ₁ and Ar ₂ are each independently, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, anthracenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, carbazolyl, dibenzofuranyl , Dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl,

Here, Ar ₁ and Ar ₂ are unsubstituted or substituted with one or more substituents each independently selected from the group consisting of C _1-20 alkyl and C _6-20 aryl,

Ar ₃ is substituted or unsubstituted biphenylyl.

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.

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

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

(Definition of Terms)

및

는 다른 치환기에 연결되는 결합을 의미한다.In this specification,

And

Means a bond connected to another substituent.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Cyano 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 heteroaryl 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 it 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 an oxygen of the ester group with a straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 25 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In 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 a linear or branched chain, 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, cycloheptylmethyl, 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 is preferably 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 having aromaticity. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group such as a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthrenyl group, a triphenylenyl group, a pyrenyl group, a perylenyl group, a chrysenyl group, and the like, but is not limited thereto.

In the present specification, heteroaryl is a heteroaryl containing at least one of O, N, Si, and S as a heterogeneous element, and the number of carbons is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of heteroaryl 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 (phenanthroline), isoxazolyl group, thiadiazolyl Group, phenothiazinyl group, dibenzofuranyl group, and the like, but are not limited thereto.

In the present specification, the aryl group in the aralkyl group, aralkenyl group, alkylaryl group, arylamine group, and arylsilyl 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 above-described description of heteroaryl 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 above-described heteroaryl 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 the 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 above-described heteroaryl may be applied except that the heterocycle is formed by bonding of two substituents.

(compound)

Meanwhile, the present invention provides a compound represented by Formula 1 above.

Specifically, the compound represented by Formula 1 is an amine-based compound in which the Ar ₃ substituent is connected to the N atom by a biphenyl-1,4-diyl linker (ortho-biphenylyl linker). At this time, the Ar ₃ substituent is a substituted or unsubstituted biphenyl group, and preferably has a monocyclic substituent structure in which two or more phenyl groups are connected. Accordingly, the compound may exhibit improved hole transport capability and improved thermal stability as compared to a compound that does not have the linker or does not have a monocyclic substituent structure in which two or more phenyl groups are connected. As a result, the organic light emitting device employing the compound may exhibit characteristics such as high efficiency, low driving voltage, and long life.

In Formula 1, preferably, L ₁ and L ₂ are each independently a single bond, phenylene. Biphenyldiyl, or naphthylene.

More preferably, L ₁ and L ₂ are a single bond or 1,4-phenylene.

.

Preferably, Ar ₁ and Ar ₂ are phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, carbazolyl, dibenzofuranyl, dibenzothiophenyl, benzonaphthofuranyl, or Benzonaphthothiophenyl, wherein Ar ₁ and Ar ₂ are unsubstituted or substituted with C _6-20 aryl.

More preferably, Ar ₁ and Ar ₂ are each independently any one selected from the group consisting of:

Above,

R is hydrogen or phenyl.

At this time, Ar ₁ and Ar ₂ may be the same as each other. Preferably, when both Ar ₁ and Ar ₂ are phenyl, the glass transition temperature (Tg) of the compound may be lowered, so it is excluded.

Alternatively, Ar ₁ and Ar ₂ can be different from each other.

Preferably, Ar ₃ is biphenylyl unsubstituted or substituted with phenyl, biphenylyl, or terphenylyl.

More preferably, Ar ₃ is biphenylyl, terphenylyl, or quarterphenylyl.

Most preferably, Ar ₃ is any one selected from the group consisting of:

.

.

Preferably, the compound is 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 Ar ₁ and Ar ₂ is as defined in Formula 1,

Ph means phenyl,

n is 0 or 1,

m is 0, 1, or 2.

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

On the other hand, the compound represented by Formula 1 may be prepared by a manufacturing method such as the following Scheme 1 as an example. The manufacturing method may be more specific in the manufacturing examples to be described later.

[Scheme 1]

In Scheme 1, the description of each substituent is as defined above. The step 1-1 is a step of preparing an intermediate compound I-1 by introducing a bromo group into the starting material S-1, and the step 1-2 is a substituent Ar ₃ at the site where bromo is substituted by a Suzuki-coupling reaction. It is a step of preparing the intermediate compound I-2 by introducing it, and it is preferable to be carried out under a palladium catalyst and a base, and in the above steps 1-3, a tertiary amine compound is introduced by introducing a substituent to the intermediate compound I-2, which is a secondary amine As a reaction for preparing the compound represented by 1, it is preferably carried out under a palladium catalyst. This manufacturing method may be more specific in the manufacturing examples to be described later.

(Organic light emitting device)

Meanwhile, 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 .

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 a hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes, and the hole injection layer, a hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 above. Including the indicated compound.

In addition, the organic material layer may include an emission layer, and the emission layer includes the compound represented by Chemical Formula 1.

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention further includes a hole injection layer and a hole transport layer between the first electrode and the emission layer, and an electron transport layer and an electron injection layer between the emission layer and the second electrode in addition to the emission layer as an organic material layer. It can have a structure to However, the structure of the organic light-emitting device is not limited thereto, and may include a smaller number or a larger number of organic layers.

In addition, in the organic light emitting device according to the present invention, the first electrode is an anode and the second electrode is a cathode, and an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate (normal type). It can be a device. In addition, in the organic light emitting device according to the present invention, the first electrode is a cathode and the second electrode is an anode, and a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate. It may be a light emitting device. 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 hole transport layer 3, a light-emitting layer 4, an electron injection and transport layer 5, and a cathode 6. In such a structure, the compound represented by Formula 1 may be included in the hole transport layer.

2 shows a substrate 1, an anode 2, a hole injection layer 7, a hole transport layer 3, an electron suppression layer 8, a light emitting layer 4, a hole blocking layer 9, an electron injection and transport layer ( 5) and a cathode 6 is shown as an example of an organic light-emitting device. In such a structure, the compound represented by Formula 1 may be included in the hole injection layer, the hole transport layer, or the electron suppression 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. Then, an organic material layer including a hole injection layer, a hole transport layer, an emission layer, and an electron transport layer may be formed thereon, and then a material that can be used as a cathode may be deposited 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); A combination of a metal and an oxide 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 an 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 a light emitting layer or a light emitting material. 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 emission layer, and the hole transport material is a material capable of transporting holes from the anode or the hole injection layer to the emission layer, and has high mobility for holes. The material is suitable. As the hole transport material, the compound represented by Formula 1 may be used, or an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion may be used, but the present invention is not limited thereto. .

The electron suppression layer is formed on the hole transport layer and is preferably provided in contact with the light emitting layer to control hole mobility and prevent excessive movement of electrons, thereby increasing the probability of hole-electron coupling, thereby increasing the efficiency of the organic light-emitting device. It refers to the layer that plays a role in improving the value. The electron-suppressing layer includes an electron-blocking material, and examples of such an electron-blocking material include a compound represented by Formula 1 or an arylamine-based organic material, but are not limited thereto.

The light-emitting material is a material capable of emitting light in a visible light region by transporting and bonding holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples of 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-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.

As described above, the emission layer may include a host material and a dopant material. The host material may further contain a condensed aromatic ring derivative or a heterocyclic-containing compound. 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, and periflanthene 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 an aryl group, silyl group, alkyl group, cycloalkyl group, and arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but are not limited thereto. In addition, the metal complex includes an iridium complex, a platinum complex, and the like, but is not limited thereto.

The hole blocking layer is formed on the light emitting layer, preferably provided in contact with the light emitting layer, to improve the efficiency of the organic light emitting device by increasing the probability of hole-electron coupling by controlling electron mobility and preventing excessive movement of holes. It means the layer that plays a role. The hole-blocking layer includes a hole-blocking material, and examples of such hole-blocking materials include: a subazine derivative including triazine; Triazole derivatives; Oxadiazole derivatives; Phenanthroline derivatives; A compound into which an electron withdrawing group such as a phosphine oxide derivative has been introduced may be used, but is not limited thereto.

The electron injection and transport layer is a layer that simultaneously serves as an electron transport layer and an electron injection layer for injecting electrons from an electrode and transporting received electrons to the emission layer, and is formed on the emission layer or the hole blocking layer. As such an electron injection and transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high mobility for electrons is suitable. Examples of specific electron injection and transport materials include Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complex; Triazine derivatives and the like, but are not limited thereto. Or fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, and their derivatives, metal complex compounds , Or a nitrogen-containing 5-membered cyclic derivative, but may be used together, but is 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 thereto.

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.

Preparation of the compound represented by Formula 1 and an 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.

Manufacturing example 1: Preparation of compound 1

Step 1-1: N-(biphenyl-4-yl)-5- Bromobiphenyl -2- Amine Produce

Compound N-([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-2-amine (100.0 g, 311.52 mmol) and NBS in a 1000 mL round bottom flask in a nitrogen atmosphere. (55.46 g, 310.52 mmol) was completely dissolved in 600 mL of DMF, and then stirred at room temperature for 5 hours. The material obtained by filtering was recrystallized with 850 mL of ethyl acetate to prepare the title compound (89.91 g, yield 72%).

MS[M+H] ⁺ = 400

Step 1-2: Preparation of compound A-1

In a 500 mL round-bottom flask in a nitrogen atmosphere, compound N-(biphenyl-4-yl)-5-bromobiphenyl-2-amine (15.0 g, 37.50 mmol) and compound b1 (7.43) prepared in step 1-1 above. g, 37.50 mmol) was completely dissolved in 300 mL of tetrahydrofuran (THF), 2M aqueous potassium carbonate solution (150 mL) was added, and tetrakis (triphenylphosphine) palladium (1.30 g, 1.13 mmol) was added. 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 320 mL of ethyl acetate to prepare compound A-1 (12.47 g, yield 70%).

MS[M+H] ⁺ = 474

Step 1-3: Preparation of compound 1

Compound A-1 (9.72 g, 20.56 mmol) and compound a1 (6.50 g, 19.58 mmol) were completely dissolved in 280 mL of xylene in a 500 mL round-bottom flask in a nitrogen atmosphere, and NaOtBu (2.82 g, 29.37 mmol) was added. Then, bis (tri-tert-butylphosphine) palladium (0) (0.20 g, 0.39 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature and removing the base by filtering, xylene was concentrated under reduced pressure and recrystallized with 230 mL of ethyl acetate to prepare compound 1 (7.44 g, yield: 52%).

MS[M+H] ⁺ = 726

Manufacturing example 2: Preparation of compound 2

Compound A-2 was prepared in the same manner as in Preparation Example 1, except that Compound b2 was used instead of Compound b1 in Preparation Example 1.

Next, compound A-2 (9.69 g, 20.48 mmol) and compound a2 (5.50 g, 19.50 mmol) were completely dissolved in 290 mL of xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and then NaOtBu (4.22 g, 43.95 mmol) was completely dissolved in 290 mL of xylene. ) Was added, and bis(tri-tert-butylphosphine) palladium (0) (0.15 g, 0.29 mmol) was added, followed by heating and stirring for 5 hours. After lowering the temperature to room temperature and removing the base by filtering, xylene was concentrated under reduced pressure and recrystallized with ethyl acetate 260 mL to prepare compound 2 (8.24 g, yield: 62%).

MS[M+H] ⁺ = 676

Manufacturing example 3: Preparation of compound 3

Compound A-3 was prepared using the same method as in Preparation Example 1, except that compound b3 was used instead of compound b1 in Preparation Example 1.

Next, compound A-3 (7.93 g, 16.76 mmol) and compound a3 (4.50 g, 15.96 mmol) were completely dissolved in 230 mL of xylene in a 500 mL round-bottom flask in a nitrogen atmosphere, and then NaOtBu (2.30 g, 23.94 mmol) was completely dissolved in 230 mL of xylene. ) Was added, and bis(tri-tert-butylphosphine) palladium (0) (0.16 g, 0.32 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature, filtering and removing the base, xylene was concentrated under reduced pressure and recrystallized with 240 mL of ethyl acetate to prepare compound 3 (6.36 g, yield: 59%).

MS[M+H] ⁺ = 676

Manufacturing example 4: Preparation of compound 4

Compound A-4 was prepared in the same manner as in Preparation Example 1, except that Compound b4 was used instead of Compound b1 in Preparation Example 1.

Next, compound B-1 (12.24 g, 22.30 mmol) and compound a4 (6.50 g, 21.24 mmol) were completely dissolved in 230 mL of xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and then NaOtBu (3.06 g, 31.86 mmol) was completely dissolved in 230 mL of xylene. ) Was added, and bis(tri-tert-butylphosphine) palladium (0) (0.22 g, 0.42 mmol) was added, followed by heating and stirring for 5 hours. After lowering the temperature to room temperature and removing the base by filtering, xylene was concentrated under reduced pressure and recrystallized with ethyl acetate 280 mL to prepare compound 4 (10.07 g, yield: 61%).

MS[M+H] ⁺ = 776

Manufacturing example 5: Preparation of compound 5

Compound A-5 was prepared in the same manner as in Preparation Example 1, except that compound b5 was used instead of compound b1 in Preparation Example 1.

Next, compound B-2 (15.23 g, 27.74 mmol) and compound a5 (6.50 g, 26.42 mmol) were completely dissolved in 260 mL of xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and then NaOtBu (3.81 g, 39.63 mmol) was completely dissolved in 260 mL of xylene. ) Was added, and bis(tri-tert-butylphosphine) palladium (0) (0.27 g, 0.53 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature, filtering and removing the base, xylene was concentrated under reduced pressure and recrystallized with 210 mL of ethyl acetate to prepare compound 5 (9.74 g, yield: 51%).

MS[M+H] ⁺ = 716

Manufacturing example 6: Preparation of compound 6

Compound A-6 was prepared in the same manner as in Preparation Example 1, except that Compound b6 was used instead of Compound b1 in Preparation Example 1.

Next, compound B-3 (12.10 g, 22.04 mmol) and compound a6 (5.50 g, 20.99 mmol) were completely dissolved in 240 mL of xylene in a 500 mL round bottom flask in a nitrogen atmosphere, and then NaOtBu (3.03 g, 31.49 mmol) was completely dissolved in 240 mL of xylene. ) Was added, and bis(tri-tert-butylphosphine) palladium (0) (0.21 g, 0.42 mmol) was added, followed by heating and stirring for 35 hours. After reducing the temperature to room temperature and removing the base by filtering, xylene was concentrated under reduced pressure and recrystallized with 230 mL of ethyl acetate to prepare compound 6 (9.74 g, yield: 51%).

MS[M+H] ⁺ = 732

Manufacturing example 7: Preparation of compound 7

Compound A-7 was prepared in the same manner as in Preparation Example 1, except that Compound b7 was used instead of Compound b1 in Preparation Example 1.

Next, compound C-1 (14.64 g, 26.66 mmol) and compound a7 (6.50 g, 25.39 mmol) were completely dissolved in 230 mL of xylene in a 500 mL round-bottom flask in a nitrogen atmosphere, and NaOtBu (3.66 g, 38.09 mmol) ) Was added, and bis(tri-tert-butylphosphine) palladium (0) (0.26 g, 0.51 mmol) was added, followed by heating and stirring for 3 hours. After lowering the temperature to room temperature, filtering and removing the base, xylene was concentrated under reduced pressure and recrystallized with 230 mL of ethyl acetate to prepare compound 7 (6.88 g, yield: 37%).

MS[M+H]+= 726

Manufacturing example 8: Preparation of compound 8

Compound A-8 was prepared using the same method as in Preparation Example 1, except that compound b8 was used instead of compound b1 in Preparation Example 1.

Next, compound C-2 (12.17 g, 22.16 mmol) and compound a8 (6.50 g, 21.10 mmol) were completely dissolved in 250 mL of xylene in a 500 mL round-bottom flask in a nitrogen atmosphere, and then NaOtBu (3.04 g, 31.66 mmol) was completely dissolved in 250 mL of xylene. ) Was added, and bis(tri-tert-butylphosphine) palladium (0) (0.22 g, 0.42 mmol) was added, followed by heating and stirring for 5 hours. After lowering the temperature to room temperature and removing the base by filtering, xylene was concentrated under reduced pressure and recrystallized with 230 mL of ethyl acetate to prepare compound 8 (11.55 g, yield: 70%).

MS[M+H] ⁺ = 778

Manufacturing example 9: Preparation of compound 9

Compound A-9 was prepared in the same manner as in Preparation Example 1, except that Compound b9 was used instead of Compound b1 in Preparation Example 1.

Next, compound D-1 (16.60 g, 27.13 mmol) and compound a9 (7.50 g, 26.60 mmol) were completely dissolved in 230 mL of xylene in a 500 mL round-bottom flask in a nitrogen atmosphere, and then NaOtBu (3.83 g, 39.89 mmol) ) Was added, and bis(tri-tert-butylphosphine) palladium (0) (0.14 g, 0.27 mmol) was added, followed by heating and stirring for 4 hours. After lowering the temperature to room temperature, filtering and removing the base, xylene was concentrated under reduced pressure and recrystallized with 230 mL of tetrahydrofuran to prepare compound 9 (13.27 g, yield: 61%).

MS[M+H]+= 778

Manufacturing example 10: Preparation of compound 10

Compound A-10 was prepared in the same manner as in Preparation Example 1, except that Compound b10 was used instead of Compound b1 in Preparation Example 1.

Next, compound D-2 (11.21 g, 17.93 mmol) and compound a10 (5.50 g, 17.08 mmol) were completely dissolved in 240 mL of xylene in a 500 mL round-bottom flask in a nitrogen atmosphere, and then NaOtBu (2.46 g, 25.62 mmol) was completely dissolved in 240 mL of xylene. ) Was added, and bis(tri-tert-butylphosphine) palladium (0) (0.17 g, 0.34 mmol) was added, followed by heating and stirring for 5 hours. After reducing the temperature to room temperature and removing the base by filtering, xylene was concentrated under reduced pressure and recrystallized with ethyl acetate 260 mL to prepare compound 10 (8.87 g, yield: 60%).

MS[M+H] ⁺ = 868

Example 1: Fabrication of an organic light emitting device

A glass substrate coated with a thin film of ITO (indium tin oxide) to a thickness of 1,000Å 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 cleaning 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 ratio of 98:2 (molar ratio) to a thickness of 100Å on the prepared anode ITO transparent electrode. A hole transport layer was formed by vacuum depositing a compound (1150Å) represented by the following formula HT1 on the hole injection layer. Subsequently, compound 1 prepared in Preparation Example 1 with a film thickness of 50Å was vacuum deposited on the hole transport layer to form an electron suppressing layer.

Subsequently, a compound represented by the following formula BH and a compound represented by the following formula BD with a film thickness of 200Å were vacuum-deposited at a weight ratio of 25:1 to form a light emitting layer.

A hole blocking layer was formed by vacuum depositing a compound represented by the following Chemical Formula HB1 with a film thickness of 50Å on the emission layer. Subsequently, a compound represented by the following formula ET1 and a compound represented by the following formula 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 310Å. Lithium fluoride (LiF) at a thickness of 12Å and aluminum at a thickness of 1,000Å were sequentially deposited on the electron injection and transport layer to form a negative electrode.

Was maintained at the deposition rate was 0.4 ~ 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was 0.3Å / sec, aluminum is deposited at a rate of 2Å / sec, the degree of vacuum upon deposition 2ⅹ10 ^-7 ~ An organic light emitting device was manufactured by maintaining 5x10 ^-6 torr.

Example 2 to Example 10

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 example 1 to 4

An organic light-emitting device was manufactured in the same manner as in Example 1, except that the compound shown in Table 1 was used instead of the compound of Preparation Example 1. The compounds of EB1, EB2, EB3 and EB4 used in Table 1 are as follows.

Experimental example One

When a current 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) Example 1 Compound 1 4.66 6.41 (0.146, 0.045) 245 Example 2 Compound 2 4.45 6.78 (0.147, 0.044) 270 Example 3 Compound 3 4.46 6.79 (0.145, 0.043) 275 Example 4 Compound 4 4.67 6.44 (0.147, 0.044) 250 Example 5 Compound 5 4.65 6.45 (0.145, 0.044) 245 Example 6 Compound 6 4.43 6.79 (0.145, 0.043) 275 Example 7 Compound 7 4.56 6.60 (0.147, 0.044) 250 Example 8 Compound 8 4.68 6.42 (0.145, 0.043) 245 Example 9 Compound 9 4.69 6.44 (0.146, 0.045) 250 Example 10 Compound 10 4.72 6.33 (0.147, 0.044) 255 Comparative Example 1 EB1 4.95 5.64 (0.144, 0.046) 80 Comparative Example 2 EB2 5.24 5.91 (0.145, 0.044) 115 Comparative Example 3 EB3 5.43 5.43 (0.146, 0.043) 140 Comparative Example 4 EB4 5.31 5.31 (0.145, 0.047) 165

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.

Specifically, in Examples 1 to 10, the organic light-emitting device using an amine-based material in which the'N atom' and the'substituted or unsubstituted biphenylyl group' are connected by biphenyl-1,4-diyl as the electron suppressing layer, Comparative Example 1 using the compound EB1 having fluorenyl as one of the substituents of the group, Comparative Example 2 using the compound EB2 in which a fluoro group is linked to biphenyl-1,4-diyl, and a substituent in biphenyl-1,4-diyl Compared to the organic light emitting device of Comparative Example 4 using the missing compound EB4 and Comparative Example 3 using the compound EB3 in which a phenyl group is connected to biphenyl-1,4-diyl, it was found to exhibit characteristics of low voltage, high efficiency, and long life.

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

Claims (8)

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

In Formula 1,
L ₁ and L ₂ are each independently a single bond; Or a substituted or unsubstituted C _6-60 arylene,
Ar ₁ and Ar ₂ are each independently, phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, anthracenyl, triphenylenyl, pyrenyl, chrysenyl, naphthacenyl, carbazolyl, dibenzofuranyl , Dibenzothiophenyl, benzonaphthofuranyl, or benzonaphthothiophenyl,
Here, Ar ₁ and Ar ₂ are unsubstituted or substituted with one or more substituents each independently selected from the group consisting of C _1-20 alkyl and C _6-20 aryl,
Ar ₃ is substituted or unsubstituted biphenylyl.
The method of claim 1,
L ₁ and L ₂ are each independently a single bond or phenylene. Biphenyldiyl, or naphthylene,
compound.
The method of claim 1,
Ar ₁ and Ar ₂ are each independently, any one selected from the group consisting of,
compound:

Above,
R is hydrogen or phenyl.
The method of claim 1,
Ar ₃ is biphenylyl, terphenylyl, or quaterphenylyl,
compound.
The method of claim 1,
Ar ₃ is any one selected from the group consisting of,
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,
Description of Ar ₁ and Ar ₂ is as defined in claim 1,
Ph means phenyl,
n is 0 or 1,
m is 0, 1, or 2.
The method of claim 1,
The compound is any one selected from the group consisting of the following compounds:

A first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound according to any one of claims 1 to 7 That is, an organic light-emitting device.

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