KR20210144979A - 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 present invention provides a compound represented by chemical formula 1. The compound represented by chemical formula 1 can be used as a material for an organic material layer of the organic light emitting device, and 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 emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, and 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 layer is often formed of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light-emitting device, and may include, for example, 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 the organic light emitting device, when a voltage is applied between the two electrodes, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer. When the injected holes and electrons meet, excitons are formed, and the excitons When it falls back to the ground state, it lights up.

The 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 comprising the same.

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

[Formula 1]

In Formula 1,

L is a substituted or unsubstituted C _6-60 arylene; _{Or substituted or unsubstituted C 2-60} heteroarylene comprising any one or more selected from the group consisting of N, O and S,

Ar ₁ is any one selected from the group consisting of

In the group,

each X ₁ is independently N or CR ₁ , with the proviso that at least two of _{X 1 are N,}

wherein R ₁ is hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl;

X ₂ is each independently O, S, or NR ₂ ,

wherein R ₂ is hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl;

Y ₁ to Y ₁₁ are each independently hydrogen, deuterium, substituted or unsubstituted C _1-20 alkyl, or substituted or unsubstituted C _6-60 aryl;

a1 to a3 are each independently an integer of 0 to 3,

a4 and a5 are each independently an integer of 0-2.

In addition, the present invention is 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 represented by Formula 1 above. .

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

FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a light emitting layer 3 , and a cathode 4 .
2 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), light emitting layer (3), hole blocking layer (7), electron transport layer (8), electron injection layer (9) and an example of an organic light emitting device including a cathode 4 .
3 shows a substrate 1, an anode 2, a hole injection layer 5, a first hole transport layer 10, a second hole transport layer 11, a light emitting layer 3, a hole blocking layer 7, an electron transport layer (8), an example of an organic light emitting device comprising an electron injection layer 9 and a cathode 4 is shown.

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

The present invention provides a compound represented by the above formula (1).

, 또는

는 다른 치환기에 연결되는 결합을 의미한다. In this specification,

, or

means a bond connected to another substituent.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; nitrile group; nitro group; hydroxyl group; carbonyl group; ester group; imid; amino group; phosphine oxide group; alkoxy group; aryloxy group; alkyl thiooxy group; arylthioxy group; an alkyl sulfoxy group; arylsulfoxy group; silyl group; boron group; an alkyl group; cycloalkyl group; alkenyl group; aryl group; aralkyl group; aralkenyl group; an alkylaryl group; an alkylamine group; an aralkylamine group; heteroarylamine group; arylamine group; an arylphosphine group; or N, O, and S atom means that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group containing one or more atoms, or substituted or unsubstituted with two or more substituents connected among the above-exemplified substituents . For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

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

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably from 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 specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. However, the present invention is not limited thereto.

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

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the number of carbon atoms in the alkyl group is 1 to 20. 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 linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the carbon number of the alkenyl group is 2 to 20. According to another exemplary embodiment, the carbon number of the alkenyl group is 2 to 10. 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 carbon number of the cycloalkyl group is 3 to 20. 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 is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 30. According to an exemplary embodiment, the carbon number of the aryl group is 6 to 20. 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 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,

etc. can be However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group including at least one of O, N, P, Si and S as a heterogeneous element, and the number of carbon atoms is not particularly limited, but it is preferably from 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazine group, an 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, thiadia and a jolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but is not limited thereto.

In the present specification, the aryl group in the aralkyl group, the aralkenyl group, the alkylaryl group, and the 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 above-described alkyl group. In the present specification, as for heteroaryl among heteroarylamines, the description of the above-described heterocyclic group may be applied. In the present specification, the alkenyl group among the aralkenyl groups is the same as the above-described examples of the alkenyl group. In the present specification, the description of the above-described aryl group may be applied except that arylene is a divalent group. In the present specification, the description of the above-described heterocyclic group may be applied, except that heteroarylene is a divalent group. In the present specification, the hydrocarbon ring is not a monovalent group, and the description of the above-described aryl group or cycloalkyl group may be applied, except that it is formed by combining two substituents. In the present specification, the heterocyclic group is not a monovalent group, and the description of the above-described heterocyclic group may be applied, except that it is formed by combining two substituents.

In the present specification, a1 represents _{the number of Y 5} , and when a1 is 2 or more, 2 or more Y ₅ may be the same or different from each other. Descriptions of a2 and a3 may be understood with reference to the description of a1 and the structure of Formula 1 above.

Preferably, L is a substituted or unsubstituted C _6-30 arylene; Or it may be _{a C 2-30} heteroarylene including any one or more selected from the group consisting of substituted or unsubstituted N, O and S.

일 수 있다.More preferably, L is unsubstituted or substituted with 2 or 4 methyl phenylene, biphenylylene, terphenylrylene, naphthylene, or

can be

Most preferably, L may be any one selected from the group consisting of:

.

.

Preferably, Ar ₁ may be any one selected from the group consisting of:

In the group,

X ₁ , X ₂ and Y ₁ to Y ₁₁ are as defined in Formula 1.

Preferably, R ₁ may be hydrogen, deuterium, substituted or unsubstituted C _1-10 alkyl, or substituted or unsubstituted C _6-20 aryl.

More preferably, R ₁ may be hydrogen, methyl, tertbutyl, or phenyl.

Preferably, R ₂ may be hydrogen, deuterium, substituted or unsubstituted C _1-10 alkyl, or substituted or unsubstituted C _6-20 aryl.

More preferably, R ₂ may be ethyl or phenyl.

Preferably, Y ₁ to Y ₁₀ may each independently be hydrogen, deuterium, substituted or unsubstituted C _1-10 alkyl, or substituted or unsubstituted C _6-20 aryl.

More preferably, Y ₁ to Y ₁₀ may each independently be hydrogen, ethyl, phenyl, phenyl substituted with 5 deuterium, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, or methyl phenyl. .

Preferably, Y ₁ and Y ₂ may each independently be phenyl, phenyl substituted with 5 deuterium, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, or methyl phenyl.

Preferably at least one of Y ₁ and Y ₂ may be phenyl, phenyl substituted with 5 deuterium, biphenylyl, or methyl phenyl.

Preferably, Y ₃ may be phenyl, or naphthyl.

Preferably, Y ₄ may be ethyl or phenyl.

Preferably, Y ₅ may be hydrogen or naphthyl.

Preferably, _{each Y 6} may independently be phenyl.

Preferably, Y ₇ and Y ₈ may each independently be phenyl.

Preferably, _{each Y 9} may independently be hydrogen, phenyl, or phenanthrenyl.

Preferably, Y ₁₀ may be phenyl.

Preferably, Y ₁₁ may be phenyl.

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

.

.

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

[Scheme 1]

In Scheme 1, L and Ar ₁ are as defined in Formula 1 above, and X is halogen, preferably X is chloro or bromo.

The Suzuki coupling reaction in Scheme 1 is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction can be changed as known in the art. The manufacturing method may be more specific in Preparation Examples to be described later.

In addition, the present invention provides an organic light emitting device including the compound represented by the formula (1). In one example, the present invention provides 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 represented by Formula 1 above. 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 multi-layer 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, a hole blocking layer, an electron transport layer, an electron injection layer, etc. 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 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, the hole transport layer, or a layer that simultaneously injects and transports holes is represented by Formula 1 It may include the indicated compound.

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

In addition, the organic layer may include a hole blocking layer, an electron transport layer, an electron injection layer, or a layer that simultaneously transports and injects electrons, and the hole blocking layer, the electron transport layer, the electron injection layer, or the electron transport and electron injection layer. The layer for simultaneous injection may include the compound represented by Formula 1 above.

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

Also, 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. Also, 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 the organic light emitting device according to an embodiment of the present invention is illustrated in FIGS. 1 to 3 .

FIG. 1 shows an example of an organic light emitting device including a substrate 1 , an anode 2 , a light emitting layer 3 , and a cathode 4 . 2 is a substrate (1), anode (2), hole injection layer (5), hole transport layer (6), light emitting layer (3), hole blocking layer (7), electron transport layer (8), electron injection layer (9) and an example of an organic light emitting device including a cathode 4 . 3 shows a substrate 1, an anode 2, a hole injection layer 5, a first hole transport layer 10, a second hole transport layer 11, a light emitting layer 3, a hole blocking layer 7, an electron transport layer (8), an example of an organic light emitting device comprising an electron injection layer 9 and a cathode 4 is shown. In such a structure, the compound represented by Formula 1 may be included in the light emitting layer, the hole blocking layer, the electron transport layer, or the electron injection layer.

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

For example, the organic light emitting device according to the present invention may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or an alloy thereof is deposited on a substrate to form an anode. and forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then 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 into 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, spraying, roll coating, and the like, but is not limited thereto.

In addition to this 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.

In one 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 generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, 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;} conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

The cathode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; and a multilayer structure material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

The hole injection layer is a layer for injecting holes from the electrode, and as a hole injection material, it has the ability to transport holes, so it has a hole injection effect at the anode, an excellent hole injection effect with respect to the light emitting layer or the light emitting material, and is produced in the light emitting layer A compound which prevents the movement of excitons to the electron injection layer or the electron injection material and is excellent in the ability to form a thin film is preferable. Preferably, the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto. Preferably, the compound represented by Formula 1 may be included as a material of the hole injection layer.

The hole transport layer is a layer that receives holes from the hole injection layer and transports them to the light emitting layer. A material capable of transporting holes from the anode or hole injection layer to the light emitting layer as a hole transport material. This is suitable. Specific examples include, but are not limited to, an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together. Preferably, the compound represented by Formula 1 may be included as a material of the hole transport layer.

The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining 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 include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, and the like, but is not limited thereto.

The emission layer may include a host material and a dopant material. The host material includes a condensed aromatic ring derivative or a compound containing a hetero ring. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

Examples of the dopant material include an aromatic amine derivative, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. 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 a substituted or unsubstituted derivative. It is a compound in which at least one arylvinyl group is substituted in the arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

The hole blocking layer is a layer placed between the electron transport layer and the light emitting layer in order to prevent the holes injected from the anode from passing to the electron transport layer without recombination in the light emitting layer, and is also called a hole blocking layer or a hole blocking 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 them to the light emitting layer. 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 may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer. Preferably, the compound represented by Formula 1 may be included as a material of the electron transport layer.

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 on the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer. A compound which prevents movement to a layer and is excellent in the ability to form a thin film is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto. Preferably, the compound represented by Formula 1 may be included as a material of the electron injection layer.

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-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

On the other hand, in the present invention, the "electron injection and transport layer" is a layer that performs both the role of the electron injection layer and the electron transport layer, and the materials serving the respective layers may be used alone or in combination, but limited thereto. doesn't happen

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

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

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

Preparation Example 1-1: Preparation of compound E1

In a nitrogen atmosphere, compound E1-A (20 g, 42.8 mmol) and compound E1-B (16.6 g, 42.8 mmol) were added to 400 ml of Diox, stirred and refluxed. After that, potassium triphosphate (27.3 g, 128.4 mmol) was dissolved in 27 ml of water, and the mixture was sufficiently stirred, followed by dibenzylideneacetone palladium (0.7 g, 1.3 mmol) and tricyclohexylphosphine (0.7 g, 2.6 mmol). was put in. After the reaction for 5 hours, the resulting solid was filtered after cooling to room temperature. The solid was dissolved in 30 times 833 mL of chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare a white solid compound E1 (17.8 g, 64%, MS: [M+H] + = 649).

Preparation 1-2: Preparation of compound E2

Compound E2 was prepared in the same manner as in Preparation Example 1-1, except that Compound E2-B was used instead of Compound E1-B.

MS: [M+H] ⁺ = 649

Preparation Example 1-3: Preparation of compound E3

Compound E3 was prepared in the same manner as in Preparation Example 1-1, except that Compound E3-B was used instead of Compound E1-B.

MS: [M+H] ⁺ = 725

Preparation Example 1-4: Preparation of compound E4

Compound E4 was prepared in the same manner as in Preparation Example 1-1, except that Compound E4-B was used instead of Compound E1-B.

MS: [M+H] ⁺ = 622

Preparation Example 1-5: Preparation of compound E5

Compound E5 was prepared in the same manner as in Preparation Example 1-1, except that Compound E5-A was used instead of Compound E1-A and Compound E5-B was used instead of Compound E1-B.

MS: [M+H] ⁺ = 735

Preparation Example 1-6: Preparation of compound E6

Compound E6 was prepared in the same manner as in Preparation Example 1-1, except that Compound E6-A was used instead of Compound E1-A and Compound E6-B was used instead of Compound E1-B.

MS: [M+H] ⁺ = 699

Preparation Example 1-7: Preparation of compound E7

Compound E7 was prepared in the same manner as in Preparation Example 1-1, except that Compound E6-A was used instead of Compound E1-A and Compound E7-B was used instead of Compound E1-B.

MS: [M+H] ⁺ = 801

Preparation Example 1-8: Preparation of compound E8

Compound E8 was prepared in the same manner as in Preparation Example 1-1, except that Compound E8-B was used instead of Compound E1-B.

MS: [M+H] ⁺ = 535

Preparation Example 1-9: Preparation of compound E9

Compound E9 was prepared in the same manner as in Preparation Example 1-1, except that Compound E9-B was used instead of Compound E1-B.

MS: [M+H] ⁺ = 562

Preparation Example 1-10: Preparation of compound E10

Compound E10 was prepared in the same manner as in Preparation Example 1-1, except that Compound E10-B was used instead of Compound E1-B.

MS: [M+H] ⁺ = 662

Preparation Example 1-11: Preparation of compound E11

Compound E11 was prepared in the same manner as in Preparation Example 1-1, except that Compound E11-A was used instead of Compound E1-A and Compound E11-B was used instead of Compound E1-B.

MS: [M+H] ⁺ = 699

Preparation Example 1-12: Preparation of compound E12

Compound E12 was prepared in the same manner as in Preparation Example 1-1, except that Compound E12-A was used instead of Compound E1-A and Compound E12-B was used instead of Compound E1-B.

MS: [M+H] ⁺ = 649

Preparation 1-13: Preparation of compound E13

Compound E13 was prepared in the same manner as in Preparation Example 1-1, except that Compound E13-B was used instead of Compound E1-B.

MS: [M+H] ⁺ = 648

Preparation Example 1-14: Preparation of compound E14

Compound E14 was prepared in the same manner as in Preparation Example 1-1, except that Compound E14-B was used instead of Compound E1-B.

MS: [M+H] ⁺ = 622

Preparation Example 1-15: Preparation of compound E15

Compound E15 was prepared in the same manner as in Preparation Example 1-1, except that Compound E6-A was used instead of Compound E1-A and Compound E15-B was used instead of Compound E1-B.

MS: [M+H] ⁺ = 610

Preparation Example 1-16: Preparation of compound E16

Compound E16 was prepared in the same manner as in Preparation Example 1-1, except that Compound E16-A was used instead of Compound E1-A and Compound E16-B was used instead of Compound E1-B.

MS: [M+H] ⁺ = 687

Preparation Example 1-17: Preparation of compound E17

Compound E17 was prepared in the same manner as in Preparation Example 1-1, except that Compound E17-B was used instead of Compound E1-B.

MS: [M+H] ⁺ = 572

Preparation Example 1-18: Preparation of compound E18

Compound E18 was prepared in the same manner as in Preparation Example 1-1, except that Compound E12-A was used instead of Compound E1-A and Compound E18-B was used instead of Compound E1-B.

MS: [M+H] ⁺ = 724

Preparation Example 1-19: Preparation of compound E19

Compound E19 was prepared in the same manner as in Preparation Example 1-1, except that Compound E19-A was used instead of Compound E1-A and Compound E19-B was used instead of Compound E1-B.

MS: [M+H] ⁺ = 724

Example 1

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. In this case, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. 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 thermal vacuum deposition of the following compound HI-A to a thickness of 600 Å on the thus prepared ITO transparent electrode. The following compound HAT 50 Å and the following compound HT-A 60 Å were sequentially vacuum deposited on the hole injection layer to form a first hole transport layer and a second hole transport layer.

Subsequently, the following compound BH and compound BD were vacuum-deposited in a weight ratio of 25:1 to a thickness of 200 Å on the second hole transport layer to form a light emitting layer.

Compound HB 50 Å was vacuum deposited on the light emitting layer to form a hole blocking layer, and the previously prepared compound E1 and the following LiQ compound were vacuum deposited in a weight ratio of 1:1 to form an electron injection and transport layer to a thickness of 300 Å. . A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 10 Å and aluminum to a thickness of 1000 Å on the electron injection and transport layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 to 0.9 Å/sec, the deposition rate of lithium fluoride of the negative electrode was maintained at 0.3 Å/sec, and the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 1×10 ^{By maintaining -7} to 5×10 ^-5 torr, an organic light emitting device was manufactured.

Examples 2 to 19

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the compounds shown in Table 1 were used instead of Compound E1 of Example 1, respectively.

Comparative Examples 1 to 12

An organic light emitting diode was manufactured in the same manner as in Example 1, except that the compounds shown in Table 1 were used instead of Compound E1 of Example 1, respectively. Compounds ET-A to ET-L of Table 1 are as follows.

Experimental example

For the organic light emitting devices prepared in Examples 1 to 19 and Comparative Examples 1 to 12, the driving voltage and luminous efficiency were measured at a current density of ^{10 mA/cm 2} , and lifetime (initial) at a current density of ^{20 mA/cm 2} The time at which it becomes 90% of the luminance (T90)) was measured. The results are shown in Table 1 below.

division compound Voltage
(V@10 mA/cm ² ) Efficiency (cd/A
@10 mA/cm ² ) color coordinates
(x, y) Lifetime (hr, T90)
@20 mA/cm ² ) Example 1 E1 4.51 4.91 (0.140, 0.094) 163 Example 2 E2 4.37 5.16 (0.140, 0.095) 122 Example 3 E3 4.42 5.20 (0.140, 0.098) 117 Example 4 E4 4.46 5.04 (0.141, 0.096) 129 Example 5 E5 4.46 4.99 (0.140, 0.095) 161 Example 6 E6 4.56 5.04 (0.140, 0.094) 114 Example 7 E7 4.60 5.01 (0.140, 0.095) 112 Example 8 E8 4.42 4.86 (0.140, 0.098) 148 Example 9 E9 4.42 4.98 (0.140, 0.094) 130 Example 10 E10 4.65 4.98 (0.140, 0.095) 139 Example 11 E11 4.37 4.86 (0.140, 0.098) 153 Example 12 E12 4.56 5.11 (0.140, 0.098) 121 Example 13 E13 4.37 5.12 (0.140, 0.098) 114 Example 14 E14 4.58 5.05 (0.140, 0.098) 114 Example 15 E15 4.42 5.01 (0.140, 0.098) 117 Example 16 E16 4.48 4.89 (0.140, 0.098) 156 Example 17 E17 4.70 4.99 (0.140, 0.098) 146 Example 18 E18 4.74 5.16 (0.140, 0.098) 112 Example 19 E19 4.33 5.13 (0.140, 0.098) 125 Comparative Example 1 ET-A 4.53 4.69 (0.140, 0.094) 20 Comparative Example 2 ET-B 4.40 4.85 (0.140, 0.095) 13 Comparative Example 3 ET-C 4.73 4.76 (0.140, 0.098) 15 Comparative Example 4 ET-D 5.11 3.74 (0.140, 0.094) 96 Comparative Example 5 ET-E 5.03 2.92 (0.140, 0.095) 63 Comparative Example 6 ET-F 4.98 2.95 (0.140, 0.098) 66 Comparative Example 7 ET-G 4.77 3.01 (0.140, 0.094) 131 Comparative Example 8 ET-H 4.81 3.04 (0.140, 0.095) 112 Comparative Example 9 ET-I 4.89 3.08 (0.140, 0.095) 125 Comparative Example 10 ET-J 4.74 3.29 (0.140, 0.098) 140 Comparative Example 11 ET-K 4.69 3.32 (0.140, 0.094) 126 Comparative Example 12 ET-L 4.68 3.54 (0.140, 0.095) 97

Comparing Examples 1 to 19 and Comparative Examples 1 to 3 of Table 1, the organic light emitting device according to an embodiment of the present invention is better than the organic light emitting device including a compound in which a cyano group is not substituted in the spirobifluorene matrix. It was confirmed that it showed remarkably excellent characteristics in terms of lifespan.

Comparing Examples 1 to 19 and Comparative Examples 4 to 6, the organic light emitting device according to an embodiment of the present invention is significantly higher in efficiency and lifespan than the organic light emitting device including a compound having a heteroaryl group as a substituent _{of Ar 1 .} It was confirmed that excellent characteristics were exhibited.

Comparing Examples 1 to 19 with Comparative Examples 7 to 9, it can be seen that the organic light emitting device according to an embodiment of the present invention exhibits significantly superior characteristics in terms of efficiency than the organic light emitting device including the compound in which L is a single bond. could

Comparing Examples 1 to 19 and Comparative Examples 10 to 12 of Table 1, the organic light emitting device according to an embodiment of the present invention is an organic light emitting device including a compound having an arylene linker between the spirobifluorene matrix and the cyano group. It was confirmed that it showed significantly superior characteristics in terms of efficiency than the light emitting device.

1: Substrate 2: Anode
3: light emitting layer 4: cathode
5: hole injection layer 6: hole transport layer
7: hole blocking layer 8: electron transport layer
9: electron injection layer 10: first hole transport layer
11: second hole transport layer

Claims (8)

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

In Formula 1,
L is a substituted or unsubstituted C _6-60 arylene; _{Or substituted or unsubstituted C 2-60} heteroarylene comprising any one or more selected from the group consisting of N, O and S,
Ar ₁ is any one selected from the group consisting of

In this group,
each X ₁ is independently N or CR ₁ , with the proviso that at least two of _{X 1 are N,}
wherein R ₁ is hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl;
X ₂ is each independently O, S, or NR ₂ ,
wherein R ₂ is hydrogen, deuterium, substituted or unsubstituted C _1-60 alkyl, or substituted or unsubstituted C _6-60 aryl;
Y ₁ to Y ₁₁ are each independently hydrogen, deuterium, substituted or unsubstituted C _1-20 alkyl, or substituted or unsubstituted C _6-60 aryl;
a1 to a3 are each independently an integer of 0 to 3,
a4 and a5 are each independently an integer of 0-2.
According to claim 1,
L is unsubstituted or substituted with 2 or 4 methyl phenylene, biphenylylene, terphenylrylene, naphthylene, or

sign,
compound.
According to claim 1,
Ar ₁ is any one selected from the group consisting of
compound:

In the group,
X ₁ , X ₂ and Y ₁ to Y ₁₁ are as defined in claim 1.
According to claim 1,
R ₁ is hydrogen, methyl, tertbutyl, or phenyl;
compound.
According to claim 1,
R ₂ is ethyl, or phenyl;
compound.
According to claim 1,
Y ₁ to Y ₁₀ are each independently hydrogen, ethyl, phenyl, phenyl substituted with 5 deuterium, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, or methyl phenyl;
compound.
According to claim 1,
The compound represented by Formula 1 is any one selected from the group consisting of
compound:

.
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 contains the compound according to any one of claims 1 to 7 doing,
organic light emitting device.

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