KR20200011733A - 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. The compound represented by chemical formula 1 or chemical formula 2 described above can be used as a material for an organic material layer of the organic light emitting device, and can improve efficiency, low driving voltage, and/or 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, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. The organic light emitting device using the organic light emitting phenomenon has a wide viewing angle, excellent contrast, fast response time, excellent brightness, driving voltage and response speed characteristics, many studies have been conducted.

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

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

Korean Patent Publication No. 10-2000-0051826

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

The present invention provides a compound represented by Formula 1 or 2 below:

[Formula 1]

[Formula 2]

In Chemical Formula 1 or 2,

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

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,

Ar is substituted or unsubstituted C _6-60 aryl,

R ₁ to R ₁₄ and R ₂₁ to R ₃₄ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Or C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.

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 comprises a compound represented by Chemical Formula 1 or 2 above. to provide.

The compound represented by Chemical Formula 1 or 2 may be used as a material of the organic material layer of the organic light emitting diode, and may improve efficiency, low driving voltage, and / or lifetime characteristics in the organic light emitting diode.

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

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

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

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

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

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

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

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

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

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

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

In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present specification, the alkenyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, stilbenyl group, styrenyl group and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a cyclic group, a biphenyl group, a terphenyl group, etc. as the monocyclic aryl group, but is not limited thereto. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

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

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

In the present specification, the heteroaryl is a heteroaryl containing one or more of O, N, Si, and S as a dissimilar element, and the carbon number is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of 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, acridil 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, thiadiazolyl Groups, phenothiazinyl groups, dibenzofuranyl groups and the like, but are not limited thereto.

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

On the other hand, the present invention provides a compound represented by Formula 1 or 2.

In Formula 1 or 2, L ₁ and L ₂ are each independently a single bond, substituted or unsubstituted phenylene, substituted or unsubstituted biphenylylene, substituted or unsubstituted naphthylene, substituted or unsubstituted Phenanthrenylene, substituted or unsubstituted anthracenylene, substituted or unsubstituted fluoranthhenylene, substituted or unsubstituted triphenylenylene, substituted or unsubstituted pyrenylene, substituted or unsubstituted carbazoylene , Substituted or unsubstituted fluorenylene, or substituted or unsubstituted spiro-fluorenylene.

For example, L ₁ and L ₂ may each independently be a single bond, phenylene, or biphenylylene, or dimethylfluorenylene.

Specifically, L ₁ may be phenylene, biphenylylene, or dimethylfluorenylene, and L ₂ may be a single bond.

In addition, Ar ₁ and Ar ₂ may each independently be C _6-20 aryl or C _2-20 heteroaryl including one to three heteroatoms selected from the group consisting of N, O, and S. .

For example, Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, dibenzofuranyl, dibenzothiophenyl, or 9-phenyl- 9H-carbazolyl.

Ar may also be C _6-20 aryl unsubstituted or substituted with halogen, C _1-10 alkyl, or C _6-10 aryl.

For example, Ar is phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, or fluorenyl,

Here, Ar may be unsubstituted or substituted with halogen, methyl, tert-butyl, or phenyl.

Specifically, for example, Ar is phenyl unsubstituted or substituted with fluoro, methyl, tert-butyl, or phenyl; Fluorenyl unsubstituted or substituted with methyl or phenyl; Biphenylyl; Terphenylyl; Naphthyl; Phenanthrenyl; Or triphenylenyl.

More specifically, for example, Ar is phenyl, fluorophenyl, methylphenyl, tert-butylphenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, biphenylyl, terphenylyl, naph It may be butyl, phenanthrenyl, or triphenylenyl

R ₁ to R ₁₄ and R ₂₁ to R ₃₄ are each independently hydrogen; heavy hydrogen; halogen; Cyano; C _1-10 alkyl; Or C _6-20 aryl.

For example, R ₁ to R ₁₄ and R ₂₁ to R ₃₄ may each independently be hydrogen, deuterium, halogen, cyano, methyl, or phenyl.

Specifically, for example, R ₁ to R ₁₄ and R ₂₁ to R ₃₄ may be hydrogen.

For example, the compound may be any one selected from the group consisting of the following compounds:

The organic light-emitting device employing the compound represented by the formula (1) or (2) is fluoranthene condensed with benzo (b) carbazole, the organic light emitting device employing the same is an organic light emitting device employing a compound having a fluoranthene condensed ring core Compared with the above, it can have high efficiency, low driving voltage, high brightness, long life, and the like.

Meanwhile, the compounds represented by Formula 1 or 2 (when R ₁ to R ₁₄ and R ₂₁ to R ₃₄ are hydrogen) may be prepared by, for example, the same method as in Scheme 1 below.

Scheme 1

In Scheme 1, the description of L ₁ , L ₂ , Ar ₁ , Ar _2, and Ar is as defined in Formula 1 above, X is halogen, preferably bromo. The reaction is a reaction for introducing a substituent into the amine, it is preferably carried out under a palladium catalyst, the production method may be more specific in the production examples described later.

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

On the other hand, the present invention provides an organic light emitting device comprising the compound represented by Formula 1 or 2. In one embodiment, 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 comprises a compound represented by Chemical Formula 1 or 2 above. to provide.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, an electron suppression layer, a light emitting layer, an electron transport layer, an electron injection layer and the like as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

The organic material layer may include a hole transport layer or an electron suppression layer, and the hole transport layer or the electron suppression layer may include a compound represented by Chemical Formula 1 or 2.

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

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

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

2 shows an example of an organic light emitting element consisting of a substrate 1, an anode 2, a hole transport layer 5, an electron suppression layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4. It is. In such a structure, the compound represented by Formula 1 or 2 may be included in one or more layers of the hole transport layer, electron suppression layer, light emitting layer and electron transport layer. For example, the compound represented by Formula 1 or 2 may be included in 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 layer of the organic material layer includes a compound represented by Chemical Formula 1 or 2. In addition, when the organic light emitting device includes a plurality of organic material layers, the organic material layers may be formed of the same material or different materials.

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

In addition, the compound represented by Chemical Formula 1 or 2 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method in the manufacture of the organic light emitting device. Here, the solution coating method means spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, etc., but is not limited thereto.

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

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

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

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

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

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

The electron suppression layer is a layer that prevents the movement of electrons so that electrons received from the light emitting layer are not transported to the hole transport layer, and the compound represented by Chemical Formula 1 or 2 may be used as the electron suppressing material, but is not limited thereto.

The light emitting material is a material capable of emitting light in the visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency with respect to fluorescence or phosphorescence is preferable. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq ₃ ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material as described above. The host material may further contain a condensed aromatic ring derivative or a heterocyclic containing compound. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocyclic containing compounds include carbazole derivatives, dibenzofuran derivatives and ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

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

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

The electron injection layer is a layer for injecting electrons from an electrode, has a capability of transporting electrons, has an electron injection effect from the cathode, excellent electron injection effect to the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer The compound which prevents the movement to a layer and is excellent in thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the derivatives thereof, metal Complex compounds, nitrogen-containing five-membered ring derivatives, and the like, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtolato) gallium, etc. It is not limited to this.

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

In addition, the compound represented by Chemical Formula 1 or 2 may be included in the organic solar cell or the organic transistor in addition to the organic light emitting device.

Preparation of the compound represented by Formula 1 or 2 and the organic light emitting device including the same will be described in detail in the following Examples. However, the following examples are only for illustrating the present invention, and the scope of the present invention is not limited thereto.

Production Example  1: Preparation of Compound 1

In a 500 mL round bottom flask in nitrogen atmosphere, Compound A (7.0 g, 20.55 mmol), and Compound a1 (4.54 g, 19.57 mmol) were completely dissolved in 150 mL of xylene, followed by addition of NaOtBu (2.44 g, 25.44 mmol), Bis (tri-tert-butylphosphine) palladium (0) (0.11 g, 0.21 mmol) was added thereto, followed by heating and stirring for 3 hours. The mixture was cooled to room temperature, filtered to remove the base, and xylene was concentrated under reduced pressure and recrystallized from 180 mL of ethyl acetate, thereby preparing Compound 1 (7.12 g, yield: 74%).

MS [M + H] ⁺ = 494

Production Example  2: Preparation of Compound 2

In a 500 mL round bottom flask in nitrogen atmosphere, Compound A (7.0 g, 20.55 mmol), and Compound a2 (6.32 g, 19.57 mmol) were completely dissolved in 150 mL of xylene, followed by addition of NaOtBu (2.44 g, 25.44 mmol), Bis (tri-tert-butylphosphine) palladium (0) (0.11 g, 0.21 mmol) was added thereto, followed by heating and stirring for 4 hours. The mixture was cooled to room temperature, filtered to remove the base, and xylene was concentrated under reduced pressure and recrystallized from 180 mL of ethyl acetate to obtain Compound 2 (5.68 g, yield: 50%).

MS [M + H] ⁺ = 585

Production Example  3: Preparation of Compound 3

In a 500 mL round bottom flask in nitrogen atmosphere, Compound A (7.0 g, 20.55 mmol), and Compound a3 (7.80 g, 19.55 mmol) were completely dissolved in 190 mL of xylene, followed by addition of NaOtBu (2.44 g, 25.44 mmol), Bis (tri-tert-butylphosphine) palladium (0) (0.11 g, 0.21 mmol) was added thereto, followed by heating and stirring for 5 hours. The mixture was cooled to room temperature, filtered to remove the base, and xylene was concentrated under reduced pressure and recrystallized from 210 mL of ethyl acetate to obtain compound 3 (8.67 g, yield: 67%).

MS [M + H] ⁺ = 661

Production Example  4: Preparation of Compound 4

In a 500 mL round bottom flask in nitrogen atmosphere, Compound A (7.0 g, 20.52 mmol), and Compound a4 (8.58 g, 19.54 mmol) were completely dissolved in 220 mL of xylene, followed by addition of NaOtBu (2.44 g, 25.44 mmol), Bis (tri-tert-butylphosphine) palladium (0) (0.11 g, 0.21 mmol) was added thereto, followed by heating and stirring for 5 hours. The mixture was cooled to room temperature, filtered to remove the base, and xylene was concentrated under reduced pressure and recrystallized from 210 mL of ethyl acetate to obtain Compound 4 (8.63 g, yield: 63%).

MS [M + H] ⁺ = 701

Production Example  5: Preparation of Compound 5

In a 500 mL round bottom flask in nitrogen atmosphere, Compound A (7.0 g, 20.52 mmol) and Compound a5 (9.05 g, 19.55 mmol) were completely dissolved in 180 mL of xylene, followed by addition of NaOtBu (2.44 g, 25.44 mmol), Bis (tri-tert-butylphosphine) palladium (0) (0.11 g, 0.21 mmol) was added thereto, followed by heating and stirring for 4 hours. The mixture was cooled to room temperature, filtered to remove the base, and xylene was concentrated under reduced pressure and recrystallized from 180 mL of ethyl acetate to obtain compound 5 (8.86 g, yield: 63%).

MS [M + H] ⁺ = 725

Production Example  6: Preparation of Compound 6

In a 500 mL round bottom flask in nitrogen atmosphere, Compound A (7.0 g, 20.54 mmol), and Compound a6 (9.37 g, 19.56 mmol) were completely dissolved in 180 mL of xylene, followed by addition of NaOtBu (2.44 g, 25.44 mmol), Bis (tri-tert-butylphosphine) palladium (0) (0.11 g, 0.21 mmol) was added thereto, followed by heating and stirring for 4 hours. The mixture was cooled to room temperature, filtered to remove the base, and xylene was concentrated under reduced pressure and recrystallized from 180 mL of ethyl acetate to obtain Compound 6 (8.13 g, yield: 56%).

MS [M + H] ⁺ = 741

Production Example  7: Preparation of compound 7

In a 500 mL round bottom flask under nitrogen atmosphere, Compound A (7.0 g, 20.54 mmol), and Compound a7 (11.21 g, 19.56 mmol) were completely dissolved in 250 mL of xylene, followed by addition of NaOtBu (2.44 g, 25.44 mmol), Bis (tri-tert-butylphosphine) palladium (0) (0.11 g, 0.21 mmol) was added thereto, followed by heating and stirring for 4 hours. The mixture was cooled to room temperature, filtered to remove the base, and xylene was concentrated under reduced pressure and recrystallized from 260 mL of tetrahydrofuran to prepare compound 7 (12.86 g, yield: 79%).

MS [M + H] ⁺ = 835

Example 1

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and ultrasonically cleaned. In this case, Fischer Co. product was used as the detergent, and distilled water was filtered secondly as a filter of Millipore Co. product. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After washing the distilled water, ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol, dried and transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.

A hole injection layer was formed by thermally vacuum depositing a compound represented by the following formula HAT on the prepared ITO transparent electrode to a thickness of 100 kPa. A compound (1250 Pa) represented by the following Chemical Formula HT1 was vacuum deposited on the hole injection layer to form a hole transport layer. Subsequently, the compound 1 of Preparation Example 1 was vacuum deposited on the hole transport layer to have a film thickness of 150 Pa, thereby forming an electron suppressing layer. Subsequently, the light emitting layer was formed by evaporating the compound represented by the following formula BH and the compound represented by the following formula BD at a weight ratio of 25: 1 on the electron suppressing layer with a film thickness of 200 kPa. A hole blocking layer was formed by vacuum depositing a compound represented by the following formula HB1 with a film thickness of 50 kPa on the light emitting layer. Subsequently, the compound represented by the following formula ET1 and the compound represented by the following formula LiQ were vacuum deposited on the hole blocking layer in a weight ratio of 1: 1 to form an electron injection and transport layer having a thickness of 310 Å. On the electron injection and transport layer, lithium fluoride (LiF) and aluminum were deposited to a thickness of 1,000 로 in order to form a cathode.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7Å / sec, the lithium fluoride of the cathode was maintained at 0.3Å / sec, the deposition rate of aluminum was 2Å / sec, the degree of vacuum during deposition is 2 증착 10 ^-7 ~ The organic light emitting device was manufactured by maintaining ⁵ × 10 ⁻⁶ torr.

Examples 2-7

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 1 of Preparation Example 1.

Comparative Examples 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 1 of Preparation Example 1. The compounds of EB1, EB2, EB3, and EB4 used in Table 1 below are as follows.

Experimental Example  One

When current was applied to the organic light emitting diodes manufactured in Examples and Comparative Examples, voltage, efficiency, color coordinates, and lifetime were measured, and the results are shown in Table 1 below. T95 means the time it takes for the luminance to decrease to 95% from the initial luminance (1600 nit).

compound
(Electron suppression layer) Voltage
(V
@ 10mA / cm ² ) efficiency
(cd / A
@ 10mA / cm ² ) Color coordinates
(x, y) T95
(hr) Example 1 Preparation Example 1 4.51 6.30 (0.140, 0.045) 285 Example 2 Preparation Example 2 4.58 6.46 (0.141, 0.047) 295 Example 3 Preparation Example 3 4.46 6.42 (0.139, 0.043) 275 Example 4 Preparation Example 4 4.44 6.33 (0.140, 0.047) 265 Example 5 Preparation Example 5 4.55 6.35 (0.141, 0.046) 280 Example 6 Preparation Example 6 4.43 6.39 (0.140, 0.044) 260 Example 7 Preparation Example 7 4.42 6.44 (0.141, 0.046) 275 Comparative Example 1 EB1 5.67 5.01 (0.139, 0.043) 125 Comparative Example 2 EB2 5.12 5.75 (0.142, 0.045) 165 Comparative Example 3 EB3 7.03 4.16 (0.143, 0.046) 80 Comparative Example 4 EB4 6.15 4.85 (0.145, 0.045) 140

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, the organic light emitting device of Examples 1 to 7 using the compound of the benzo (b) carbazole type core, Comparative Examples 1 and 4 (EB1 and EB4), benzo ( c) low driving voltage, high efficiency and remarkably higher than the organic light emitting device of Comparative Example 2 (EB2) using the compound of the carbazole type core and Comparative Example 3 (EB3) using the compound of the benzo (a) carbazole type core Long life.

Accordingly, the compound according to the present invention is excellent in electron blocking ability, it can be seen that it can be applied as a material of the electron suppression layer of the organic light emitting device.

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

Claims (9)

Compound represented by the following formula (1) or (2):
[Formula 1]

[Formula 2]

In Chemical Formula 1 or 2,
L ₁ and L ₂ are each independently a single bond; Substituted or unsubstituted C _6-60 arylene; Or C _2-60 heteroarylene containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted O, N, Si, and S,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted C _6-60 aryl; Or C _2-60 heteroaryl containing 1 to 3 heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S,
Ar is substituted or unsubstituted C _6-60 aryl,
R ₁ to R ₁₄ and R ₂₁ to R ₃₄ are each independently hydrogen; heavy hydrogen; halogen; Cyano; Nitro; Amino; Substituted or unsubstituted C _1-60 alkyl; Substituted or unsubstituted C _1-60 haloalkyl; Substituted or unsubstituted C _1-60 alkoxy; Substituted or unsubstituted C _1-60 haloalkoxy; Substituted or unsubstituted C _3-60 cycloalkyl; Substituted or unsubstituted C _2-60 alkenyl; Substituted or unsubstituted C _6-60 aryl; Substituted or unsubstituted C _6-60 aryloxy; Or C _2-60 heteroaryl containing one or more heteroatoms selected from the group consisting of substituted or unsubstituted N, O and S.
The method of claim 1,
L ₁ and L ₂ are each independently a single bond, phenylene, biphenylylene, or dimethylfluorenylene,
compound.
The method of claim 1,
L ₁ is phenylene, biphenylylene, or dimethylfluorenylene,
L ₂ is a single bond,
compound.
The method of claim 1,
Ar ₁ and Ar ₂ are each independently phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, dibenzofuranyl, dibenzothiophenyl, or 9-phenyl-9H-carbazolyl sign,
compound.
The method of claim 1,
Ar is phenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, triphenylenyl, or fluorenyl,
Wherein Ar is unsubstituted or substituted with halogen, methyl, tert-butyl, or phenyl,
compound.
The method of claim 1,
Ar is phenyl, fluorophenyl, methylphenyl, tert-butylphenyl, 9,9-dimethylfluorenyl, 9,9-diphenylfluorenyl, biphenylyl, terphenylyl, naphthyl, phenanthrenyl, or Triphenylenyl,
compound.
The method of claim 1,
R ₁ to R ₁₄ and R ₂₁ to R ₃₄ are each independently hydrogen, deuterium, halogen, cyano, methyl, or phenyl,
compound.
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 comprises a compound according to any one of claims 1 to 8. That is, an organic light emitting device.

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