KR102081473B1 - Nitrogen-containing compound and organic electronic device using the same - Google Patents

Abstract

The present specification provides a nitrogen compound and an organic light emitting device including the same.

Description

Nitrogen-containing compound and organic light emitting device comprising the same {NITROGEN-CONTAINING COMPOUND AND ORGANIC ELECTRONIC DEVICE USING THE SAME}

The present specification relates to a nitrogen-containing compound and an organic light emitting device including the same.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode and an organic material layer therebetween. In this case, the organic material layer is often made of a multi-layer 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 continuing need for the development of new materials for such organic light emitting devices.

International Patent Application Publication No. 2003-012890

In this specification, a nitrogen compound and an organic light emitting device including the same are described.

An exemplary embodiment of the present specification provides a compound represented by Formula 1:

[Formula 1]

In Chemical Formula 1,

R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

L 1 is a direct bond; Substituted or unsubstituted arylene group; Or substituted or unsubstituted heteroarylene,

Ar1 and Ar2 are the same as or different from each other, and each substituted or unsubstituted alkyl group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or may combine with each other to form a ring,

a is an integer of 1 to 5, b and c are integers of 1 to 4, d is an integer of 1 to 3, and when a to d are 2 or more, the substituents in parentheses are the same or different.

In addition, an exemplary embodiment of the present specification includes 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 of Formula 1.

The compound described herein can be used as the material of the organic material layer of the organic light emitting device. The compound according to at least one embodiment may improve efficiency, low driving voltage, and / or lifespan characteristics in the organic light emitting device.

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 injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4. It is.

Hereinafter, the present specification will be described in more detail.

An exemplary embodiment of the present specification provides a compound represented by Chemical Formula 1.

Examples of the substituents are described below, but are not limited thereto.

As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Nitrile group; Nitro group; Amino group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted alkenyl group; Substituted or unsubstituted aryl group; Substituted or unsubstituted heterocyclic group; A substituted or unsubstituted aralkyl group; A substituted or unsubstituted aralkenyl group; Substituted or unsubstituted alkylaryl group; Substituted or unsubstituted alkylamine group; Substituted or unsubstituted heteroarylamine group; And it is substituted or unsubstituted with one or more substituents selected from the group consisting of a substituted or unsubstituted arylamine group, or substituted or unsubstituted two or more substituents of 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.

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, 4-methylhexyl, 5-methylhexyl, and the like, 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 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 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 aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, 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.

,

,

및

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

And

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

In the present specification, the heterocyclic group is a heterocyclic group including one or more of O, N, S, Si, and Se as heterologous elements, and the number of carbon atoms is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophene group, furan group, pyrrole group, imidazole group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridyl group, bipyridyl group, pyrimidyl group, triazine group, triazole 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, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, phenanthroline group, thiazolyl group, Isooxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group, dibenzofuranyl group, and the like, 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 may be described with respect to the aforementioned aryl group.

In the present specification, the alkyl group among the aralkyl group, the alkylaryl group, and the alkylamine group may be described with respect to the alkyl group described above.

In the present specification, the heteroaryl of the heteroarylamine may be applied to the description of the aforementioned heterocyclic group.

In the present specification, the alkenyl group of the alkenyl group may be applied to the description 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 heterocyclic group may be applied except that the heteroarylene is a divalent group.

In the present specification, the meaning of bonding to each other to form a ring means that adjacent groups are bonded to each other to form a substituted or unsubstituted aliphatic hydrocarbon ring; Substituted or unsubstituted aromatic hydrocarbon ring; Substituted or unsubstituted aliphatic heterocycle; Or to form a substituted or unsubstituted aromatic heterocycle.

In the present specification, the aliphatic hydrocarbon ring means a ring composed only of carbon and hydrogen atoms as a ring which is not aromatic.

In the present specification, examples of the aromatic hydrocarbon ring include, but are not limited to, benzene, naphthalene, anthracene, and the like.

In the present specification, the aliphatic heterocycle means an aliphatic ring including one or more of the hetero reactors.

In the present specification, the aromatic heterocycle means an aromatic ring containing one or more of the hetero atoms.

In the present specification, the aliphatic hydrocarbon ring, aromatic hydrocarbon ring, aliphatic hetero ring and aromatic hetero ring may be monocyclic or polycyclic.

In one embodiment of the present specification, Chemical Formula 1 is represented by the following Chemical Formula 2.

 [Formula 2]

In Formula 2, R 1 to R 4, L 1, Ar 1, Ar 2, and a to d are the same as defined in Formula 1.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or may combine with each other to form a ring.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms, or may be bonded to each other to form a ring.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or may be bonded to each other to form a ring.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted terphenyl group; Substituted or unsubstituted fluorene group; Substituted or unsubstituted triphenylene group; Substituted or unsubstituted phenanthrene group; Substituted or unsubstituted phenoxazine group; Substituted or unsubstituted phenothiazine group (phenothiazine); Substituted or unsubstituted benzonaphthothiophene group; Substituted or unsubstituted dibenzothiophene group; Substituted or unsubstituted benzonaphthofuran group; Substituted or unsubstituted dibenzofuran group; Substituted or unsubstituted carbazole group; Substituted or unsubstituted benzocarbazole group; It may be a substituted or unsubstituted arylamine group, or may be bonded to each other to form a ring.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted terphenyl group; Substituted or unsubstituted fluorene group; Substituted or unsubstituted dibenzothiophene group; Substituted or unsubstituted dibenzofuran group; Substituted or unsubstituted carbazole group; It may be a substituted or unsubstituted arylamine group, or may be bonded to each other to form a ring.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with a substituent selected from the group consisting of an aryl group, a heterocyclic group, and an amine group; Biphenyl group; Terphenyl group; A fluorene group unsubstituted or substituted with an alkyl group; Dibenzothiophene group; Dibenzofuran group; Unsubstituted carbazole groups substituted with aryl groups; Or an arylamine group, or may be bonded to each other to form a ring.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently selected from the following structural formulas, or may be bonded to each other to form a ring.

In one embodiment of the present specification, L1 is a direct bond; A substituted or unsubstituted arylene group having 6 to 60 carbon atoms; Or substituted or unsubstituted heteroarylene having 2 to 60 carbon atoms.

In one embodiment of the present specification, L1 is a direct bond; A substituted or unsubstituted arylene group having 6 to 30 carbon atoms; Or substituted or unsubstituted heteroarylene having 2 to 30 carbon atoms.

In one embodiment of the present specification, L1 is a direct bond; Or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In one embodiment of the present specification, L1 is a direct bond; Substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylylene group; Substituted or unsubstituted terphenyl group; A substituted or unsubstituted quarterphenyl group; Substituted or unsubstituted naphthalene group; Substituted or unsubstituted anthracene group; Substituted or unsubstituted fluorene group; Substituted or unsubstituted phenanthrene group; Substituted or unsubstituted pyrene group; Or a substituted or unsubstituted triphenylene group.

In one embodiment of the present specification, L1 is a direct bond; A phenylene group unsubstituted or substituted with an aryl group; A biphenylylene group unsubstituted or substituted with an aryl group; Terphenyl group unsubstituted or substituted with an aryl group; A quarterphenyl group unsubstituted or substituted with an aryl group; A naphthalene group unsubstituted or substituted with an aryl group; Anthracene groups unsubstituted or substituted with an aryl group; Aryl group or alkyl group substituted or unsubstituted fluorene group; Phenanthrene groups unsubstituted or substituted with an aryl group; Pyrene groups unsubstituted or substituted with aryl groups; Or a triphenylene group unsubstituted or substituted with an aryl group.

In one embodiment of the present specification, L1 is a direct bond; Phenylene group; Biphenylylene group; Terphenyl group; Quarter-phenyl group; Naphthalene group substituted with phenyl group; Anthracene groups; Dimethyl fluorene group; Phenanthrene groups; Pyrene group; Or a triphenylene group.

In one embodiment of the present specification, R1 to R4 are hydrogen.

In one embodiment of the present specification, Chemical Formula 1 is selected from the following structural formulas.

The heterocyclic compound according to one embodiment of the present specification may be prepared by the method of Preparation of Schemes 1 to 3 described below.

Scheme 1

Scheme 2

Scheme 3

The reaction conditions and materials described in the above scheme may be used as those known in the art, and the type or number of substituents not described in the above scheme may also be changed by the reaction conditions and materials known in the art.

In addition, the present specification provides an organic light emitting device including the compound described above.

In one embodiment of the present specification, the 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.

The organic material layer of the organic light emitting device of the present specification 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 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 an exemplary embodiment of the present specification, the organic material layer includes a hole injection layer, a hole transport layer, or a layer for simultaneously injecting and transporting holes, and the hole injection layer, a hole transport layer, or a layer for simultaneously injecting and transporting holes is Compound.

In an exemplary embodiment of the present specification, the organic material layer includes a hole injection layer or a hole transport layer, and the hole injection layer or the hole transport layer includes the compound.

In another exemplary embodiment, the organic material layer includes a light emitting layer, and the light emitting layer includes the compound.

In one embodiment of the present specification, the organic material layer includes an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes the compound.

In an exemplary embodiment of the present specification, the electron transport layer, the electron injection layer or the layer for simultaneously transporting and electron injection includes the compound.

In another exemplary embodiment, the organic material layer includes a light emitting layer and an electron transport layer, and the electron transport layer includes the compound.

In an exemplary embodiment of the present application, the organic material layer includes an electron blocking layer or a hole blocking layer, and the electron blocking layer or the hole blocking layer includes the compound.

In an exemplary embodiment of the present application, the organic material layer includes an electron blocking layer, and the electron blocking layer includes the compound.

In one embodiment of the present application, the organic light emitting device is one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, an electron blocking layer and a hole blocking layer. It includes more.

In another exemplary embodiment, the organic light emitting diode may be an organic light emitting diode having a structure in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.

 In another exemplary embodiment, the organic light emitting device may be an organic light emitting device having 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 diode according to one embodiment of the present specification 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 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 injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8 and a cathode 4. It is. In such a structure, the compound may be included in one or more layers of the hole injection layer, the hole transport layer, the light emitting layer and the electron transport layer.

The organic light emitting device of the present specification may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer includes the compound of the present specification, that is, the compound of Formula 1.

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.

 The organic light emitting device of the present specification may be manufactured by materials and methods known in the art, except that at least one layer of the organic material layer includes the compound, that is, the compound represented by Chemical Formula 1.

For example, the organic light emitting device of the present specification 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. And an organic material layer including a hole injection layer, a hole transporting layer, a light emitting layer, and an electron transporting layer thereon, and then depositing a material that can be used as a cathode 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 of Chemical Formula 1 may be formed as an organic 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 one embodiment of the present specification, the first electrode is an anode, and the second electrode is a cathode.

In another exemplary embodiment, 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 to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention 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); ZnO: Al or SnO ₂ : Combination of metals and oxides such as 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 material is a layer for injecting holes from an electrode, and the hole injection material has a capability of transporting holes. The hole injection material has a hole injection effect at an anode, and has an excellent hole injection effect for a light emitting layer or a light emitting material. The compound which prevents the movement of the excited excitons 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. As a hole transport material, 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 light emitting material is a material capable of emitting light in the visible region by receiving and combining holes and electrons from the hole transporting layer and the electron transporting 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. The host material may be a condensed aromatic ring derivative or a hetero ring-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 a styrylamine compound may be substituted or unsubstituted. At least one arylvinyl group is substituted with the substituted 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, 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 transporting material 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. This is suitable. Specific examples thereof 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 according to 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 that injects electrons from an electrode, has an ability of transporting electrons, has an electron injection effect from a cathode, an electron injection effect with respect to a light emitting layer or a 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 specification may be a top emission type, a bottom emission type, or a double-sided emission type according to a material used.

In one embodiment of the present specification, the compound of 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 Chemical 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 intended to illustrate the present specification, and the scope of the present specification is not limited thereto.

< Production Example >

< Production Example  1>

[Compound 1]

Compound A (10.0g, 28.33mmol), (4- (di ([1,1'-biphenyl] -4-yl) amino) phenyl) boronic acid (13.74g, 31.16mmol) in 500ml round bottom flask under nitrogen atmosphere ) Was completely dissolved in 310 ml of tetrahydrofuran, 2M aqueous potassium carbonate solution (150 ml) was added thereto, and tetrakis- (triphenylphosphine) palladium (0.98 g, 0.85 mmol) was added thereto, followed by stirring for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 260 ml of ethyl acetate to obtain Compound 1 (17.79 g, 88%).

MS [M + H] ⁺ = 715

< Production Example  2>

[Compound 2]

Compound A (10.0 g, 28.33 mmol), (4-([1,1'-biphenyl] -4-yl (9,9-dimethyl-9H-fluoren-2-yl) in a 500 ml round bottom flask under nitrogen atmosphere ) Amino) phenyl) boronic acid (14.99g, 31.16mmol) is completely dissolved in 280ml of tetrahydrofuran, then 2M aqueous potassium carbonate solution (140ml) is added, and tetrakis- (triphenylphosphine) palladium (0.98g, 0.85mmol) ) Was added and the mixture was heated and stirred for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 260 ml of ethyl acetate to obtain Compound 2 (16.47 g, 77%).

MS [M + H] ⁺ = 755

< Production Example  3>

[Compound 3]

Compound A (10.0 g, 28.33 mmol), (4-([1,1'-biphenyl] -2-yl ([1,1'-biphenyl] -4-yl), in a 500 ml round bottom flask under nitrogen atmosphere) Amino) phenyl) boronic acid (13.74g, 31.16mmol) is completely dissolved in 240ml of tetrahydrofuran, then 2M aqueous potassium carbonate solution (120ml) is added, and tetrakis- (triphenylphosphine) palladium (0.98g, 0.85mmol) After stirring, the mixture was heated and stirred for 3 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 210 ml of ethyl acetate to obtain compound 3 (13.21 g, 65%).

MS [M + H] ⁺ = 715

< Production Example  4>

[Compound 4]

In a 500 ml round bottom flask in a nitrogen atmosphere, Compound A (10.0 g, 28.33 mmol), (4-([1,1'-biphenyl] -2-yl ([1,1 ': 4', 1 ''-ter Phenyl] -4-yl) amino) phenyl) boronic acid (16.11 g, 31.16 mmol) is completely dissolved in 400 ml of tetrahydrofuran, then 2M aqueous potassium carbonate solution (200 ml) is added, and tetrakis- (triphenylphosphine) palladium (0.98 g, 0.85 mmol) was added thereto, and the resulting mixture was heated and stirred for 5 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 210 ml of ethyl acetate to obtain Compound 4 (19.92 g, 89%).

MS [M + H] ⁺ = 790

< Production Example  5>

[Compound 5]

Compound A (10.0 g, 28.33 mmol), N-([1,1'-biphenyl] -2-yl)-[1,1 ': 4', 1 ''-ter, in a 500 ml round bottom flask in a nitrogen atmosphere Phenyl] -4-amine (12.37 g, 31.16 mmol) was dissolved completely in 180 ml of xylene, followed by addition of sodium tert-butoxide (3.27 g, 33.99 mol), and bis (tri- tert-butylphosphine) palladium (0) (Bis (tri- tert -butylphosphine) palladium (0)) (0.14 g, 0.28 mmol) was added thereto, followed by heating and stirring for 2 hours. After the temperature was lowered to room temperature and filtered to remove the salt, xylene was concentrated under reduced pressure and recrystallized with 180 ml of tetrahydrofuran to prepare Compound 5 (12.36 g, yield: 61%).

MS [M + H] ⁺ = 715

< Production Example  6>

[Compound 6]

Compound A (10.0 g, 28.33 mmol), N-([1,1'-biphenyl] -4-yl)-[1,1 ': 4', 1 ''-ter, in a 500 ml round bottom flask in a nitrogen atmosphere Phenyl] -4-amine (12.37 g, 31.16 mmol) was dissolved completely in 180 ml of xylene, followed by addition of sodium tert-butoxide (3.27 g, 33.99 mol), and bis (tri-tert-butyl Phosphine) palladium (0) (Bis (tri- tert -butylphosphine) palladium (0)) (0.14g, 0.28mmol) was added thereto, and the mixture was heated and stirred for 2 hours. After cooling to room temperature to remove the salt by filtration and xylene was concentrated under reduced pressure and recrystallized with 180ml tetrahydrofuran to prepare the compound 6 (16.78g, yield: 83%).

MS [M + H] ⁺ = 715

< Production Example  7>

[Compound 7]

Compound A (10.0 g, 28.33 mmol), N-([1,1'-biphenyl] -4-yl) -9,9-dimethyl-9H-fluoren-2-amine in a 500 ml round bottom flask under nitrogen atmosphere (11.25 g, 31.16 mmol) was dissolved completely in 220 ml of xylene, followed by addition of sodium tert-butoxide (3.27 g, 33.99 mol) and bis (tri-tert-butylphosphine) palladium (0 ) (Bis (tri- tert -butylphosphine) palladium (0)) (0.14 g, 0.28 mmol) was added thereto, followed by heating and stirring for 3 hours. After cooling to room temperature to remove the salt by filtration and xylene was concentrated under reduced pressure and recrystallized with 180ml tetrahydrofuran to prepare the compound 7 (11.08g, yield: 58%).

MS [M + H] ⁺ = 679

< Production Example  8>

[Compound 8]

Compound A (10.0 g, 28.33 mmol), N-([1,1'-biphenyl] -4-yl) -9,9-dimethyl-9H-fluoren-2-amine in a 500 ml round bottom flask under nitrogen atmosphere (10.0 g, 31.16 mmol) was completely dissolved in 260 ml of xylene, followed by addition of sodium tert-butoxide (3.27 g, 33.99 mol), and bis (tri-tert-butylphosphine) palladium (0 ) (Bis (tri- tert -butylphosphine) palladium (0)) (0.14g, 0.28mmol) was added thereto, followed by heating and stirring for 6 hours. After cooling to room temperature to remove the salt by filtration and xylene was concentrated under reduced pressure and recrystallized with 180ml tetrahydrofuran to prepare the compound 8 (12.57g, yield: 69%).

MS [M + H] ⁺ = 639

< Production Example  9>

[Compound 9]

Compound A (10.0 g, 28.33 mmol), N- (4- (dibenzo [b, d] furan-4-yl) phenyl) -9,9-dimethyl-9H-fluorene in a 500 ml round bottom flask in a nitrogen atmosphere 2-amine (14.05 g, 31.16 mmol) was dissolved completely in 220 ml of xylene, followed by addition of sodium tert-butoxide (3.27 g, 33.99 mol), and bis (tri-tert-butylphosphine). Palladium (0) (Bis (tri- tert -butylphosphine) palladium (0)) (0.14 g, 0.28 mmol) was added thereto, followed by heating and stirring for 6 hours. After cooling to room temperature to remove the salt by filtration and xylene was concentrated under reduced pressure and recrystallized with 260ml of tetrahydrofuran to prepare the compound 9 (15.29g, yield: 70%).

MS [M + H] ⁺ = 769

< Production Example  10>

[Compound 10]

Compound A (10.0 g, 28.33 mmol), N- (4- (dibenzo [b, d] thiophen-4-yl) phenyl) -9,9-dimethyl-9H-flu in a 500 ml round bottom flask under nitrogen atmosphere Orene-2-amine (14.55 g, 31.16 mmol) was dissolved completely in 220 ml of xylene, followed by addition of sodium tert-butoxide (3.27 g, 33.99 mol) and bis (tri-tert-butylphosphine Palladium (0) (Bis (tri- tert -butylphosphine) palladium (0)) (0.14g, 0.28mmol) was added thereto, and the mixture was heated and stirred for 7 hours. After cooling to room temperature to remove the salt by filtration and xylene was concentrated under reduced pressure and recrystallized with 220ml tetrahydrofuran to prepare the compound 10 (16.67g, yield: 75%).

MS [M + H] ⁺ = 784

< Production Example  11>

[Compound 11]

Compound A (10.0 g, 28.33 mmol), (4-((4 '-(diphenylamine)-[1,1'-biphenyl] -4-yl) (phenyl) amino) in a 500 ml round bottom flask under nitrogen atmosphere ) Phenyl) boronic acid ((4-((4 '-(diphenylamino)-[1,1'-biphenyl] -4-yl) (phenyl) amino) phenyl) boronic acid) (16.58 g, 31.16 mmol) After completely dissolved in 310 ml of hydrofuran, 2M aqueous potassium carbonate solution (150 ml) was added thereto, and tetrakis- (triphenylphosphine) palladium (0.98 g, 0.85 mmol) was added thereto, followed by heating and stirring for 12 hours. The temperature was lowered to room temperature, the water layer was removed, dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and recrystallized with 210 ml of ethyl acetate to obtain compound 11 (12.27 g, 54%).

MS [M + H] ⁺ = 806

< Experimental Example  1-1>

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. At this time, Fischer Co. product was used as a detergent, and distilled water filtered secondly as a filter of Millipore Co. product was used as distilled water. 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.

The hexanitrile hexaazatriphenylene (HAT) of the following formula was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer.

[HAT]

The following compound 4-4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB) (300 Pa), which is a material for transporting holes on the hole injection layer, was vacuum deposited to form a hole transport layer. It was.

[NPB]

Subsequently, the following compound 1 was vacuum deposited to a film thickness of 100 kPa on the hole transport layer to form an electron blocking layer.

[Compound 1]

Subsequently, the light emitting layer was formed by vacuum depositing the following BH and BD in a weight ratio of 25: 1 on the electron blocking layer with a film thickness of 300 GPa.

[BH]

[BD]

[ET1]

[LiQ]

The compound ET1 and the compound LiQ (Lithium Quinolate) were vacuum-deposited on the emission layer in a weight ratio of 1: 1 to form an electron injection and transport layer having a thickness of 300 kPa. On the electron injection and transport layer, lithium fluoride (LiF) and aluminum were deposited to a thickness of 2,000 kPa in order to form a cathode.

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

<Experimental Example 1-2>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 2 was used instead of compound 1 in Experimental Example 1-1.

<Experimental Example 1-3>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 3 was used instead of compound 1 in Experimental Example 1-1.

<Experimental Example 1-4>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 4 was used instead of compound 1 in Experimental Example 1-1.

<Experimental Example 1-5>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 5 was used instead of compound 1 in Experimental Example 1-1.

<Experimental Example 1-6>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 8 was used instead of compound 1 in Experimental Example 1-1.

<Experimental Example 1-7>

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 9 was used instead of compound 1 in Experimental Example 1-1.

Comparative Example 1

An organic light emitting diode was manufactured according to the same method as Experimental Example 1-1 except for using the following EB1 compound instead of compound 1 in Experimental Example 1-1.

[EB1]

When the electric current was applied to the organic light emitting element produced by Experimental Example 1-1 to 1-7 and Comparative Example 1, the result of Table 1 was obtained.

compound
(Electronic jersey) Voltage
(V @ 10mA / cm ² ) efficiency
(cd / A @ 10mA / cm ² ) Color coordinates
(x, y) Experimental Example 1-1 Compound 1 3.63 6.37 (0.137, 0.126) Experimental Example 1-2 Compound 2 3.77 6.22 (0.136, 0.127) Experimental Example 1-3 Compound 3 3.68 6.31 (0.137, 0.127) Experimental Example 1-4 Compound 4 3.74 6.28 (0.136, 0.127) Experimental Example 1-5 Compound 5 3.68 6.31 (0.137, 0.127) Experimental Example 1-6 Compound 8 3.74 6.28 (0.136, 0.127) Experimental Example 1-7 Compound 9 3.60 6.56 (0.136, 0.127) Comparative Example 1 EB1 4.15 5.94 (0.136, 0.127)

As shown in Table 1, the organic light emitting device manufactured by using the compound of the present invention as an electron blocking layer exhibits excellent characteristics in terms of efficiency, driving voltage and / or stability of the organic light emitting device.

Compared to the core of the present invention, the compound of Comparative Example 1 in which the ring is formed in a similar structure to the organic light emitting device manufactured using the electron blocking layer exhibits lower voltage and higher efficiency.

As shown in the results of Table 1, it was confirmed that the other compounds in the present invention is excellent in the electron blocking ability can be applied to the organic light emitting device.

< Experimental Example  2-1>

Except for using the following EB2 material as the electron blocking layer in Experimental Example 1, and using a compound 2 instead of NPB as the hole transport layer was the same experiment.

[EB2]

Experimental Example 2-2

Except for using the compound 6 instead of NPB as the hole transport layer in Experimental Example 2 and was the same experiment.

Experimental Example 2-3

Except for using the compound 7 instead of NPB as the hole transport layer in Experimental Example 2 and was the same experiment.

Experimental Example 2-4

Except for using the compound 8 instead of NPB in the hole transport layer in Experimental Example 2 and was the same experiment.

Experimental Example 2-5

Except for using the compound 9 instead of NPB as the hole transport layer in Experimental Example 2 was the same experiment.

Experimental Example 2-6

Except for using the compound 10 instead of NPB as the hole transport layer in Experimental Example 2 and was the same experiment.

Experimental Example 2-7

Except for using the compound 11 instead of NPB as the hole transport layer in Experimental Example 2 and was the same experiment.

Comparative Example 2

The organic light emitting device was manufactured by the same method as Experimental Example 2, except that the following compound of HT1 was used instead of compound 1 in Experimental Example 2-1.

[HT1]

When the electric current was applied to the organic light emitting element produced by Experimental Example 2-1 to 2-7 and Comparative Example 2, the result of Table 2 was obtained.

compound
(Hole transport layer) Voltage
(V @ 10mA / cm ² ) efficiency
(cd / A @ 10mA / cm ² ) Color coordinates
(x, y) Experimental Example 2-1 Compound 2 4.45 5.65 (0.138, 0.127) Experimental Example 2-2 Compound 6 4.52 5.59 (0.138, 0.127) Experimental Example 2-3 Compound 7 4.48 5.62 (0.138, 0.126) Experimental Example 2-4 Compound 8 4.43 5.66 (0.138, 0.127) Experimental Example 2-5 Compound 9 4.57 5.45 (0.138, 0.127) Experimental Example 2-6 Compound 10 4.56 5.47 (0.136, 0.127) Experimental Example 2-7 Compound 11 4.42 5.70 (0.136, 0.127) Comparative Example 2 HT1 5.07 5.02 (0.136, 0.127)

As shown in Table 2, the organic light emitting device manufactured by using the compound of the present invention as a hole transport layer is a compound of the present invention when compared with the case of using the material of Comparative Example 2 which is often used as a hole transport layer material It plays a role and shows excellent characteristics in terms of efficiency, driving voltage and / or stability of the organic light emitting device.

Specifically, Experimental Examples 2-1 to 2-7, as in the result of Comparative Example 2, it was confirmed that the other compounds in the present invention can be applied to the organic light emitting device excellent in the hole blocking ability as well as the electron blocking ability.

Although preferred embodiments of the present invention (electronic blocking layer, hole transport layer) have been described above, the present invention is not limited thereto, and various modifications can be made within the scope of the claims and the detailed description of the invention. This also belongs to the scope of the invention.

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

Claims (11)

Nitrogen-containing compound represented by the following formula (1):
[Formula 1]

In Chemical Formula 1,
R1 to R4 are the same as or different from each other, and each independently hydrogen; Or deuterium,
L 1 is a direct bond; Or an arylene group,
Ar1 and Ar2 are the same as or different from each other, and each independently an alkyl group, an aryl group, an arylamine group, or an aryl group unsubstituted or substituted with a heterocyclic group including O or S; Or a heterocyclic group containing O or S,
a is an integer of 1 to 5, b and c are integers of 1 to 4, d is an integer of 1 to 3, and when a to d are 2 or more, the substituents in parentheses are the same or different. delete The nitrogen-containing compound of claim 1, wherein Ar 1 and Ar 2 are the same as or different from each other, and are each independently selected from the following structural formulas:

The method according to claim 1, wherein L1 is a direct bond; Phenylene group; Biphenyl group; Terphenyl group; Quarter-phenyl group; Naphthalene group; Anthracene groups; Fluorene group; Phenanthrene groups; Pyrene group; Or a triphenylene group. The nitrogen-containing compound of claim 1, wherein R 1 to R 4 are hydrogen. The method of claim 1, wherein Formula 1 is any one nitrogen-containing compound selected from the following structural formula:

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 of any one of claims 1 and 3 to 6 Light emitting element. The method according to claim 7,
The organic material layer includes a hole injection layer or a hole transport layer,
The hole injection layer or the hole transport layer is an organic light emitting device comprising the compound. The method according to claim 7,
The organic material layer includes an electron transport layer or an electron injection layer,
The electron transport layer or the electron injection layer is an organic light emitting device comprising the compound. The method according to claim 7,
The organic material layer includes a light emitting layer,
The light emitting layer is an organic light emitting device comprising the compound. The method according to claim 7, wherein the organic layer comprises an electron blocking layer,
The electron blocking layer is an organic light emitting device comprising the compound.

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