KR101940694B1 - Heterocyclic compound and organic light emitting device containing the same - Google Patents

Abstract

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a heterocyclic compound of formula (I) and an organic light emitting device including the same.

Description

HETEROCYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE CONTAINING THE SAME [0002]

This application claims the benefit of the filing date of Korean Patent Application No. 10-2016-0057784 filed on May 11, 2016 with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

TECHNICAL FIELD The present invention relates to heterocyclic compounds and organic light emitting devices comprising the same.

The organic light emission phenomenon is one example in which current is converted into visible light by an internal process of a specific organic molecule. The principle of organic luminescence phenomenon is as follows.

When an organic layer is positioned between the anode and the cathode, when a voltage is applied between the two electrodes, electrons and holes are injected into the organic layer from the cathode and the anode, respectively. Electrons and holes injected into the organic material layer recombine to form an exciton, and the exciton falls back to the ground state to emit light. An organic light emitting device using such a principle may be generally composed of an organic material layer including a cathode, an anode and an organic material layer disposed therebetween, for example, a hole injecting layer, a hole transporting layer, a light emitting layer, and an electron transporting layer.

As a material used in an organic light emitting device, a pure organic material or a complex in which an organic material and a metal form a complex is mostly used. Depending on the application, a hole injecting material, a hole transporting material, a light emitting material, an electron transporting material, . As the hole injecting material and the hole transporting material, an organic material having a p-type property, that is, an organic material that is easily oxidized and electrochemically stable at the time of oxidation is mainly used. On the other hand, as an electron injecting material or an electron transporting material, an organic material having an n-type property, that is, an organic material that is easily reduced and electrochemically stable when being reduced is mainly used. As the light emitting layer material, a material having both a p-type property and an n-type property, that is, a material having both a stable form in oxidation and in a reduced state is preferable, and a material having a high luminous efficiency for converting an exciton into light desirable.

BACKGROUND ART [0002] In order to improve the performance, life or efficiency of an organic light emitting device, development of an organic thin film material is continuously required.

International Patent Application Publication No. 2003-012890

The present invention provides a compound and an organic light emitting device comprising the same.

An embodiment of the present invention provides a compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1,

A and B are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A nitrile group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

L is a substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

n is an integer of 1 to 7, and when n is 2 or more, A is the same as or different from each other,

p is 1 or 2, and when p is 2, L is the same or different from each other,

m is an integer of 1 to 7, and when m is 2 or more, B is the same or different from each other.

The present invention also provides an organic light emitting device comprising a first electrode, a second electrode facing the first electrode, and at least one organic layer provided between the first electrode and the second electrode, wherein at least one of the organic layers One is an organic light emitting device comprising the compound of Formula 1.

The compound according to one embodiment of the present application is used in an organic light emitting device to lower the driving voltage of the organic light emitting device, improve the light efficiency, and improve the lifetime characteristics of the device by the thermal stability of the compound.

1 to 4 are structural cross-sectional views of an organic light emitting device according to an embodiment of the present invention.
5 shows the result of mass spectrometry of Compound 34. Fig.
Fig. 6 shows mass analysis results of Compound 42. Fig.

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

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

The term "substituted" means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the substituted position is not limited as long as the substituent is a substitutable position, , Two or more substituents may be the same as or different from each other.

As used herein, the term " substituted or unsubstituted " A halogen group; A nitrile group; Carbonyl group; An ester group; A hydroxy group; An alkyl group; A cycloalkyl group; An aryl group; And a heterocyclic group, or that two or more of the substituents in the above-exemplified substituents are substituted with a substituent to which they are linked, or have no substituent. For example, "a substituent to which at least two substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

는 다른 치환기 또는 결합부에 결합되는 부위를 의미한다.In the present specification,

Quot; refers to a moiety bonded to another substituent or bond.

In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec- N-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-hexyl, Cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like.

In the present specification, the cycloalkyl group is not particularly limited, but is preferably a group having 3 to 30 carbon atoms. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, But are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, isobutyl, sec-butyl, It is not.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 30 carbon atoms. Specific examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group, and the like, but are not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. And preferably 10 to 30 carbon atoms. Specific examples of the polycyclic aryl group include, but are not limited to, a naphthyl group, an anthracenyl group, a phenanthryl group, a triphenyl group, a pyrenyl group, a perylenyl group, a klycenyl group and a fluorenyl group.

In the present specification, the fluorenyl group may be substituted, and adjacent groups may combine with each other to form a ring.

,

,

및

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

,

,

And

And the like. However, the present invention is not limited thereto.

In the present specification, the heteroaryl group includes at least one non-carbon atom and at least one hetero atom. Specifically, the hetero atom may include one or more atoms selected from the group consisting of O, N, Se and S, and the like. The number of carbon atoms is not particularly limited, but is preferably 2 to 30 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include a thiophene group, a furanyl group, a pyrrolyl group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, A substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, , An isoquinolinyl group, an indolyl group, a carbazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a benzocarbazolyl group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, Phenanthroline, isoxazolyl group, thiadiazolyl group, phenothiazinyl group, and dibenzofuranyl group, but the present invention is not limited thereto.

In the present specification, the heterocyclic group may be monocyclic or polycyclic, and may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and examples thereof may be selected from the above heteroaryl groups.

In the present specification, the aromatic ring group may be monocyclic or polycyclic, and examples of the aryl group may be selected.

In the present specification, the 2- to 4-valent aromatic ring group may be monocyclic or polycyclic, meaning that the aryl group has 2 to 4 bonding positions, that is, 2 to 4 bonds. The description of the aryl group described above can be applied, except that these are each 2 to 4 groups.

In the present specification, the ring is a substituted or unsubstituted hydrocarbon ring; Or a substituted or unsubstituted heterocycle.

In the present specification, the hydrocarbon ring may be an aromatic, aliphatic or aromatic and aliphatic condensed ring, and may be selected from the examples of the cycloalkyl group or the aryl group except the univalent hydrocarbon ring.

In this specification, the aromatic ring may be monocyclic or polycyclic and may be selected from the examples of the aryl group except that it is not monovalent.

In the present specification, the hetero ring includes one or more non-carbon atoms and hetero atoms. Specifically, the hetero atom may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. The heterocyclic ring may be monocyclic or polycyclic, and may be aromatic, aliphatic or aromatic and aliphatic condensed rings, and may be selected from the examples of the heteroaryl group except that it is not monovalent.

In the present specification, an arylene group means a divalent group having two bonding positions in an aryl group. The description of the aryl group described above can be applied except that each of these is 2 groups.

In the present specification, the heteroarylene group means that the heteroaryl group has two bonding positions, that is, divalent. The description of the above-mentioned heteroaryl groups can be applied, except that they are each 2 groups.

In one embodiment of the present disclosure, A is hydrogen.

In one embodiment of the present invention, B is an aryl group having 6 to 30 carbon atoms.

In one embodiment of the present specification, L is a substituted or unsubstituted aryl group.

In one embodiment of the present specification, L is an aryl group.

In one embodiment of the present specification, L is a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthylene group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted An anthracenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted triphenylene group, a substituted or unsubstituted pyrenyl group, a substituted or unsubstituted perylenyl group, a substituted or unsubstituted creicenyl group or a substituted Or an unsubstituted fluorenyl group.

In one embodiment of the present specification, L may be selected from among the following structural formulas.

In the above structural formulas, A1 and A2 are the same as or different from each other, and each independently hydrogen; An alkyl group; An aryl group, or they may be bonded to each other to form a ring.

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to be.

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to be.

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to be.

In one embodiment of the present specification, A is hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

In one embodiment of the present invention, A is hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms substituted or unsubstituted with deuterium.

In one embodiment of the present disclosure, A is a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms which is substituted with hydrogen, deuterium, an alkyl group having 1 to 10 carbon atoms, or deuterium.

In one embodiment of the present specification, A is hydrogen, deuterium, a t-butyl group, or a phenyl group.

In one embodiment of the present specification, B is hydrogen, deuterium, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

In one embodiment of the present specification, B is hydrogen, deuterium, an alkyl group having 1 to 10 carbon atoms, or a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms, which is substituted or unsubstituted with deuterium.

In one embodiment of the present invention, B is a hydrogen, a t-butyl group, a phenyl group substituted or unsubstituted with deuterium, or a biphenyl group.

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

[Compound 1] [Compound 2] [Compound 3]

[Compound 4] [Compound 5] [Compound 6]

[Compound 7] [Compound 8] [Compound 9]

[Compound 10] [Compound 11] [Compound 12]

[Compound 13] [Compound 14] [Compound 15]

[Compound 16] [Compound 17] [Compound 18]

[Compound 19] [Compound 20] [Compound 21]

[Compound 22] [Compound 23] [Compound 24]

[Compound 25] [Compound 26] [Compound 27]

[Compound 28] [Compound 29] [Compound 30]

[Compound 31] [Compound 32] [Compound 33]

[Compound 34] [Compound 35] [Compound 36]

[Compound 37] [Compound 38] [Compound 39]

[Compound 40] [Compound 41] [Compound 42]

[Compound 43] [Compound 44] [Compound 45]

[Compound 46] [Compound 47] [Compound 48]

According to one embodiment, the compound of formula 1 described above can be prepared according to the following reaction scheme.

[Reaction Scheme]

In the above reaction formula, X is Br, Cl, I, OTf, or ONf, which may be the same or different. The compound of Formula 1 can be prepared through Suzuki coupling and borylation reactions as shown in the above reaction scheme.

The present invention also provides an organic light emitting device comprising the above-described compound.

In one embodiment of the present application, the organic light emitting device includes a first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers includes the compound.

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 in this specification may have a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer 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 one embodiment of the present invention, the organic material layer includes a hole injecting layer, a hole transporting layer, or a layer simultaneously injecting and transporting holes, and the hole injecting layer, the hole transporting layer, (1).

In one embodiment of the present invention, the organic material layer includes an electron injecting layer, an electron transporting layer, or a layer simultaneously injecting and transporting electrons, and the electron injecting layer, the electron transporting layer, (1).

In one embodiment of the present invention, the electron injection layer comprises the compound of Formula 1 as a host.

In one embodiment of the present invention, the electron injection layer includes the compound of Formula 1 as a host, and includes a dopant.

In one embodiment of the present invention, the electron injection layer comprises the compound of Formula 1 as a host, and includes one or more n-type dopants selected from among alkali metals and alkaline earth metals.

In one embodiment of the present invention, the electron injecting layer contains the compound of Formula 1 and one or more n-type dopants selected from alkali metals and alkaline earth metals in a mass ratio of 1: 1000 to 1000: 1 do.

In one embodiment of the present invention, the electron injection layer contains the n-type dopant in a range of 0.01 wt% to 50 wt% relative to the compound of the formula (1).

In one embodiment of the present invention, the electron injection layer contains the n-type dopant in a range of 0.1 wt% to 10 wt% relative to the compound of the formula (1).

In one embodiment of the present invention, the organic material layer includes two or more light emitting layers, and a charge generation layer including an n-type electron generating layer and a p-type hole generating layer is provided between the two or more light emitting layers, The electron generating layer comprises the above compound.

In another embodiment, the n-type electron generating layer comprises one or more n-type dopants selected from the compound of Chemical Formula 1 and an alkali metal and an alkaline earth metal. For example, Li may be included as an n-type dopant.

In another embodiment, the n-type electron generating layer comprises one or more n-type dopants selected from the group consisting of the compound of Formula 1 and an alkali metal and an alkaline earth metal in a mass ratio of 1: 1000 to 1000: 1 do.

In another embodiment, the n-type electron generating layer contains the n-type dopant in an amount of 0.01 wt% to 50 wt% relative to the compound of the formula (1).

In another embodiment, the n-type electron generating layer comprises the n-type dopant in an amount of 0.1 wt% to 10 wt% relative to the compound of the formula (1).

In another embodiment, the organic layer includes a light-emitting layer, and the light-emitting layer includes the compound of the general formula (1).

When a member is referred to herein as being "on " another member, it includes not only a member in contact with another member but also another member between the two members.

Whenever a component is referred to as "comprising ", it is understood that it may include other components as well, without departing from the other components unless specifically stated otherwise.

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

In one embodiment of the present application, the organic layer includes a light emitting layer, and the light emitting layer includes the compound.

In one embodiment of the present application, the organic 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 one embodiment of the present application, the organic material layer includes an electron transporting layer or an electron injecting layer, and the electron transporting layer or the electron injecting layer includes the above compound.

In one embodiment of the present application, the organic 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 one embodiment of the present application, the organic light emitting device includes a first electrode; A second electrode facing the first electrode; And a light emitting layer provided between the first electrode and the second electrode; At least one of the two or more organic layers includes two or more organic layers disposed between the light emitting layer and the first electrode or between the light emitting layer and the second electrode.

In one embodiment of the present application, the two or more organic layers may be selected from the group consisting of an electron transport layer, an electron injection layer, a layer that simultaneously transports electrons and electrons, and a hole blocking layer.

In one embodiment of the present application, the organic material layer includes two or more electron transporting layers, and at least one of the two or more electron transporting layers includes the above compound. Specifically, in one embodiment of the present specification, the compound may be contained in one of the two or more electron transporting layers, and may be included in each of two or more electron transporting layers.

In the embodiment of the present application, when the compound is contained in each of the two or more electron transporting layers, the materials other than the above compounds may be the same or different from each other.

In one embodiment of the present application, the organic layer further includes a hole injection layer or a hole transport layer containing a compound containing an arylamino group, a carbazolyl group or a benzocarbazolyl group in addition to the organic compound layer containing the compound.

In another embodiment, the organic light emitting device may be a normal type organic light emitting device in which an anode, at least one organic layer, and a cathode are sequentially stacked on a substrate.

In another embodiment, the organic light emitting device may be an inverted type organic light emitting device in which a cathode, at least one organic material layer, and an anode are sequentially stacked on a substrate.

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

1 illustrates a structure of an organic light emitting device in which a substrate 101, an anode 102, a light emitting layer 103, and a cathode 104 are sequentially laminated. In such a structure, the compound may be included in the light emitting layer.

2 illustrates the structure of an organic light emitting device in which a substrate 101, an anode 102, a hole transporting layer 105, a light emitting layer 103, an electron transporting layer 106, and a cathode 104 are sequentially laminated. In such a structure, the compound may be contained in at least one of the hole transporting layer 103, the light emitting layer 104, and the electron transporting layer 105.

In particular, the electron-transporting layer may contain the compound.

3 shows an organic light emitting device in which a substrate 101, an anode 102, a hole injecting layer 107, a hole transporting layer 105, a light emitting layer 103, an electron transporting layer 106 and a cathode 104 are sequentially laminated Structure is illustrated. In such a structure, the compound may be included in at least one of the hole injection layer 107, the hole transport layer 103, the light emitting layer 104, and the electron transport layer 105.

In particular, the electron-transporting layer may contain the compound.

Fig. 4 is a cross-sectional view of an organic EL device according to a second embodiment of the present invention. Fig. 4 is a cross-sectional view of a substrate 101, an anode 102, a hole injecting layer 107, a hole transporting layer 105a, an electron blocking layer 110a, a light emitting layer 103a, an electron transporting layer 106, The hole injection layer 108, the p-type hole generation layer 109, the hole transport layer 105b, the electron blocking layer 110b, the light emitting layer 103b, the electron injection and electron transport layer 111, the LiF 112, The structure of the organic light emitting device is illustrated. In such a structure, the compound may be included in at least one of the hole injection layer 107, the hole transport layer 103, the light emitting layer 104, and the electron transport layer 105.

In particular, the electron-transporting layer, the n-type electron-generating layer, or the electron injecting and electron-transporting layer may contain the above compound.

In FIGS. 2 to 4, the hole injecting layer, the hole transporting layer, the electron blocking layer, the electron transporting layer, the LiF, the electron injecting and transporting layer may be omitted if necessary.

The organic light emitting device of the present application may be manufactured by materials and methods known in the art, except that one or more of the organic layers include the compound of the present application, i.e., the compound.

When the organic light emitting diode includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

The organic light emitting device of the present application can be produced by materials and methods known in the art, except that one or more of the organic layers include the above compound, that is, the compound represented by the above formula (1).

For example, the organic light emitting device of the present application can be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a PVD (physical vapor deposition) method such as a sputtering method or an e-beam evaporation method, a metal or a metal oxide having conductivity or an alloy thereof is deposited on the substrate to form a positive electrode Forming an organic material layer including a hole injecting layer, a hole transporting layer, a light emitting layer and an electron transporting layer thereon, and depositing a material usable as a cathode thereon. In addition to such a method, an organic light emitting device can be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

In addition, the compound of Formula 1 may be formed into an organic material layer by a solution coating method as well as a vacuum evaporation method in the production of an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating and the like, but is not limited thereto.

In addition to such a method, an organic light emitting device may be fabricated by sequentially depositing an organic material layer and a cathode material on a substrate from a cathode material (International Patent Application Publication No. 2003/012890). However, the manufacturing method is not limited thereto.

In one embodiment of the present application, the first electrode is an anode and the second electrode is a cathode.

In another embodiment, the first electrode is a cathode and the second electrode is a cathode.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode 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), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline.

The negative electrode material is preferably 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; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

The hole injecting material is a layer for injecting holes from the electrode. The hole injecting material has a hole injecting effect, a hole injecting effect in the anode, and an excellent hole injecting effect in the light emitting layer or the light emitting material. A compound which prevents the exciton from migrating to the electron injection layer or the electron injection material and is also excellent in the thin film forming ability is preferable. It is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material be between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrin, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene- , Anthraquinone, polyaniline and polythiophene-based conductive polymers, but the present invention is not limited thereto.

The hole transport layer is a layer that transports holes from the hole injection layer 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 include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; 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 is a condensed aromatic ring derivative or a heterocyclic compound. Specific examples of the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds. Examples of heterocycle-containing compounds include compounds, dibenzofuran derivatives, ladder furan compounds , Pyrimidine derivatives, and the like, but are not limited thereto.

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

The electron injection layer is a layer for injecting electrons from the electrode. The electron injection layer has the ability to transport electrons, has an electron injection effect from the cathode, and has an excellent electron injection effect with respect to the light emitting layer or the light emitting material. A compound which prevents migration of a layer and is excellent in a thin film forming ability is preferable. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A complex compound and a nitrogen-containing five-membered ring derivative, 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- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, But is not limited thereto.

The hole blocking layer prevents holes from reaching the cathode, and may be formed under the same conditions as those of the hole injecting layer. Specific examples thereof include, but are not limited to, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes and the like.

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

The preparation of the compound represented by Formula 1 and the organic light emitting device comprising 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.

< Manufacturing example >

&Lt; Preparation Example 1 & Preparation of [Compound 2]

   [Compound A] [Compound B] [Compound 2]

[Compound A] (10 g, 25.8 mmol) and [Compound B] (10.5 g, 25.8 mmol) were placed in 150 mL of dioxane. 100 ml of 2M K ₃ PO ₄ , 0.4 g of Pd (dba) _{2 and} 0.4 g of PCy ₃ were added, and the mixture was refluxed for 6 hours. The resulting solid was recrystallized from chloroform and ethanol to give [Compound 2] (11.8 g, yield 77%, MS: [M + H] ⁺ = 592).

PREPARATION EXAMPLE 2 Preparation of [Compound 4]

[Compound C] [Compound B] [Compound 4]

[Compound C] (10 g, 25.8 mmol) and [Compound B] (10.5 g, 25.8 mmol) were placed in 150 mL of dioxane. 100 ml of 2M K ₃ PO ₄ , 0.4 g of Pd (dba) _{2 and} 0.4 g of PCy ₃ were added, and the mixture was refluxed for 8 hours. The mixture was cooled to room temperature, filtered, and the resulting solid was recrystallized from chloroform and ethanol to give [Compound 4] (10.8 g, yield 71%, MS: [M + H] ⁺ = 592).

PREPARATION EXAMPLE 3 Preparation of [Compound 22]

[Compound A] [Compound D] [Compound 22]

[Compound A] (10 g, 25.8 mmol) and [Compound D] (10.8 g, 25.8 mmol) were added to 150 mL of dioxane. 100 ml of 2M K ₃ PO ₄ , 0.4 g of Pd (dba) _{2 and} 0.4 g of PCy ₃ were added, and the mixture was refluxed with stirring for 10 hours. The resulting solid was recrystallized from chloroform and ethanol to obtain [Compound 22] (10.9 g, yield 66%, MS: [M + H] ⁺ = 642).

PREPARATION EXAMPLE 4 Preparation of [Compound 27]

[Compound A] [Compound E] [Compound 27]

[Compound A] (10 g, 25.8 mmol) and [Compound E] (12.4 g, 25.8 mmol) were placed in 150 mL of dioxane. 100 ml of 2M K ₃ PO ₄ , 0.4 g of Pd (dba) _{2 and} 0.4 g of PCy ₃ were added, and the mixture was refluxed for 3 hours. The mixture was cooled to room temperature, filtered, and the resulting solid was recrystallized from chloroform and ethanol to give Compound [27] (11.2 g, yield 68%, MS: [M + H] ⁺ = 642).

PREPARATION EXAMPLE 5 Preparation of [Compound 34]

[Compound A] [Compound F] [Compound 34]

[Compound A] (10 g, 25.8 mmol) and [Compound F] (11.2 g, 25.8 mmol) were placed in 150 mL of dioxane. 100 ml of 2M K ₃ PO ₄ , 0.4 g of Pd (dba) _{2 and} 0.4 g of PCy ₃ were added, and the mixture was refluxed for 2 hours. The mixture was cooled to room temperature, filtered, and the resulting solid was recrystallized from chloroform and ethanol to give Compound (34) (12.2 g, yield 75%, MS: [M + H] ⁺ = 616).

5 shows the result of mass spectrometry of Compound 34. Fig.

Preparation Example 6 Preparation of [Compound 42]

[Compound A] [Compound G] [Compound 42]

[Compound A] (10 g, 25.8 mmol) and [Compound G] (11.8 g, 25.8 mmol) were placed in 150 mL of dioxane. 100 ml of 2M K ₃ PO ₄ , 0.4 g of Pd (dba) _{2 and} 0.4 g of PCy ₃ were added, and the mixture was refluxed for 2 hours. The reaction mixture was cooled to room temperature, filtered, and the resulting solid was recrystallized from chloroform and ethanol to obtain [Compound 42] (11.6 g, yield 70%, MS: [M + H] ⁺ = 640).

Fig. 6 shows mass analysis results of Compound 42. Fig.

PREPARATION EXAMPLE 7 Preparation of [Compound 49]

[Compound A] [Compound H] [Compound 49]

[Compound A] (10 g, 25.8 mmol) and [Compound H] (11.2 g, 25.8 mmol) were added to 150 mL of dioxane. 100 ml of 2M K ₃ PO ₄ , 0.4 g of Pd (dba) _{2 and} 0.4 g of PCy ₃ were added, and the mixture was refluxed for 2 hours. The resulting solid was recrystallized from chloroform and ethanol to obtain [Compound 49] (10.0 g, yield 63%, MS: [M + H] ⁺ = 616).

PREPARATION EXAMPLE 8 Preparation of [Compound 52]

[Compound A] [Compound I] [Compound 52]

[Compound A] (10 g, 25.8 mmol) and [Compound I] (13.7 g, 25.8 mmol) were placed in 150 mL of dioxane. 100 ml of 2M K ₃ PO ₄ , 0.4 g of Pd (dba) _{2 and} 0.4 g of PCy ₃ were added, and the mixture was refluxed for 2 hours. The mixture was cooled to room temperature, filtered, and the resulting solid was recrystallized from chloroform and ethanol to give 16.0 g (yield 82%, MS: [M + H] ⁺ = 756).

< Example 1 >

[Example 1-1]

A thin glass substrate coated with ITO (indium tin oxide) having a thickness of 1300 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, Fischer Co. product was used as a detergent, and distilled water filtered by a filter of Millipore Co. was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

The following compound [HI-A] was thermally vacuum deposited on the ITO transparent electrode prepared above to a thickness of 600 Å to form a hole injection layer. The following compound [HAT-CN] (50 Å) and the following compound [HT-A] (600 Å) were sequentially vacuum-deposited on the hole injection layer to form a hole transport layer.

Subsequently, the following compounds [BH] and [BD] were vacuum deposited on the hole transport layer at a weight ratio of 25: 1 at a thickness of 200 ANGSTROM to form a light emitting layer.

[Compound 2] was vacuum deposited on the light emitting layer to a thickness of 300 Å to form an electron injection and transport layer. Lithium fluoride (LiF) and aluminum having a thickness of 1,000 Å were sequentially deposited on the electron injecting and transporting layer to form a cathode.

The deposition rate of the organic material was maintained at 0.4 to 0.9 Å / sec, the lithium fluoride at the cathode was maintained at a deposition rate of 0.3 Å / sec, and the deposition rate of aluminum was maintained at 2 Å / sec. by keeping the ^-7 to 5 × 10 ^-8 torr, an organic light emitting device was produced.

           [HI-A] [HAT-CN]

         [HT-A] [BH] [LiQ]

           [BD] [ET-A]

[ET-B] [ET-C]

[Example 1-2]

An organic luminescent device was fabricated in the same manner as in [Example 1-1], except that [Compound 4] was used in place of [Compound 2] in [Example 1-1].

[Example 1-3]

An organic luminescent device was fabricated in the same manner as in [Example 1-1], except that [Compound 22] was used in place of [Compound 2] in [Example 1-1].

[Example 1-4]

An organic luminescent device was fabricated in the same manner as in [Example 1-1], except that [Compound 27] was used in place of [Compound 2] in [Example 1-1].

[Example 1-5]

An organic luminescent device was fabricated in the same manner as in [Example 1-1], except that [Compound 34] was used in place of [Compound 2] in [Example 1-1].

[Example 1-6]

An organic luminescent device was fabricated in the same manner as in [Example 1-1], except that [Compound 42] was used in place of [Compound 2] in [Example 1-1].

[Example 1-6]

An organic luminescent device was fabricated in the same manner as in [Example 1-1], except that [Compound 49] was used in place of [Compound 2] in [Example 1-1].

[Example 1-6]

An organic luminescent device was fabricated in the same manner as in [Example 1-1], except that [Compound 52] was used in place of [Compound 2] in [Example 1-1].

[Comparative Example 1-1]

An organic luminescent device was fabricated in the same manner as in [Example 1-1], except that [ET-A] was used in place of [Compound 2] in [Example 1-1].

[Comparative Example 1-2]

An organic luminescent device was fabricated in the same manner as in [Example 1-1], except that [ET-B] was used in place of [Compound 2] in [Example 1-1].

[Comparative Example 1-3]

An organic luminescent device was fabricated in the same manner as in [Example 1-1], except that [ET-C] was used instead of [Compound 2] in [Example 1-1].

The driving voltage and the luminous efficiency of the organic light emitting device manufactured by the above-described method were measured at a current density of 10 mA / cm ^2. The results are shown in Table 1 below.

Voltage (V) Efficiency (Cd / A) The color coordinates (x, y) Example 1-1 3.87 6.42 (0.131, 0.133) Examples 1-2 3.80 6.75 (0.131, 0.133) Example 1-3 3.77 6.59 (0.131, 0.134) Examples 1-4 3.75 6.92 (0.131, 0.133) Examples 1-5 3.83 6.88 (0.131, 0.132) Examples 1-6 3.88 6.71 (0.131, 0.134) Examples 1-7 3.79 6.58 (0.131, 0.133) Comparative Example 1-1 4.01 5.53 (0.131, 0.138) Comparative Example 1-2 4.41 5.12 (0.131, 0.137) Comparative Example 1-3 4.05 5.82 (0.131, 0.136)

From the results shown in Table 1, it can be confirmed that the compound represented by Chemical Formula 1 according to one embodiment of the present invention can be used to inject electrons into an organic light emitting device. In general, it is known that when LiF / Al is used as the cathode, Li ions are released due to Al high temperature deposition, and Li doping effect is generated, thereby maximizing electron injection. In particular, the compound represented by Formula 1 according to the present invention has a structure capable of maximizing the doping effect of Li ions and can be combined with the released Li ions to lower the driving voltage of the device and increase the efficiency. As seen in the comparative example, as the Li bond position is decreased, the electron injection effect is lowered and the voltage is increased and the efficiency is lowered.

&Lt; Example 2 >

[Example 2-1]

A glass substrate coated with ITO (indium tin oxide) having a thickness of 500 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. At this time, Fischer Co. product was used as a detergent, and distilled water filtered by a filter of Millipore Co. was used as distilled water. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

[HAT-CN] was thermally vacuum deposited on the ITO transparent electrode prepared above to a thickness of 50 Å to form a hole injection layer. A hole transport layer was formed on the hole injection layer by vacuum evaporation of the following chemical formula [NPB] to a thickness of 1100 Å. [HT-A] was vacuum deposited on the hole transport layer to a thickness of 200 Å to form an electron blocking layer.

[BH] and [BD] were vapor deposited at a weight ratio of 25: 1 on the electron blocking layer to a thickness of 200 ANGSTROM to form a light emitting layer.

On the light emitting layer, an electron transport layer was formed by vacuum evaporation of the following chemical formula [ET-1] to a thickness of 200 Å. [Compound 4] and [Li] were vacuum deposited on the electron transport layer at a weight ratio of 99: 1 to form an n-type electron generating layer having a thickness of 100 Å.

The above-mentioned chemical formula [HAT-CN] was thermally vacuum deposited on the n-type electron generating layer to a thickness of 50 Å to form a p-type hole generating layer. A hole transport layer was formed on the p-type hole-transporting layer by vacuum evaporation of the following chemical formula [NPB] to a thickness of 200 Å. [HT-A] was vacuum deposited on the hole transport layer to a thickness of 200 Å to form an electron blocking layer.

[YGD] and [YGH] were vapor-deposited at a weight ratio of 1:10 on the electron blocking layer to a thickness of 350 ANGSTROM to form a light emitting layer.

On the light emitting layer, the following chemical formula [ET-2] was vacuum-deposited to a thickness of 300 Å to form an electron injection and transport layer. LiF was deposited to a thickness of 10 Å on the electron injecting and electron transporting layer, and aluminum was deposited to a thickness of 1,000 Å to form a cathode.

[NPB] [ET-1] [ET-2]

[YGH] [YGD]

The deposition rate of the organic material was maintained at 0.4 to 0.9 Å / sec, the lithium fluoride at the cathode was maintained at a deposition rate of 0.3 Å / sec, and the deposition rate of aluminum was maintained at 2 Å / sec. ^-7 to 5 x 10 &lt; ^-8 &gt; torr to produce an organic light emitting device.

[Example 2-2]

An organic luminescent device was fabricated in the same manner as in [Example 2-1] except that [Compound 34] was used in place of [Compound 4] in [Example 2-1].

[Example 2-3]

An organic luminescent device was fabricated in the same manner as in [Example 2-1] except that [Compound 42] was used instead of [Compound 4] in [Example 2-1].

[Comparative Example 2-1]

An organic luminescent device was fabricated in the same manner as in [Example 2-1] except that [ET-B] was used instead of [Compound 4] in [Example 2-1].

The driving voltage and the luminous efficiency were measured at a current density of 10 mA / cm &lt; ² &gt; and the driving voltage change was measured after driving for 100 hours at a current density of 20 mA / cm &lt; ^{2 &} gt ;. The results are shown in Table 2 below.

Voltage (V) Efficiency (Cd / A) The color coordinates (x, y) Voltage change (? V) Example 2-1 7.9 69.1 (0.365, 0.389) 0.06 Example 2-2 7.8 68.2 (0.365, 0.388) 0.07 Example 2-3 7.7 68.6 (0.365, 0.388) 0.04 Comparative Example 2-1 9.5 58.2 (0.364, 0.387) 0.25

From the results of Table 2, it can be seen that the compound represented by Formula 1 according to one embodiment of the present invention can be used as an n-type electron generating layer of an organic light emitting device.

The compound represented by the formula (1) according to the present invention is excellent in thermal stability and can be used by mixing the n-type dopant such as an alkali metal or an alkaline earth metal using the compound of formula (1) as a host. The compound represented by Formula 1 has low driving voltage and high efficiency, and can improve the stability of the device by hole stability of the compound.

In particular, the compound represented by Formula 1 according to the present invention has a structure capable of maximizing the doping effect of Li ions and can be combined with doped Li ions to lower the driving voltage of the device and increase the efficiency. As seen in the comparative example, as the Li bond position is decreased, the n-type electron generating effect is lowered and the voltage is increased and the efficiency is lowered. In addition, the more the Li ion bonding position is, the more effective it is to prevent the migration of Li ions, and the longer the driving stability of the device can be improved, the smaller the voltage change is.

From the results of the above Table 2, it can be seen that electrons are generated smoothly from the p-type hole-generating layer to the n-type electron-generating layer when the compound represented by the formula 1 is formed into the n-type electron- And thus an organic light emitting device having an effective tandem structure can be realized.

101: substrate
102: anode
103, 103a, and 103b:
104: cathode
105, 105a, and 105b: a hole transport layer
106: electron transport layer
107: Hole injection layer
108: n-type electron generating layer
109: p-type hole-generating layer
110a, 110b: electronic blocking layer
111: electron injection and electron transport layer
112: LiF layer

Claims (9)

A compound represented by the following formula (1):

In Formula 1,
A and B are the same or different from each other, and each independently hydrogen; Or a phenyl group,
L is a phenylene group, a naphthalene group, a divalent phenylene group, a divalent phenanthrene group, or a divalent diphenylfluorene group,
n is an integer of 1 to 7, and when n is 2 or more, A is the same or different from each other,
p is 1 or 2, and when p is 2, L is the same or different from each other,
m is an integer of 1 to 7, and when m is 2 or more, B is the same or different from each other. The method according to claim 1,
Wherein L is selected from among the following structural formulas:

In the above structural formulas, A1 and A2 are phenyl groups.
The method according to claim 1,
Wherein said compound is selected from the following structural formula:

[Compound 1] [Compound 2] [Compound 3]

[Compound 4] [Compound 5] [Compound 6]

[Compound 7]

[Compound 10] [Compound 11] [Compound 12]

[Compound 17] [Compound 18]

[Compound 22] [Compound 23] [Compound 24]

[Compound 25] [Compound 26] [Compound 27]

[Compound 28] [Compound 29]

[Compound 42]

[Compound 46] [Compound 47] [Compound 48]

A first electrode;
A second electrode facing the first electrode; And
And at least one organic compound layer provided between the first electrode and the second electrode,
Wherein at least one of the organic layers includes a compound according to any one of claims 1 to 3. The method of claim 4,
Wherein the organic material layer includes an electron injection layer, an electron transport layer, or an electron injection and electron transport layer,
Wherein the electron injection layer, the electron transport layer, or the electron injection and electron transport layer contain the compound. The method of claim 4,
Wherein the organic material layer includes a hole injection layer or a hole transport layer, and the hole injection layer or the hole transport layer comprises the compound. The method of claim 4,
Wherein the organic layer includes a light emitting layer, and the light emitting layer comprises the compound. The method of claim 5,
Wherein the electron injection layer comprises one or more n-type dopants selected from a host material represented by Formula 1 and an alkali metal and an alkaline earth metal. [Claim 4] The organic electroluminescent device of claim 4, wherein the organic layer includes two or more light emitting layers, and a charge generation layer including an n-type electron generating layer and a p-type hole generating layer is provided between the two or more light emitting layers, Wherein the compound is a compound represented by the following formula (1).

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