KR20170095756A - Heterocyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

The present application provides a heterocyclic compound and an organic electroluminescent device comprising the same. According to one embodiment of the present application, the heterocyclic compound may be used in the organic electroluminescent device to reduce driving voltage of the organic electroluminescent device, improve light efficiency thereof, and improve lifetime characteristics of the device by thermal stability of the compound. Additionally, the organic electroluminescent device comprises: a first electrode; a second electrode disposed to face the first electrode; and one or more organic material layers, wherein at least one layer of the organic material layers comprises the heterocyclic compound.

Description

TECHNICAL FIELD [0001] The present invention relates to a heterocyclic compound and an organic electroluminescent device including the heterocyclic compound and an organic electroluminescent device including the same.

The present invention relates to a heterocyclic compound and an organic electroluminescent device including the same.

This specification claims the benefit of Korean Patent Application No. 10-2016-0017264 filed on Feb. 15, 2016, filed with the Korean Intellectual Property Office, the entire contents of which are incorporated herein by reference.

An electroluminescent device is one type of self-luminous display device, and has advantages of wide viewing angle, excellent contrast, and high response speed.

The organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic light emitting device having such a structure, electrons and holes injected from the two electrodes couple to each other in the organic thin film and form a pair, which then extinguishes and emits light. The organic thin film may be composed of a single layer or a multilayer, if necessary.

The material of the organic thin film may have a light emitting function as needed. For example, as the organic thin film material, a compound capable of forming a light emitting layer by itself may be used, or a compound capable of serving as a host or a dopant of a host-dopant light emitting layer may be used. In addition, as the material of the organic thin film, a compound capable of performing a role such as hole injection, hole transport, electron blocking, hole blocking, electron transport or electron injection may be used.

In order to improve the performance, lifetime or efficiency of an organic electroluminescent device, development of a material for an organic thin film is continuously required.

Korean Patent Publication No. 2000-0051826

The present invention provides a heterocyclic compound and an organic electroluminescent device including the same.

The present application provides a heterocyclic compound represented by the following formula (1).

[Chemical Formula 1]

In Formula 1, Ar1 and Ar2 are the same or different and each independently represents a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

L1 to L3 are the same or different from each other and are each independently a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,

R1 to R3 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; Cyano; A substituted or unsubstituted silyl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

a and c are integers of 0 to 3, b is an integer of 0 to 4, and the substituents in parentheses are the same or different when a to c are two or more.

The present application also includes a first electrode; A second electrode facing 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 above-described heterocyclic compound do.

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

Fig. 1 shows an example of an organic electroluminescent device in which a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially laminated.
2 shows an organic electroluminescent device 1 in which a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 3, an electron transporting layer 7 and a cathode 4 are sequentially stacked. Fig.
Figure 3 is an LC / MS spectrum of formula (1A) of Scheme 1.
4 is an LC / MS spectrum of Compound 1 of Synthesis Example 1. Fig.
5 is an LC / MS spectrum of Compound 2 of Synthesis Example 2. Fig.
6 is an LC / MS spectrum of Compound 7 of Synthesis Example 7. Fig.

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

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

Examples of substituents herein 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; Cyano; A nitro group; A hydroxy group; Phosphine oxide groups; Silyl group; An alkyl group; A cycloalkyl group; An alkenyl group; An alkoxy group; An aryl group; And a heterocyclic group, or that at least two of the substituents exemplified in the above exemplified substituents are substituted with a connected substituent, 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.

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

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. 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 preferably has 3 to 60 carbon atoms, and specifically includes cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, But are not limited to, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert- butylcyclohexyl, cycloheptyl, Do not.

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specific examples include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n Butyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like. But is not limited thereto.

In the present specification, the alkenyl group may be straight-chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Butenyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, (Diphenyl-1-yl) vinyl-1-yl, stilbenyl, stilenyl, and the like.

In the present specification, when the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 25 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 has 10 to 24 carbon atoms. Specific examples of the polycyclic aryl group include naphthyl, anthracenyl, phenanthryl, pyrenyl, perylenyl, klychenyl, fluorenyl, and the like.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may be bonded to each other to form a ring.

,

이 될 수 있으나, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

But is not limited thereto.

), 피리다지닐기, 피라지닐기, 퀴놀리닐기, 퀴나졸리닐기, 퀴녹살리닐기, 프탈라지닐기, 피리도피리미디닐기, 피리도피라지닐기, 피라지노피라지닐기, 이소퀴놀리닐기, 인돌기, 카바졸릴기, 벤즈옥사졸릴기, 벤즈이미다졸릴기, 벤조티아졸릴기, 벤조카바졸릴기, 디벤조카바졸릴기, 벤조티오페닐기, 디벤조티오페닐기, 벤조퓨라닐기, 디벤조퓨라닐기; 벤조실롤기; 디벤조실롤기; 페난트롤리닐기(phenanthrolinyl group), 이소옥사졸릴기, 티아디아졸릴기, 페노티아지닐기, 페노옥사지닐기, 및 이들의 축합구조 등이 있으나, 이들에만 한정되는 것은 아니다. 이외에도 헤테로고리기의 예로서, 술포닐기를 포함하는 헤테로고리 구조, 예컨대,

등이 있다.In the present specification, the heterocyclic group includes at least one non-carbon atom and at least one hetero atom. Specifically, the hetero atom may include at least one atom selected from the group consisting of O, N, Se, Si and S have. The number of carbon atoms of the heterocyclic group is not particularly limited, but is preferably 2 to 60 carbon atoms. Examples of the heterocyclic group include thiophenyl group, furanyl group, pyrrolyl group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, triazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, Group, an acridyl group, a hydroacridyl group (e.g.,

), A pyridazinyl group, a pyrazinyl group, a quinolinyl group, a quinazolinyl group, a quinoxalinyl group, a phthalazinyl group, a pyridopyrimidinyl group, a pyridopyranyl group, a pyrazinopyrazinyl group, an isoquinolinyl group , An indole group, a carbazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a benzocarbazolyl group, a dibenzocarbazolyl group, a benzothiophenyl group, a dibenzothiophenyl group, a benzofuranyl group, A furanyl group; Benzosyl group; Dibenzosilyl groups; A phenanthrolinyl group, an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, a phenoxazinyl group, a condensed structure thereof, and the like, but are not limited thereto. In addition, examples of the heterocyclic group include a heterocyclic structure including a sulfonyl group,

.

등이 될 수 있으나, 이에 한정되는 것은 아니다.In the present specification, the condensed structure may be a structure in which an aromatic carbon-hydrogen ring is condensed with the substituent. For example, as a condensation ring of benzimidazole

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

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, an "adjacent" group may mean a substituent in which the substituent is substituted with an atom directly connected to the substituted atom, or another substituent in which the substituent is substituted with a substituted atom. For example, two substituents substituted at the ortho position in the benzene ring and two substituents substituted at the same carbon in the aliphatic ring may be interpreted as "adjacent" groups to each other.

In one embodiment of the present specification, Ar1 and Ar2 are the same or different and each independently represents a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.

In one embodiment of the present specification, Ar 1 and Ar 2 are the same or different and each independently represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

In one embodiment of the present specification, Ar1 and Ar2 are the same or different and are each independently a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted triphenylene group; A substituted or unsubstituted dimethylfluorene group; A substituted or unsubstituted dibenzofurane group; A substituted or unsubstituted dibenzothiophene group; Or a substituted or unsubstituted carbazole group.

In one embodiment of the present specification, Ar1 and Ar2 are the same or different and each independently represents a phenyl group substituted or unsubstituted with an aryl group; A biphenyl group substituted or unsubstituted with an aryl group; A terphenyl group substituted or unsubstituted with an aryl group; A triphenylene group substituted or unsubstituted with an aryl group; A dimethylfluorene group substituted or unsubstituted with an aryl group; A dibenzofurane group substituted or unsubstituted with an aryl group; A dibenzothiophene group substituted or unsubstituted with an aryl group; Or a carbazol group substituted or unsubstituted with an aryl group.

In one embodiment of the present specification, Ar1 and Ar2 are the same or different and each independently represents a phenyl group substituted or unsubstituted with a phenyl group; A biphenyl group substituted or unsubstituted with a phenyl group; A terphenyl group substituted or unsubstituted with a phenyl group; A triphenylene group substituted or unsubstituted with a phenyl group; A dimethylfluorene group substituted or unsubstituted with a phenyl group; A dibenzofurane group substituted or unsubstituted with a phenyl group; A dibenzothiophene group substituted or unsubstituted with a phenyl group; Or a carbazol group substituted or unsubstituted with a phenyl group.

In one embodiment of the present specification, Ar1 and Ar2 are the same or different and each independently represents a phenyl group substituted or unsubstituted with a phenyl group; Biphenyl group; A terphenyl group; Triphenylene group; A dimethylfluorene group substituted or unsubstituted with a phenyl group; A dibenzofurane group substituted or unsubstituted with a phenyl group; A dibenzothiophene group substituted or unsubstituted with a phenyl group; Or a carbazol group substituted or unsubstituted with a phenyl group.

In one embodiment of the present disclosure, L1 is a direct bond; A substituted or unsubstituted arylene group having 6 to 30 carbon atoms; Or a substituted or unsubstituted divalent heterocyclic group having 2 to 60 carbon atoms.

In one embodiment of the present disclosure, L1 is a direct bond; A substituted or unsubstituted arylene group having 6 to 20 carbon atoms; Or a substituted or unsubstituted divalent heterocyclic group having 2 to 30 carbon atoms.

In one embodiment of the present disclosure, L1 is a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted divalent dibenzofuranyl group; A substituted or unsubstituted divalent dibenzothiophenyl group; Or a substituted or unsubstituted divalent fluorenyl group.

In one embodiment of the present disclosure, L1 is a direct bond; A phenylene group substituted or unsubstituted with an alkyl group; A divalent dibenzofuranyl group substituted or unsubstituted with an alkyl group; A divalent dibenzothiophenyl group substituted or unsubstituted with an alkyl group; Or a divalent fluorenyl group substituted or unsubstituted with an alkyl group.

In one embodiment of the present disclosure, L1 is a direct bond; A phenylene group; A divalent dibenzofuranyl group; A divalent dibenzothiophenyl group; A divalent fluorenyl group; Or a divalent dimethylfluorenyl group.

In one embodiment of the present invention, L2 and L3 are the same or different and are each independently a direct bond or a substituted or unsubstituted arylene group.

In one embodiment of the present invention, L2 and L3 are the same or different from each other, and each independently is a direct bond or an arylene group.

In one embodiment of the present invention, L2 and L3 are the same or different from each other, and each independently is a direct bond or a phenylene group.

In one embodiment of the present disclosure, R 1 to R 3 are hydrogen.

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

The compound according to one embodiment of the present specification can be produced by a production method described below.

[Reaction Scheme 1]

1) Preparation of formula (I-a)

(1.0 eq) of 9H-carbazole and 100.74 g (1.5 eq) of KOtBu were added to 1 L of DMF (dimethylformamide), and the mixture was heated and stirred. At the start of the reflux, 149.33 g (1.2 eq) of 1-bromo-3-chloro-2-fluorobenzene was added. After the reaction was completed after 5 hours, the reaction product was poured into water and the crystals were dropped and filtered. The filtered solid was completely dissolved in CHCl ₃ , washed with water, and then decompressed to remove the solvent, which was purified by column chromatography. 191.22 g (yield 90%) of the compound of the formula 1-a was obtained. [M + 2H] = 356

2) Preparation of compound of formula 1A

To 191.22 g (1.0 eq) of the compound of the formula 1-a was added Pd (t-Bu ₃ P) ₂ 1.19 g (0.005 eq) of K ₂ CO _{3 and} 129.74 g (2.00 eq) of K ₂ CO _{3 were} placed in 1 L of dimethylacetamide, and the mixture was refluxed and stirred. After 3 hours, the reaction mixture was poured into water, and crystals were dropped and filtered. The filtered solid was completely dissolved in ethyl acetate and washed with water. The solution in which the product was dissolved was concentrated under reduced pressure and purified by column chromatography. To obtain 107.15 g (yield: 83%) of the formula (1A). [M] = 275

The present invention also provides an organic electroluminescent device comprising the aforementioned compound.

In one embodiment of the present application, the first electrode; A second electrode facing 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 heterocyclic compound .

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 to be understood that the component may include other components as well, without departing from the scope of the present invention.

The organic material layer of the organic electroluminescent 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 representative example of the organic electroluminescent device of the present invention, the organic electroluminescent device may have a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, an electron injecting layer, etc. as an organic material layer. However, the structure of the organic electroluminescent device is not limited thereto and may include a smaller number of organic layers.

In one embodiment of the present application, the thickness of the organic material layer is 1 to 1000 angstroms.

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

In one embodiment of the present application, the organic material layer includes a hole injecting layer or a hole transporting layer, and the hole injecting layer or the hole transporting layer includes the heterocyclic compound.

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

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

In one embodiment of the present application, the organic electroluminescent 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; And 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, and at least one of the two or more organic layers includes the heterocyclic compound.

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 heterocyclic compound. Specifically, in one embodiment of the present specification, the heterocyclic 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 addition, in one embodiment of the present application, when the heterocyclic compound is included in each of the two or more electron transporting layers, the materials other than the heterocyclic compound may be the same or different.

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

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

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

For example, the structure of an organic electroluminescent device according to one embodiment of the present application is illustrated in Figs. 1 and 2. Fig.

1 shows a structure of an organic electroluminescent device in which a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4 are sequentially laminated. In such a structure, the heterocyclic compound may be included in the light emitting layer (3).

2 shows an organic electroluminescent device 1 in which a substrate 1, an anode 2, a hole injecting layer 5, a hole transporting layer 6, a light emitting layer 3, an electron transporting layer 7 and a cathode 4 are sequentially stacked. Are illustrated. In such a structure, the heterocyclic compound may be contained in at least one of the hole injection layer 5, the hole transport layer 6, the light emitting layer 3, and the electron transport layer 7.

In such a structure, the heterocyclic compound may be contained in at least one of the hole injecting layer, the hole transporting layer, the light emitting layer, and the electron transporting layer.

The organic electroluminescent device of the present application can be produced by materials and methods known in the art, except that at least one of the organic layers includes the heterocyclic compound of the present invention, i.e., the heterocyclic compound.

When the organic electroluminescent device includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

 The organic electroluminescent device of the present application can be manufactured by materials and methods known in the art, except that at least one of the organic layers includes the heterocyclic compound, that is, the compound represented by the above formula (1).

For example, the organic electroluminescent 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 electroluminescent device can be manufactured by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

The heterocyclic compound of Formula 1 may be formed into an organic layer by a solution coating method as well as a vacuum deposition method in the production of an organic electroluminescent 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 electroluminescent device can also 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 to 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 electroluminescent device according to the present invention may be a front emission type, a back emission type, or a both-sided emission type, depending on the material used.

Hereinafter, the present invention will be described in detail by way of examples with reference to the drawings. However, the embodiments according to the present disclosure can be modified in various other forms, and the scope of the present application is not construed as being limited to the embodiments described below. The embodiments of the present application are provided to enable those skilled in the art to more fully understand the present invention.

Synthesis Example 1: Compound 1

10.1 g (1.0 eq) of the compound represented by the formula 1A, 11.19 g (1.1 (3-tert-butylphenyl) the eq), NaOtBu 6.98 g (2.0 eq), Pd (t-Bu 3 P) 2 0.09 g (0.005 eq) was stirred under reflux and dissolved in 90 ml of xylene (xylene). After 1 hour, the reaction was terminated and the solvent was removed under reduced pressure. After that, it was completely dissolved in CHCl ₃ , washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 20.56 g (yield: 87%) of Compound 1. [M + H] = 651

Synthesis Example 2. Compound 2

11.19 g (1.1 eq.) Of the compound represented by the formula 1A (1.0 eq) and 11.19 g of N- (4- (9,9-dimethyl-9H-fluoren- the eq), NaOtBu 6.98 g (2.0 eq), Pd (t-Bu 3 P) 2 0.09 g (0.005 eq) was stirred under reflux and dissolved in 90 ml of xylene (xylene). After 1 hour, the reaction was terminated and the solvent was removed under reduced pressure. After that, it was completely dissolved in CHCl ₃ , washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 20.16 g (yield: 82%) of Compound 2. [M + H] < + > = 677

Synthesis Example 3: Compound 3

(1, 1 ': 3', 1 " -terphenyl] -5 ' -amine was stirred and 11.19 g (1.1 eq), NaOtBu 6.98 g (2.0 eq), a _{Pd (t-Bu 3 P)} 2 0.09 g (0.005 eq) and xylene (xylene) under reflux and dissolved in 90 ml. After 1 hour, the reaction was terminated and the solvent was removed under reduced pressure. After that, it was completely dissolved in CHCl ₃ , washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 22.70 g (yield 86%) of Compound 3. [ [M] = 726

SYNTHESIS EXAMPLE 4 Compound 4

(1.0 eq), (4 - ([1,1 ': 3', 1 "-terphenyl] -5'-yl (4- (dibenzo [b, ) phenyl) amino) phenyl) boronic acid 24.28 g (1.1 eq), dissolved in water _{40ml K 3 PO 4 15.43 g (} 2.0 eq), Pd (t-Bu 3 P) 2 0.09 g (0.005 eq) of dioxane 90 ml, refluxed and stirred. After 1 hour, the reaction was terminated and the solvent was removed under reduced pressure. After that, it was completely dissolved in CHCl ₃ , washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 25.08 g (yield 86%) of Compound 4. [ [M + H] < + > = 803

Synthesis Example 5: Compound 5

10.0 g (1.0 eq) of the compound represented by the formula 1A, (4 - ([1,1'-biphenyl] -4- ) boronic acid 8.39 g (1.1 eq), dissolved in water _{40ml K 3 PO 4 15.43 g (} 2.0 eq), Pd (t-Bu 3 P) 2 0.09 g (0.005 eq) of dioxane was stirred under reflux and dissolved in 90 ml did. After 1 hour, the reaction was terminated and the solvent was removed under reduced pressure. After that, it was completely dissolved in CHCl ₃ , washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 22.70 g (yield: 83%) of Compound 5. [M + H] = 753

Synthesis Example 6: Compound 6

(1.0 eq.), (4 - ([1,1'-biphenyl] -4- (dibenzo [b, d] furan- 15.93 g (2.0 eq) of K ₃ PO _{4 and} 0.09 g (0.005 eq) of Pd (t-Bu ₃ P) ₂ dissolved in 9.89 g (1.1 eq) of acid and 40 ml of water were dissolved in 90 ml of dioxane and refluxed and stirred. After 1 hour, the reaction was terminated and the solvent was removed under reduced pressure. After that, it was completely dissolved in CHCl ₃ , washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 22.44 g (yield: 85%) of Compound 6. [M + H] < + > = 727

Synthesis Example 7: Compound 7

(1.0 eq), 6.13 g (1.0 eq) of (4 - ((4- (dibenzo [b, d] furan-4-yl) phenyl) (triphenylene- 1.1 eq), 15.43 g (2.0 eq) of K ₃ PO ₄ dissolved in 40 ml of water and 0.09 g (0.005 eq) of Pd (t-Bu ₃ P) ₂ were dissolved in 90 ml of dioxane and refluxed and stirred. After 1 hour, the reaction was terminated and the solvent was removed under reduced pressure. After that, it was completely dissolved in CHCl ₃ , washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 23.27 g (yield 80%) of Compound 7. [M + H] < + > = 801

Synthesis Example 8: Compound 8

(Triphenylen-2-yl) amino) phenyl) boronic acid 25.24 g (1.0 eq), (4 - 15.43 g (2.0 eq) of K ₃ PO _{4 and} 0.09 g (0.005 eq) of Pd (t-Bu ₃ P) ₂ dissolved in 40 ml of water were dissolved in 90 ml of dioxane and refluxed with stirring. After 1 hour, the reaction was terminated and the solvent was removed under reduced pressure. After that, it was completely dissolved in CHCl ₃ , washed with water and decompressed again to remove about 50% of the solvent. Ethyl acetate was added in the refluxing state, and the crystals were dropped and cooled, followed by filtration. This was subjected to column chromatography to obtain 24.33 g (yield 81%) of Compound 8. [M + H] < + > = 827

<Comparative Example>

The glass substrate coated with ITO (indium tin oxide) thin film with a thickness of 1,000 Å was immersed in distilled water containing detergent and washed with ultrasonic waves. In this case, Fischer Co. 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.

Hexaazatriphenylene (HAT-CN) of the following chemical formula was thermally vacuum deposited on the ITO transparent electrode thus prepared to a thickness of 150 Å to form a hole injection layer. The following compound HT (1150 ANGSTROM), which is a material for transporting holes, was vacuum deposited on the hole injection layer to form a hole transport layer. Subsequently, the following compound EB was vacuum deposited on the hole transport layer to a thickness of 150 ANGSTROM to form an electron blocking layer. Subsequently, the following BH and BD were vapor-deposited at a weight ratio of 25: 1 on the electron blocking layer to a thickness of 30 ANGSTROM to form a light emitting layer. The compound ET and the compound LiQ (Lithium Quinolate) were vacuum deposited on the light emitting layer at a weight ratio of 1: 1 to form an electron injecting and transporting layer having a thickness of 360 Å. Lithium fluoride (LiF) and aluminum were deposited to a thickness of 2000 Å on the electron injecting and transporting layer sequentially to form a cathode. Was maintained at the deposition rate was 0.4 ~ 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was 0.3Å / sec, aluminum is deposited at a rate of 2Å / sec, During the deposition, a vacuum 2 × 10 ^{- 7} to 5 x 10 &lt; ^-6 &gt; torr. Thus, an organic electroluminescent device was fabricated.

<Experimental Example 1-1>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example except for using Compound 1 instead of Compound EB in the above Comparative Examples.

<Experimental Example 1-2>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example except for using Compound 2 instead of Compound EB in the above Comparative Examples.

<Experimental Example 1-3>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example except that Compound 3 was used instead of Compound EB in the above Comparative Examples.

<Experimental Example 1-4>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example except for using Compound 4 instead of Compound EB in the above Comparative Examples.

<Experimental Example 1-5>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example, except that Compound 5 was used instead of Compound EB in the above Comparative Examples.

<Experimental Example 1-6>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example except for using Compound 6 instead of Compound EB in the above Comparative Examples.

<Experimental Example 1-7>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example except for using Compound 7 instead of Compound EB in the above Comparative Examples.

<Experimental Example 1-8>

An organic electroluminescent device was fabricated in the same manner as in Comparative Example except for using Compound 8 instead of Compound EB in the above Comparative Examples.

&Lt; Comparative Example 1 &

An organic electroluminescent device was fabricated in the same manner as in the above Comparative Example, except that the above compound H-1 was used instead of the compound EB in the above Comparative Example.

&Lt; Comparative Example 2 &

An organic electroluminescent device was fabricated in the same manner as in the above Comparative Example, except that the above compound H-2 was used instead of the compound EB.

&Lt; Comparative Example 3 &

An organic electroluminescent device was fabricated in the same manner as in the above Comparative Example, except that the above compound H-3 was used instead of the compound EB.

&Lt; Comparative Example 4 &

An organic electroluminescent device was fabricated in the same manner as in the above Comparative Example, except that the above compound H-4 was used instead of the compound EB.

&Lt; Comparative Example 5 &

An organic electroluminescent device was fabricated in the same manner as in the above Comparative Example, except that the above compound H-5 was used instead of the compound EB.

&Lt; Comparative Example 6 >

An organic electroluminescent device was fabricated in the same manner as in the above Comparative Example, except that the above compound H-6 was used instead of the compound EB.

Current density, luminance, color coordinate and lifetime were measured when current was applied to the organic electroluminescent device fabricated according to Experimental Examples 1-1 to 1-8 and Comparative Examples 1 to 6, and the results are shown in Table 1 ]. T95 means the time required for the luminance to decrease from the initial luminance (650 nits) to 95%.

Electronic stop layer Voltage V
(@ 10 mA / cm ² ) Efficiency cd / A
(@ 10 mA / cm ² ) Luminous color T95 Experimental Example 1-1 Compound 1 3.87 5.29 blue 230 Experimental Example 1-2 Compound 2 3.83 5.35 blue 215 Experimental Example 1-3 Compound 3 3.89 5.25 blue 210 Experimental Examples 1-4 Compound 4 3.85 5.35 blue 200 Experimental Examples 1-5 Compound 5 3.77 5.38 blue 205 Experimental Example 1-6 Compound 6 3.74 5.41 blue 240 Experimental Example 1-7 Compound 7 3.72 5.47 blue 230 Experimental Examples 1-8 Compound 8 3.72 5.45 blue 225 Comparative Example 1 H-1 4.19 4.82 blue 158 Comparative Example 2 H-2 4.13 4.91 blue 163 Comparative Example 3 H-3 4.25 4.68 blue 170 Comparative Example 4 H-4 4.22 4.73 blue 175 Comparative Example 5 H-5 4.05 5.02 blue 185 Comparative Example 6 H-6 4.10 4.95 blue 176

As shown in Table 1, the organic electroluminescent device manufactured 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 electroluminescent device.

The core of the present invention exhibits characteristics of low voltage, high efficiency, and long life, compared with organic electroluminescent devices manufactured using the compounds of Comparative Examples 1 to 6 as electron blocking layers. Voltage was reduced by 5 ~ 10% and efficiency increased by more than 10%. The orientation of amines linked to the existing indolo [3,2,1-jk] carbazole at # 2, # 10, and # 11, as in the compound of the present invention, And the stability of the core indole [3,2,1-jk] carbazole itself is also improved by showing an increase in efficiency, a decrease in voltage and a long life when connected in a losing direction. In addition, since the core and amine are connected to each other in a large amount, they are also excellent in thermal stability.

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

Claims (12)

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

In Formula 1, Ar1 and Ar2 are the same or different and each independently represents a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
L1 to L3 are the same or different from each other and are each independently a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,
R1 to R3 are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; Cyano; A substituted or unsubstituted silyl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
a and c are integers of 0 to 3, b is an integer of 0 to 4, and when a to c are 2 or more, the substituents in parentheses are the same or different. [2] The compound according to claim 1, wherein Ar1 and Ar2 are the same or different and each independently represents 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. [2] The compound according to claim 1, wherein Ar1 and Ar2 are the same or different from each other and are each independently a phenyl group substituted or unsubstituted with a phenyl group; A biphenyl group substituted or unsubstituted with a phenyl group; A terphenyl group substituted or unsubstituted with a phenyl group; A triphenylene group substituted or unsubstituted with a phenyl group; A dimethylfluorene group substituted or unsubstituted with a phenyl group; A dibenzofurane group substituted or unsubstituted with a phenyl group; A dibenzothiophene group substituted or unsubstituted with a phenyl group; Or a carbazole group substituted or unsubstituted with a phenyl group. [2] The compound according to claim 1, wherein L1 is a direct bond; A phenylene group; A divalent dibenzofuranyl group; A divalent dibenzothiophenyl group; A divalent fluorenyl group; Or a divalent dimethylfluorenyl. [3] The compound according to claim 1, wherein L2 and L3 are the same or different from each other, and each independently is a direct bond; Or a phenylene group. 2. The heterocyclic compound according to claim 1, wherein R1 to R3 are hydrogen. The heterocyclic compound according to claim 1, wherein the compound of formula (1) is selected from the following structural formulas:

A first electrode; A second electrode facing 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 a heterocyclic compound according to any one of claims 1 to 7 Organic electroluminescent device. The organic electroluminescent device according to claim 8, wherein the organic layer includes a light emitting layer, and the light emitting layer includes the heterocyclic compound. [Claim 9] The organic electroluminescent device according to claim 8, wherein the organic material layer comprises a hole injection layer or a hole transport layer, and the hole injection layer or the hole transport layer comprises the heterocyclic compound. The organic electroluminescent device according to claim 8, wherein 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 heterocyclic compound. The organic electroluminescent device according to claim 8, wherein the organic material layer includes an electron blocking layer, and the electron blocking layer includes the heterocyclic compound.

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