KR20170116843A - Heterocyclic compound and organic light emitting device using the same - Google Patents

Abstract

The present invention provides a heterocyclic compound and an organic light emitting device using the heterocyclic compound.

Description

TECHNICAL FIELD [0001] The present invention relates to a heterocyclic compound and an organic light emitting device using the heterocyclic compound. [0002]

The present invention relates to heterocyclic compounds and organic light emitting devices using the same.

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, life or efficiency of an organic light emitting device, development of materials for organic thin films is continuously required.

International Patent Application Publication No. 2003-012890

The present invention provides a heterocyclic compound and an organic light emitting device including the heterocyclic compound.

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

 [Chemical Formula 1]

In Formula 1,

A is a naphthalene ring, a to e are each independently 0 or 1,

R 1 to R 5 are represented by the following formula (2)

(2)

In Formula 2, L represents a direct bond; A substituted or unsubstituted arylene group; A substituted or unsubstituted heteroarylene group,

Ar1 and Ar2 are the same or different from each other, and each independently hydrogen; A substituted or unsubstituted aryl group; A substituted or unsubstituted arylalkyl group; A substituted or unsubstituted arylalkenyl group; A substituted or unsubstituted heterocyclic group,

는 화학식 1과 결합하는 부분을 의미한다.p is an integer of 0 to 3,

Means a moiety bonded to the formula (1).

The present application also 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 heterocyclic compound described above.

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 shows an example of an organic light emitting 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 light emitting device 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 laminated FIG.

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

The present invention provides a 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; An alkyl group; A cycloalkyl group; An alkenyl group; An alkoxy group; A substituted or unsubstituted phosphine oxide 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, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, N-hexyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, 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, the phosphine oxide group specifically includes a diphenylphosphine oxide group, dinaphthylphosphine oxide, and the like, but is not limited thereto.

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.

,

,

,

,

,

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

,

,

,

,

,

And the like, but the present invention 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), 티아졸릴기, 이소옥사졸릴기, 옥사디아졸릴기, 티아디아졸릴기, 벤조티아졸릴기, 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 or hetero atom, and specifically, the hetero atom may include at least one atom selected from the group consisting of O, N, Se and S, and the like. 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, a thiazolyl group, an isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, a phenoxazinyl group, and condensation structures thereof , But are not limited thereto. In addition, examples of the heterocyclic group include a heterocyclic structure including a sulfonyl group,

,

.

In the present specification, the aryl group in the arylalkyl group, arylalkenyl group, alkylaryl group and arylamine group can be applied to the description of the aryl group described above.

In the present specification, the alkyl group, the alkylaryl group and the alkyl group in the alkylamine group may be the same as the alkyl group described above.

In the present specification, the heteroaryl among the heteroarylamines can be applied to the aforementioned heterocyclic group.

In the present specification, the alkenyl group in the arylalkenyl group can be applied to the description of the alkenyl group described above.

In the present specification, the description of the aryl group described above can be applied except that arylene is a divalent group.

In the present specification, the description of the above-mentioned heterocyclic group can be applied except that the heteroarylene is a divalent group.

In one embodiment of the present invention, the formula (1) is represented by any one of the following formulas (3) to (5).

(3)

 [Chemical Formula 4]

[Chemical Formula 5]

In the above formulas (3) to (5), the definitions of R1 to R5 and a to e are as shown in formula (1).

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

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

In one embodiment of the present disclosure, L is a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted fluorene 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 disclosure, L is a direct bond; A phenylene group; Biphenyl group; Naphthyl group; A fluorene group substituted or unsubstituted with one substituent selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group; A dibenzofurane group; A dibenzothiophene group; Or a carbazole group substituted or unsubstituted with an alkyl group.

In one embodiment of the present disclosure, L is selected from a direct bond or the following structural formulas.

In the above structural formulas, the dotted line represents the position of bonding to formula (1) and -N (Ar1) (Ar2), respectively.

In one embodiment of the present specification, Ar1 and Ar2 are the same or different from each other and each independently hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted arylalkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted arylalkenyl group having 2 to 40 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms.

In one embodiment of the present specification, Ar1 and Ar2 are the same or different from each other and each independently hydrogen; A substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted quaterphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted anthracene group; A substituted or unsubstituted phenanthrenyl group; A substituted or unsubstituted triphenylenyl group; A substituted or unsubstituted pyrenyl group; A substituted or unsubstituted crecenyl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted carbazole group; A substituted or unsubstituted dibenzofurane group; Or a substituted or unsubstituted dibenzothiophene group.

In one embodiment of the present specification, Ar1 and Ar2 are the same or different from each other and each independently hydrogen; A phenyl group biphenyltriphenyl group substituted or unsubstituted with an allyl group or a heterocyclic group; A quaterphenyl group; Naphthyl group; Anthracene group; A phenanthrenyl group; A triphenylrenyl group; Pyrenyl; A crycenyl group; A fluorenyl group substituted or unsubstituted with at least one substituent selected from the group consisting of an alkyl group, a cycloalkyl group and an aryl group; A carbazolyl group substituted or unsubstituted with an aryl group; A dibenzofurane group substituted or unsubstituted with an aryl group; Or a dibenzothiophene group substituted or unsubstituted with an aryl group.

In one embodiment of the present specification, Ar1 and Ar2 are the same or different from each other and independently selected from the following structural formulas.

A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, A cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, or combine with each other to form a ring.

In one embodiment of the present invention, at least one of a to e is 1.

In one embodiment of the present disclosure, a is 1 and b to e are 0.

In one embodiment of the present disclosure, b is 1, and a and c to e are zero.

In one embodiment of the present disclosure, c is 1 and a, b, d, and e are zero.

In one embodiment of the present disclosure, d is 1, and a to c and e are zero.

In one embodiment of the present disclosure, e is 1 and a to d are zero.

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 application can be produced by a production method described below.

For example, the compound of Chemical Formula 1 may be prepared in the following manner. Substituent groups may be attached by methods known in the art, and the type, position or number of substituent groups may be varied according to techniques known in the art.

<Production Example>

PREPARATION EXAMPLE 1 Synthesis of A-1 and A-2

 [Synthesis of A-1]

(5.7 g, 21.8 mmol), Cu (0.5 g, 7.1 mmol), CuI (0.34 g, 1.8 mmol) and potassium carbonate (4.2 g, 30.4 mmol) was added to 1,2-dichlorobenzene (30 ml), and the mixture was heated and stirred in a nitrogen atmosphere for 12 hours. After lowering the temperature to room temperature and terminating the reaction, it was extracted with methylene chloride. The solvent was removed, and the residue was recrystallized with ethanol to obtain the above compound A-1 as a yellow solid (5.4 g, yield 89%).

MS [M + H] &lt; + &gt; = 302.11

[Synthesis of A-2]

The above synthesized A-1 (2.0 g, 6.6 mmol) and polyphosphoric acid (10 mL) were heated and stirred at 180 ° C for 4 hours. Extraction with methylene chloride. After removing the solvent, the resulting product was subjected to column chromatography to obtain the above compound A-2, yellow solid (1.2 g, yield 60%).

MS [M + H] &lt; + &gt; = 270.08

PREPARATION EXAMPLE 2 Synthesis of B-1 and B-2

[Synthesis of B-1]

NBS (19.5 g, 110 mmol) and AIBN (2 g, 0.01 mmol) were added to carbon tetrachloride (400 ml) and the mixture was heated with stirring for 3 hours.

After lowering the temperature to room temperature and terminating the reaction, the filtrate is treated with triethylamine (28 ml) for 24 hours. To obtain Compound B-1, pink oil (1.2 g, yield 60%).

MS [M + H] &lt; + &gt; = 231.07

[Synthesis of B-2]

B-1 (4 g, 25 mmol) synthesized above was heated and stirred with dimethylformamide (30 mL) at 130 ° C for 16 hours. After lowering the temperature to room temperature and terminating the reaction, the solvent was removed and the resulting product was subjected to column chromatography to obtain Compound B-2 as a red solid (2.9 g, yield 80%).

MS [M + H] &lt; + &gt; = 270.08

PREPARATION EXAMPLE 3 Synthesis of C-1 to C-4, D-1, and E-1 to E-5

[Synthesis of C-1]

After adding naphthalene-1-boronic acid and 2-bromo-4-chloro-1-iodobenzene to 300 ml of tetrahydrofuran, 2M potassium carbonate aqueous solution (100 ml) Palladium was added, and the mixture was heated and stirred for 4 hours. After the temperature was lowered to room temperature and the reaction was terminated, the potassium carbonate solution was removed and the layers were separated. After removal of the solvent, the compound C-1 was prepared by recrystallization from ethyl acetate and hexane.

MS [M + H] &lt; + &gt; = 316.97

 [Synthesis of C-2]

Bromo-4-chloro-2-iodobenzene was used instead of 2-bromo-4-chloro-1-iodobenzene in the synthesis of C-1, 2 was prepared

MS [M + H] &lt; + &gt; = 316.97

[Synthesis of C-3]

Bromo-3-chloro-2-iodobenzene was used instead of 2-bromo-4-chloro-1-iodobenzene in the synthesis of C-1, 3 was prepared

MS [M + H] &lt; + &gt; = 316.97

[Synthesis of C-4]

(5-Chloronaphthalen-1-yl) boronic acid was used instead of naphthalene-1-boronic acid in the synthesis of C-1, except that 1-bromo- - iodobenzene, the compound C-4 was prepared

MS [M + H] &lt; + &gt; = 316.97

[Synthesis of D-1]

Carbazole, sodium-t-butoxide was added to dimethylacetamide, and 2-bromo-4-chloro-1-fluorobenzene was slowly added dropwise under heating with stirring. After the temperature was lowered to room temperature and the reaction was terminated, water was added and the mixture was filtered. This was then recrystallized from ethyl acetate and hexane to obtain the compound D-1.

MS [M + H] &lt; + &gt; = 355.98

[Synthesis of E-1]

After the compound C-1 was dissolved in THF (250 ml), the temperature was lowered to -78 ° C, 2.5 M n-BuLi (ml) was added dropwise and 30 minutes later, C-2 (g, mmol) And the mixture was stirred at RT for 1 hour. Add 1 N HCl (ml) and stir for 30 minutes. Separate the solvent by layer, recrystallize with chloroform and ethyl acetate, and dry. The dried white solid was added to acetic acid (250 ml), 3 ml of anhydrous sulfuric acid was added dropwise, and the mixture was refluxed with stirring. The temperature was lowered to room temperature, neutralized with water, and the filtered solid was recrystallized from chloroform and ethyl acetate to prepare a compound E-1.

MS [M + H] &lt; + &gt; = 490.13

[Synthesis of E-2]

Compound E-2 was prepared by the same method except for using Compound C-2 instead of Compound C-1 in the synthesis of E-1

MS [M + H] &lt; + &gt; = 490.13

[Synthesis of E-3]

Compound E-3 was prepared by the same method except for using Compound C-3 instead of Compound C-1 in the synthesis of E-1 above

MS [M + H] &lt; + &gt; = 490.13

[Synthesis of E-4]

Compound E-4 was prepared by the same method except for using Compound C-4 instead of Compound C-1 in the synthesis of E-1

MS [M + H] &lt; + &gt; = 490.13

[Synthesis of E-5]

Compound E-5 was prepared by the same method except for using Compound D-1 instead of Compound C-1 and B-2 instead of A-2 in the synthesis of E-1

MS [M + H] &lt; + &gt; = 490.13

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

In one embodiment of the present application, the 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.

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 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 injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting 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 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 a hole injecting layer, a hole transporting layer, or a hole injecting and transporting layer, and the hole injecting layer, the hole transporting layer, or the hole injecting and transporting layer includes the above compound.

In one embodiment of the present application, the organic layer includes a hole control layer, and the hole control layer includes the compound.

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 heterocyclic compound is a phosphorescent host material or a fluorescent host material.

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 injecting layer, an electron transporting layer, or an electron injecting and transporting layer, and the electron injecting layer, the electron transporting layer, or the electron injecting and electron transporting layer.

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.

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

1 shows a structure of an organic light emitting 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 compound may be included in the light emitting layer (3).

2 shows an organic light emitting device 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 laminated Structure is illustrated. In such a structure, the compound may be contained in at least one of the hole injecting layer 5, the hole transporting layer 6, the light emitting layer 3, and the electron transporting layer 7.

In such a structure, the 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 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 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 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.

Synthesis Examples Synthesis of Compounds 1 to 9

&Lt; Synthesis Example 1 > [Synthesis of Compound (1)

(4 mmol) of N-phenyl- [1,1'-biphenyl] -4-amine and sodium-t-butoxide were added to xylene, heated and stirred, Butylphosphine)] palladium (2 mmol%). After the temperature was lowered to room temperature and the reaction was terminated, compound 1 was prepared by recrystallization using tetrahydrofuran and ethyl acetate.

MS [M + H] &lt; ⁺ &gt; = 699.27

Synthesis Example 2 [Synthesis of Compound 2]

Except that di ([1,1'-biphenyl) -4-yl) amine was used instead of N-phenyl- [1,1'-biphenyl] -4- amine in Synthesis of Compound 1 Compound 2 was prepared by synthesis.

MS [M + H] &lt; ⁺ &gt; = 775.30

Synthesis Example 3 [Synthesis of Compound 3]

(1, 1'-biphenyl) -4-yl) -9,9-dimethyl-9H-fluorene in place of N-phenyl- [ 2-amine, the compound 3 was prepared.

MS [M + H] &lt; ⁺ &gt; = 815.33

Synthesis Example 4 [Synthesis of Compound 4]

E-1 and N, N-diphenyl-4- (4,4,5,5-tetramethyl-1,3,2-dioxaborolane-2-yl) aniline were added to dioxane Then, 2M potassium carbonate aqueous solution (100 ml) was added, tetrakistriphenylphosphinopalladium was added, and the mixture was heated and stirred for 4 hours. After the temperature was lowered to room temperature and the reaction was terminated, the potassium carbonate solution was removed and the layers were separated. The solvent was removed, and the residue was recrystallized from tetrahydrofuran tube ethyl acetate to give Compound 4.

MS [M + H] &lt; ⁺ &gt; = 699.27

Synthesis Example 5 [Synthesis of Compound 5]

Synthesis was carried out in the same manner as in the synthesis of the compound 1, except that E-2 was used instead of E-1 and diphenylamine was used instead of N-phenyl- [1,1'-biphenyl] -4- .

MS [M + H] &lt; ⁺ &gt; = 622.24

&Lt; Synthesis Example 6 > [Synthesis of Compound 6]

E-3 was used instead of E-1 in the synthesis of Compound 1, and di ([1,1'-biphenyl) -4-yl) amine Was used to prepare Compound Compound 6.

MS [M + H] &lt; ⁺ &gt; = 775.30

Synthesis Example 7 [Synthesis of Compound 7]

E-3 was used instead of E-1 in the synthesis of Compound 1, and N- (1,1'-biphenyl-4-yl) - 9,9-dimethyl-9H-fluorene-2-amine was used in place of 9,9-dimethyl-9H-fluorene-2-amine.

MS [M + H] &lt; ⁺ &gt; = 815.33

Synthesis Example 8 [Synthesis of Compound 8]

E-4 was used instead of E-1 in the synthesis of Compound 1, and N-phenyl- [1,1 ': 4', 1 '' - Phenyl] -2-amine, the compound 8 was prepared.

MS [M + H] &lt; ⁺ &gt; = 775.30

Synthesis Example 9 [Synthesis of Compound 9]

Compound No. 9 was synthesized by the same method except that E-5 was used instead of E-1 in the synthesis of Compound 1 above.

MS [M + H] &lt; ⁺ &gt; = 699.27

< Example  1>

A glass substrate (corning 7059 glass) coated with ITO (indium tin oxide) at a thickness of 1,000 Å was immersed in distilled water containing a dispersing agent and washed with ultrasonic waves. The detergent was a product of Fischer Co. The distilled water was supplied by Millipore Co. Distilled water, which was secondly filtered with a filter of the product, was used. After the ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After the distilled water was washed, ultrasonic washing was performed in the order of isopropyl alcohol, acetone, and methanol solvent, followed by drying.

Hexanitrile hexaazatriphenylene was thermally vacuum deposited on the prepared ITO transparent electrode to a thickness of 500 Å to form a hole injection layer. Compound 1 (900 Å) synthesized in the above Synthesis Example 1, which is a hole transporting material, was vacuum-deposited thereon, and then HT2 was vacuum-deposited on the hole transport layer to a film thickness of 100 Å to form a hole control layer. A host H1 and a dopant D1 compound (25: 1) were vacuum deposited to a thickness of 300 Å as a compound light emitting layer. Then, an E1 compound (300 ANGSTROM) was sequentially vacuum-deposited by electron injection and transport layer. Lithium fluoride (LiF) having a thickness of 12 Å and aluminum having a thickness of 2,000 Å were sequentially deposited on the electron transporting layer to form a cathode, thereby preparing an organic light emitting device.

In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the deposition rate of lithium fluoride was 0.2 Å / sec, and the deposition rate of aluminum was 3 to 7 Å / sec.

[Hexanitrile hexaazatriphenylgylene] [HT1]

< Example  2>

The same experiment was conducted as in Example 1 except that Compound 2 was used instead of Compound 1 synthesized in Synthesis Example 1 as a hole transporting layer.

< Example  3>

The same experiment was conducted as in Example 1 except that Compound 3 was used instead of Compound 1 synthesized in Synthesis Example 1 as the hole transport layer.

< Example  4>

The same experiment was conducted as in Example 1 except that Compound 4 was used instead of Compound 1 synthesized in Synthesis Example 1 as the hole transport layer.

< Example  5>

The same experiment was conducted as in Example 1 except that Compound 5 was used instead of Compound 1 synthesized in Synthesis Example 1 as a hole transporting layer.

< Example  6>

The same experiment was conducted as in Example 1 except that Compound 8 was used instead of Compound 1 synthesized in Synthesis Example 1 as a hole transporting layer.

< Example  7>

The same experiment was carried out as in Example 1 except that Compound 9 was used instead of Compound 1 synthesized in Synthesis Example 1 as a hole transporting layer.

< Comparative Example  1>

The same experiment was conducted except that HT1 was used instead of the compound 1 synthesized in Synthesis Example 1 as the hole transport layer in Example 1.

< Comparative Example  2>

The same experiment was conducted except that HT3 was used instead of the compound 1 synthesized in Synthesis Example 1 as the hole transport layer in Example 1.

Table 1 shows the results of the organic light emitting device manufactured by using each compound as a hole transporting layer material as in Examples 1 to 7 and Comparative Examples 1 and 2.

Experimental Example
50 mA / cm 2 Hole transport material Voltage (V) Current efficiency (cd / A) Comparative Example 1 HT1 4.11 5.32 Comparative Example 2 HT3 3.98 5.45 Example 1 Compound 1 3.70 5.61 Example 2 Compound 2 3.46 5.75 Example 3 Compound 3 3.59 5.88 Example 4 Compound 4 3.66 5.91 Example 5 Compound 5 3.71 5.55 Example 6 Compound 8 3.65 5.78 Example 7 Compound 9 3.56 5.87

As shown in Table 1, the compounds used in Examples 1 to 7 were used as a hole transport layer in an organic light emitting device, and exhibited lower voltage and higher efficiency characteristics than Comparative Example 1, which is a benzidine type material, It can be seen that the characteristics of high efficiency are maintained. By introducing a naphthyl group, the hole transporting ability is improved, and thus the device exhibits excellent performance.

< Example  8>

A glass substrate (corning 7059 glass) coated with ITO (indium tin oxide) at a thickness of 1,000 Å was immersed in distilled water containing a dispersing agent and washed with ultrasonic waves. The detergent was a product of Fischer Co. The distilled water was supplied by Millipore Co. Distilled water, which was secondly filtered with a filter of the product, was used. After the ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After the distilled water was washed, ultrasonic washing was performed in the order of isopropyl alcohol, acetone, and methanol solvent, followed by drying.

Hexanitrile hexaazatriphenylene was thermally vacuum deposited on the prepared ITO transparent electrode to a thickness of 500 Å to form a hole injection layer. HT1 (900 Å), which is a material for transporting holes, was vacuum deposited on the hole transport layer, followed by vacuum evaporation of Compound 6 to a thickness of 100 Å on the hole transport layer to form a hole control layer. A host H1 and a dopant D1 compound (25: 1) were vacuum deposited to a thickness of 300 Å as a compound light emitting layer. Then, an E1 compound (300 ANGSTROM) was sequentially vacuum-deposited by electron injection and transport layer. Lithium fluoride (LiF) having a thickness of 12 Å and aluminum having a thickness of 2,000 Å were sequentially deposited on the electron transporting layer to form a cathode, thereby preparing an organic light emitting device.

In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the deposition rate of lithium fluoride was 0.2 Å / sec, and the deposition rate of aluminum was 3 to 7 Å / sec.

[Hexanitrile hexaazatriphenylgylene] [HT1]

< Example  9>

The same experiment was conducted as in Example 8 except that Compound 7 was used instead of Compound 6 synthesized in Synthesis Example 6 as the hole control layer.

< Comparative Example  3>

The same experiment was conducted except that HT2 was used instead of the compound 6 synthesized in Synthesis Example 6 as the hole control layer in Example 8.

Table 2 shows the results of the organic light emitting device manufactured by using each compound as a hole control layer material as in Examples 8 to 9 and Comparative Example 3. [

Experimental Example
50 mA / cm 2 Hole-regulating material Voltage (V) Current efficiency (cd / A) Comparative Example 3 HT2 4.02 5.11 Example 8 Compound 6 3.88 5.55 Example 9 Compound 7 3.68 5.42

As shown in Table 2, the compounds used in Examples 8 to 9 were used as the hole-controlling layer in the organic light-emitting device, and exhibited lower voltage and higher efficiency characteristics than the carbazole type HT2 used in Comparative Example 2.

The compound represented by the chemical formula according to the present invention can function as a hole transporting and hole controlling in an organic electronic device including an organic light emitting device, and the device according to the present invention exhibits excellent characteristics in terms of efficiency, driving voltage and 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,
A is a naphthalene ring, a to e are each independently 0 or 1,
R 1 to R 5 are represented by the following formula (2)
(2)

In Formula 2, L represents a direct bond; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
Ar1 and Ar2 are the same or different from each other, and each independently hydrogen; A substituted or unsubstituted aryl group; A substituted or unsubstituted arylalkyl group; A substituted or unsubstituted arylalkenyl group; Or a substituted or unsubstituted heterocyclic group,
p is an integer of 0 to 3,

Means a moiety bonded to the formula (1). The heterocyclic compound according to claim 1, wherein the formula (1) is represented by any one of the following formulas (3) to (5)
(3)

[Chemical Formula 4]

[Chemical Formula 5]

In the above formulas (3) to (5), the definitions of R1 to R5 and a to e are as shown in formula (1). 2. The compound of claim 1, wherein L is a direct bond or a heterocyclic compound selected from the following structural formulas:

In the above structural formulas, the dotted line represents the position of bonding to formula (1) and -N (Ar1) (Ar2), respectively. 2. The heterocyclic compound of claim 1, wherein Ar1 and Ar2 are the same or different and are each independently selected from the following structural formulas:

A substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, A cycloalkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, or combine with each other to form a ring. 2. The heterocyclic compound according to claim 1, wherein at least one of a to e is 1. The heterocyclic compound according to claim 1, wherein the formula (1) is selected from the following structural formulas:

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 heterocyclic compound according to any one of claims 1 to 6 Organic light emitting device. [Claim 7] The organic light emitting device according to claim 7, wherein the organic compound layer comprises a hole injection layer, a hole transport layer or a hole injection and transport layer, and the hole injection layer, the hole transport layer or the hole injection and transport layer comprises the compound. [Claim 7] The organic light emitting device of claim 7, wherein the organic layer includes a hole adjusting layer, and the hole adjusting layer comprises the compound. The organic light emitting device according to claim 7, wherein the organic layer includes a light emitting layer, and the light emitting layer comprises the compound. [Claim 7] The organic light emitting device according to claim 7, wherein the organic layer includes an electron injection layer, an electron transport layer or an electron injection and transport layer, and the electron injection layer, electron transport layer or electron injection and electron layer comprise the compound. [Claim 7] The organic light emitting device according to claim 7, wherein the heterocyclic compound is a phosphorescent host material or a fluorescent host material.

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