KR102067854B1 - Amine-based compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

Amine compound and organic light emitting device including the same {AMINE-BASED COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME}

The present specification relates to an amine compound and an organic light emitting device including the same.

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

There is a continuing need for the development of new materials for such organic light emitting devices.

Korean Unexamined Patent Publication No. 2011-0110718

Herein, an amine compound and an organic light emitting device including the same are described.

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

[Formula 1]

In Chemical Formula 1,

Ar is hydrogen; heavy hydrogen; Or a substituted or unsubstituted aryl group,

X is any one of formula B-1 to formula B-4,

Y is any one of formula B-1 to formula B-6,

[Formula B-1]

[Formula B-2]

[Formula B-3]

[Formula B-4]

[Formula B-5]

[Formula B-6]

In Chemical Formulas B-1 to B-4,

R ₁ to R ₁₈ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amino group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted heteroarylamine group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted aryl phosphine group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

a, f, o and p are the same as or different from each other, and each independently an integer of 0 to 5,

b, c, e, g, h, j, k, l, m and q are the same as or different from each other, each independently represent an integer of 0 to 4,

d, i, n and r are the same as or different from each other, and each independently an integer of 0 to 3,

When a, b, c, d, e, f, g, h, i, j, k, l, m, n, o, p and r are each two or more, the structures in parentheses are the same or different from each other.

In addition, an exemplary embodiment of the present specification includes a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound of Formula 1.

The compound described herein can be used as the material of the organic material layer of the organic light emitting device. The compound according to at least one exemplary embodiment may improve efficiency, low driving voltage, and / or lifetime characteristics in the organic light emitting diode. In particular, the compounds described herein can be used as hole injection, hole transport, hole injection and hole transport, electron suppression, luminescence, hole suppression, electron transport, or electron injection material.

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

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

An exemplary embodiment of the present specification provides a compound represented by Chemical Formula 1. The compound of Formula 1 is an aromatic amine compound having a large steric hindrance structure, and has an effect of improving the efficiency of an organic light emitting device including the same. In addition, when X and Y have a structure having few steric hindrances in the formulas B-1 to B-4, the efficiency of the organic light emitting device is lower than that of the structure having a large steric hindrance.

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

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

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

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

In the present specification, the oxygen of the ester group may be substituted with a linear, branched or cyclic alkyl group having 1 to 40 carbon atoms or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

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

In the present specification, the silyl group may be represented by a chemical formula of -SiR _a R _b R _c , wherein R _a , R _b and R _c are each hydrogen; Substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group. Specific examples of the silyl group include trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, and phenylsilyl group. Do not.

In the present specification, the boron group may be represented by the formula of -BR _a R _b , wherein R _a and R _b are each hydrogen; Substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group. The boron group may include, but is not limited to, trimethylboron group, triethylboron group, t-butyldimethylboron group, triphenylboron group, and phenylboron group.

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

In the present specification, the alkoxy group may be linear, branched or cyclic. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C40. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy and the like It may be, but is not limited thereto.

Substituents comprising alkyl groups, alkoxy groups and other alkyl group moieties described herein include both straight and pulverized forms.

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

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 40 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but is not limited thereto.

In the present specification, the alkylamine group is not particularly limited in carbon number, but is preferably 1 to 40. Specific examples of the alkylamine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 9-methyl-anthracenylamine Groups, diphenylamine groups, phenylnaphthylamine groups, ditolylamine groups, phenyltolylamine groups, triphenylamine groups and the like, but are not limited thereto.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group, may be a polycyclic aryl group. The arylamine group including two or more aryl groups may simultaneously include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group.

Specific examples of the aryl amine group include phenylamine, naphthylamine, biphenylamine, anthracenylamine, 3-methyl-phenylamine, 4-methyl-naphthylamine, 2-methyl-biphenylamine, 9-methyl-anthra Cenylamine, diphenyl amine group, phenyl naphthyl amine group, ditolyl amine group, phenyl tolyl amine group, carbazole and triphenyl amine group and the like, but are not limited thereto.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroaryl group in the heteroarylamine group may be a monocyclic hetero ring group or may be a polycyclic hetero ring group. The heteroarylamine group including two or more heterocyclic groups may simultaneously include a monocyclic hetero ring group, a polycyclic hetero ring group, or a monocyclic hetero ring group and a polycyclic hetero ring group.

In the present specification, the arylheteroarylamine group means an amine group substituted with an aryl group and a heterocyclic group.

In the present specification, examples of the arylphosphine group include a substituted or unsubstituted monoarylphosphine group, a substituted or unsubstituted diarylphosphine group, or a substituted or unsubstituted triarylphosphine group. The aryl group in the arylphosphine group may be a monocyclic aryl group, may be a polycyclic aryl group. The arylphosphine group containing two or more aryl groups may simultaneously include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group.

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

In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.

,

등의 스피로플루오레닐기,

(9,9-디메틸플루오레닐기), 및

(9,9-디페닐플루오레닐기) 등의 치환된 플루오레닐기가 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

Spirofluorenyl groups, such as

(9,9-dimethylfluorenyl group), and

Substituted fluorenyl groups such as (9,9-diphenylfluorenyl group). However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group including one or more of N, O, P, S, Si, and Se as hetero atoms, and carbon number is not particularly limited, but is preferably 1 to 60 carbon atoms. According to an exemplary embodiment, the heterocyclic group has 1 to 30 carbon atoms. Examples of the heterocyclic group include, for example, pyridyl group, pyrrole group, pyrimidyl group, pyridazinyl group, furanyl group, thiophenyl group, imidazole group, pyrazole group, oxazole group, isoxazole group, thiazole group, isoazole group, Triazole group, oxadiazole group, thiadiazole group, dithiazole group, tetrazole group, pyranyl group, thiopyranyl group, pyrazinyl group, oxazinyl group, thiazinyl group, deoxyyl group, triazinyl group, tetrazinyl group, quinone Nolinyl group, isoquinolinyl group, quinolyl group, quinazolinyl group, quinoxalinyl group, naphthyridinyl group, acriridyl group, xanthenyl group, phenanthridinyl group, diazanaphthalenyl group, triazaininyl group, indole group , Indolinyl group, indolinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, benzothiazole group, benzoxazole group, benzimidazole group, benzothiophene group , Benzofuranyl group, dibenzothiophenyl group, dibenzofuranyl , Carbazole group, benzocarbazole group, dibenzocarbazole group, indolocarbazole group, indenocarbazole group, phenazinyl group, imidazopyridine group, phenoxazinyl group, phenanthridine group, phenanthroline group, phenanthroline group, phenanthroline group Phenothiazine, imidazopyridine and imidazophenanthridine groups. Although there exists a benzoimidazoquinazoline group or a benzoimidazophenanthridine group, it is not limited only to these.

In the present specification, the description of the aforementioned hetero ring group may be applied except that the heteroaryl group is aromatic.

In the present specification, the aryl group in the aryloxy group, arylthioxy group, aryl sulfoxy group, aryl phosphine group, aralkyl group, aralkylamine group, aralkenyl group, alkylaryl group, arylamine group, arylheteroarylamine group is described above. The description of one aryl group may apply.

In the present specification, the alkyl group among the alkyl thioxy group, the alkyl sulfoxy group, the aralkyl group, the aralkyl amine group, the alkyl aryl group, and the alkyl amine group may be described with respect to the alkyl group described above.

In the present specification, the heteroaryl group, the heteroarylamine group, and the arylheteroarylamine group, except that the heteroaryl group is aromatic, the description of the heterocyclic group may be applied.

In the present specification, the alkenyl group of the alkenyl group may be applied to the description of the alkenyl group described above.

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

In the present specification, the description of the aforementioned hetero ring group may be applied except that the heteroarylene group is an aromatic divalent group.

In one embodiment of the present invention, Ar is hydrogen; heavy hydrogen; It is a substituted or unsubstituted aryl group.

In one embodiment of the present invention, Ar is hydrogen; heavy hydrogen; Or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

In one embodiment of the present invention, Ar is hydrogen; heavy hydrogen; It is a C6-C30 monocyclic or polycyclic substituted or unsubstituted aryl group.

In one embodiment of the present invention, Ar is hydrogen; heavy hydrogen; Substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; Substituted or unsubstituted terphenyl group; Substituted or unsubstituted naphthyl group; Substituted or unsubstituted phenanthrenyl group; Substituted or unsubstituted triprylenyl group; Or a substituted or unsubstituted fluorenyl group.

In another embodiment, Ar is hydrogen; heavy hydrogen; Phenyl group; A phenyl group unsubstituted or substituted with an aryl group; Biphenyl group; Terphenyl group; Naphthyl group; Phenanthrenyl group; Triprylenyl group; Fluorenyl group; It is a fluorenyl group substituted with one or more substituents selected from the group consisting of an alkyl group and an aryl group.

In one embodiment, Ar is hydrogen; heavy hydrogen; Or any one selected from the following structures.

The structures are deuterium; Halogen group; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amine group; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; An alkyl group; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Alkylamine group; Aralkyl amine groups; Heteroarylamine group; Arylamine group; Aryl heteroaryl amine group; Aryl phosphine group; And it may be substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group.

In one embodiment of the present invention, Ar is hydrogen; heavy hydrogen; Phenyl group; A phenyl group unsubstituted or substituted with a naphthyl group; Biphenyl group; Terphenyl group; Naphthyl group; Phenanthrenyl group; Triprylenyl group; Fluorenyl group; It is a fluorenyl group substituted with at least one substituent selected from the group consisting of a methyl group and a phenyl group.

In one embodiment of the present invention, R ₁ to R ₁₈ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Hydroxyl group; Carbonyl group; Ester group; Imide group; Amino group; Substituted or unsubstituted silyl group; Substituted or unsubstituted boron group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted heteroarylamine group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted aryl phosphine group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group.

In one embodiment of the present invention, R ₁ to R ₁₈ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted heteroarylamine group; Substituted or unsubstituted arylamine group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group.

In one embodiment of the present invention, R ₁ to R ₁₈ are hydrogen.

In one embodiment of the present invention, the compound of Formula 1 may be any one selected from the following compounds.

The compound of Formula 1 may be prepared by the following reaction, but the preparation method is not limited thereto.

In the above scheme, Z is any one selected from the following structures, A is the same as the definition of X or Y in formula (1).

In addition, the organic light emitting device according to the present invention is an organic light emitting device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, at least one of the organic layer It is characterized by including the compound.

The organic light emitting device of the present invention may be manufactured by a conventional method and material for manufacturing an organic light emitting device, except that at least one organic material layer is formed using the above-described compound.

The compound may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method in the manufacture of the organic light emitting device. Here, the solution coating method means spin coating, dip coating, inkjet printing, screen printing, spraying method, roll coating and the like, but is not limited thereto.

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

Accordingly, in the organic light emitting device of the present invention, the organic material layer may include at least one layer of a hole injection layer, a hole transport layer, and a layer for simultaneously injecting holes and transporting holes, wherein at least one of the layers is represented by Formula 1 It may include a compound represented by.

In another exemplary embodiment, the organic material layer may include an electron blocking layer, and the electron blocking layer may include the compound.

In one exemplary embodiment, the organic material layer includes a light emitting layer, and the light emitting layer includes a compound represented by Chemical Formula 1. As one example, the compound represented by Formula 1 may be included as a host of the light emitting layer. As another example, the compound represented by Chemical Formula 1 may be included as a phosphorescent host of the emission layer.

As another example, the organic material layer including the compound represented by Chemical Formula 1 may include the compound represented by Chemical Formula 1 as a host, and may include another organic compound, a metal, or a metal compound as a dopant.

As another example, the organic material layer including the compound represented by Chemical Formula 1 may include the compound represented by Chemical Formula 1 as a host, and may be used together with an iridium-based (Ir) dopant.

In addition, the organic material layer may include one or more layers of an electron transport layer, an electron injection layer, and a layer for simultaneously transporting and transporting electrons, and one or more of the layers may include the compound.

In another exemplary embodiment, the organic material layer of the organic electronic device includes a hole transport layer, and the hole transport layer includes a compound represented by Chemical Formula 1.

In the organic layer of the multilayer structure, the compound may be included in a light emitting layer, a layer for simultaneously injecting / holes transporting and emitting light, a layer for simultaneously transporting holes and emitting light, or a layer for simultaneously transporting electrons and emitting light.

For example, the structure of the organic light emitting device of the present invention may have a structure as shown in FIGS. 1 and 2, but is not limited thereto.

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

2 illustrates an organic light emitting device in which an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 7, an electron transport layer 8, and a cathode 4 are sequentially stacked on a substrate 1. The structure is illustrated. In such a structure, the compound may be included in the hole injection layer 5, the hole transport layer 6, the light emitting layer 7, or the electron transport layer 8.

For example, the organic light emitting device according to the present invention uses a metal vapor deposition (PVD) method such as sputtering or e-beam evaporation, and has a metal oxide or a metal oxide or an alloy thereof on a substrate. It can be prepared by depositing an anode to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

The organic material layer may have a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. In addition, the organic layer may be prepared by using a variety of polymer materials, and by using a method such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer, rather than a deposition method. It can be prepared in layers.

As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); A combination of a metal and an oxide such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as poly (3-methyl compound), poly [3,4- (ethylene-1,2-dioxy) compound] (PEDT), polypyrrole and polyaniline, and the like, but are not limited thereto.

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

The hole injection material is a material capable of well injecting holes from the anode at a low voltage, and the highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organics, hexanitrile hexaazatriphenylene-based organics, quinacridone-based organics, and perylene-based Organic compounds, anthraquinones and polyaniline and poly-compounds of conductive polymers, and the like, but are not limited thereto.

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

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

The organic material layer including the compound represented by Chemical Formula 1 includes the compound represented by Chemical Formula 1 as a host, and may be used together with an iridium-based (Ir) dopant.

Iridium complex used as a dopant is as follows.

Ir (piq) ₃ [Btp ₂ Ir (acac)]

[Ir (ppy) ₃ ] [Ir (ppy) ₂ (acac)]

Ir (mpyp) ₃ [F ₂ Irpic]

[(F ₂ ppy) ₂ Ir (tmd)] [Ir (dfppz) ₃ ]

　　　

　　　

As the electron transporting material, a material capable of injecting electrons well from the cathode and transferring the electrons to the light emitting layer is suitable. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto.

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

The compound according to the present invention may also operate on a principle similar to that applied to organic light emitting devices in organic electronic devices including organic solar cells, organic photoconductors, organic transistors and the like.

The preparation method of the compound of Formula 1 and the preparation of the organic light emitting device using the same will be described in detail in the following Examples. However, the following examples are intended to illustrate the present invention, and the scope of the present invention is not limited thereto.

< Production Example >

The structures of the intermediates A to F used in the preparation examples of the present specification are as follows.

Production Example  One: Synthesis of Compound 1

[Compound A] [Compound 1]

Compound A (10.0 g, 19.96 mmol) and aniline (0.84 g, 8.98 mmol) were completely dissolved in 180 ml of xylene in a 500 ml round bottom flask in nitrogen atmosphere, followed by sodium tert-butoxide (1.05 g, 10.98 mol) was added, bis (tri-tert-butylphosphine) palladium (0) (Bis (tri-tert-butylphosphine) palladium (0)) (0.10 g, 0.20 mmol) was added thereto, and the mixture was heated and stirred for 3 hours. . After cooling to room temperature to remove salts by filtration, xylene was concentrated under reduced pressure and tetrahydrofuran: hexane = 1:12 to prepare the compound 1 (13.35g, yield: 71%).

MS [M + H] ⁺ = 936

Production Example  2: Synthesis of Compound 2

[Compound B] [Compound 2]

Sodium tert-butoxide (1.02g, 10.64) after dissolving Compound B (10.0g, 19.34mmol) and aniline (0.81g, 8.70mmol) in 180ml of xylene in a 500ml round bottom flask under nitrogen atmosphere. mol) was added, bis (tri-tert-butylphosphine) palladium (0) (Bis (tri-tert-butylphosphine) palladium (0)) (0.10 g, 0.19 mmol) was added thereto, and the mixture was heated and stirred for 5 hours. . After the temperature was lowered to room temperature and filtered to remove the salt, xylene was concentrated under reduced pressure and tetrahydrofuran: hexane = 1:15 to prepare Compound 2 (10.98 g, yield: 58%).

MS [M + H] ⁺ = 968

Production Example  3: Synthesis of Compounds 3 to 6

Compounds 3 to 6 were prepared in the same manner as in Preparation Example 1, except that Compound C, D, E, and F were used instead of Compound A as a starting material.

compound MS [M + H] ⁺ Yield (g) % Yield 3 726 8.45 60 4 932 15.54 86 5 964 13.19 71 6 722 10.22 73

Production Example  4: Synthesis of Compound 7

[Compound A] [Compound 7]

Compound A (10.0 g, 19.96 mmol), [1,1'-biphenyl] -4-amine ([1,1'-biphenyl] -4-amine) (1.52 g, 8.98 in a 500 ml round bottom flask in a nitrogen atmosphere. mmol) was completely dissolved in 180 ml of xylene, followed by addition of sodium tert-butoxide (1.05 g, 10.98 mol), and bis (tri-tert-butylphosphine) palladium (0) (Bis (tri -tert-butylphosphine) palladium (0)) (0.10 g, 0.20 mmol) was added thereto, and the mixture was heated and stirred for 5 hours. After cooling to room temperature to remove the salt by filtration and xylene was concentrated under reduced pressure, and then, tetrahydrofuran: hexane = 1: 12 to prepare a compound 7 (16.67g, yield: 83%).

MS [M + H] ⁺ = 1012

Production Example  5: Synthesis of Compounds 8-13

Compounds 8 to 12 were prepared in the same manner as in Preparation Example 4, except that Compounds B, C, D, E, and F were used instead of Compound A as starting materials.

compound MS [M + H] ⁺ Yield (g) yield(%) 8 1044 14.28 69 9 802 12.11 76 10 1008 17.85 89 11 1040 17.63 85 12 798 10.34 65

Production Example  6: Synthesis of Compound 13

[Compound A] [Compound 13]

Compound A (10.0 g, 19.96 mmol), [1,1'-biphenyl] -2-amine ([1,1'-biphenyl] -2-amine) (1.52 g, 8.98 in a 500 ml round bottom flask in nitrogen atmosphere. mmol) was completely dissolved in 210 ml of xylene, followed by addition of sodium tert-butoxide (1.05 g, 10.98 mol), and bis (tri-tert-butylphosphine) palladium (0) (Bis (tri -tert-butylphosphine) palladium (0)) (0.10 g, 0.20 mmol) was added thereto, followed by heating and stirring for 2 hours. After cooling to room temperature to remove the salt by filtration and xylene was concentrated under reduced pressure, and then, tetrahydrofuran: hexane = 1: 8 to prepare a compound 13 (16.67g, yield: 83%).

MS [M + H] ⁺ = 1012

Production Example  7: Synthesis of Compound 14

[Compound C] [Compound 14]

In a 500 ml round bottom flask in nitrogen atmosphere, Compound C (10.0 g, 25.25 mmol) and triphenylen-2-amine (2.76 g, 11.36 mmol) were completely dissolved in 250 ml of xylene, followed by sodium tert- Sodium tert-butoxide (1.33 g, 13.89 mol) was added and bis (tri-tert-butylphosphine) palladium (0) (Bis (tri-tert-butylphosphine) palladium (0)) (0.13 g , 0.25mmol) was added thereto, followed by stirring for 7 hours. After cooling to room temperature to remove the salt by filtration and xylene was concentrated under reduced pressure and recrystallized with 220ml of ethyl acetate to give the compound 14 (20.14g, yield: 91%).

MS [M + H] ⁺ = 876

Production Example  8: Synthesis of Compound 15

[Compound F] [Compound 15]

Compound F (10.0 g, 25.25 mmol), 9,9-dimethyl-9H-fluoren-2-amine (9,9-dimethyl-9H-fluoren-2-amine) (2.38 g) in a 500 ml round bottom flask under nitrogen atmosphere , 11.36 mmol) was completely dissolved in 250 ml of xylene, followed by addition of sodium tert-butoxide (1.33 g, 13.89 mol), and bis (tri-tert-butylphosphine) palladium (0) (Bis (tri-tert-butylphosphine) palladium (0)) (0.13 g, 0.25 mmol) was added thereto, followed by heating and stirring for 6 hours. After cooling to room temperature to remove salts by filtration, xylene was concentrated under reduced pressure and recrystallized with 380 ml of tetrahydrofuran to prepare the compound 15 (16.78 g, yield: 79%).

MS [M + H] ⁺ = 838

< Experimental Example  1>

Experimental Example  1-1

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

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

[HAT]

Compound N-([1,1'-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (9-phenyl-9H-carba), which is a substance for transporting holes on the hole injection layer, Zol-3-yl) phenyl) -9H-fluoren-2-amine (N-([1,1'-biphenyl] -4-yl) -9,9-dimethyl-N- (4- (9-phenyl -9H-carbazol-3-yl) phenyl) -9H-fluoren-2-amine) (300 Pa) was vacuum deposited to form a hole transport layer.

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

[Compound 1]

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

[BH] [BD]

[ET1] [LiQ]

The compound ET1 and the compound LiQ (Lithium Quinolate) were vacuum-deposited on the emission layer in a weight ratio of 1: 1 to form an electron injection and transport layer at a thickness of 300 Pa. The cathode was formed by sequentially depositing lithium fluoride (LiF) and aluminum at a thickness of 2,000 Å on the electron injection and transport layer sequentially.

Was maintained at a vapor deposition rate of 0.4 to 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, the degree of vacuum upon deposition ⅹ10 2 ^-7 The organic light emitting device was manufactured by maintaining the ratio of 5 to 10 ⁻⁶ torr.

Experimental Example  1-2

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

Experimental Example  1-3

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

Experimental Example  1-4

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 6 was used instead of compound 1 in Experimental Example 1-1.

Experimental Example  1-5

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 7 was used instead of compound 1 in Experimental Example 1-1.

Experimental Example  1-6

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

Experimental Example  1-7

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 10 was used instead of compound 1 in Experimental Example 1-1.

Experimental Example  1-8

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 12 was used instead of compound 1 in Experimental Example 1-1.

Experimental Example  1-9

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 13 was used instead of compound 1 in Experimental Example 1-1.

Experimental Example  1-10

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 14 was used instead of compound 1 in Experimental Example 1-1.

Experimental Example  1-11

The organic light emitting device was manufactured by the same method as Experimental Example 1-1, except that compound 15 was used instead of compound 1 in Experimental Example 1-1.

Comparative example  1-1

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

[EB 1]

Comparative example  1-2

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

[EB 2]

Comparative example  1-3

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

[EB 3]

When the electric current was applied to the organic light emitting element produced by Experimental Examples 1-1 to 1-11 and Comparative Examples 1-1 to 1-3, the result of Table 3 was obtained.

compound
(Electron suppression layer) Voltage
(V @ 10mA / cm ² ) efficiency
(cd / A @ 10mA / cm ² ) Color coordinates
(x, y) Experimental Example 1-1 Compound 1 3.65 5.75 (0.137, 0.126) Experimental Example 1-2 Compound 3 3.62 5.78 (0.137, 0.126) Experimental Example 1-3 Compound 4 3.71 5.61 (0.137, 0.127) Experimental Example 1-4 Compound 6 3.72 5.62 (0.137, 0.126) Experimental Example 1-5 Compound 7 3.74 5.63 (0.137, 0.125) Experimental Example 1-6 Compound 9 3.76 5.67 (0.136, 0.127) Experimental Example 1-7 Compound 10 3.78 5.68 (0.136, 0.125) Experimental Example 1-8 Compound 12 3.64 5.51 (0.137, 0.125) Experimental Example 1-9 Compound 13 3.63 5.58 (0.138, 0.125) Experimental Example 1-10 Compound 14 3.68 5.52 (0.136, 0.125) Experimental Example 1-11 Compound 15 3.69 5.47 (0.137, 0.125) Comparative Example 1 EB 1 4.26 4.98 (0.138, 0.124) Comparative Example 2 EB 2 4.31 4.82 (0.139, 0.125) Comparative Example 3 EB 3 4.42 4.75 (0.139, 0.124)

As shown in Table 3, it can be seen that the compounds of Experimental Examples 1-1 to 1-11 exhibit the characteristics of lower voltage and higher efficiency than Comparative Examples 1-1 to 1-3 in the organic light emitting device.

The compound derivative of the formula according to the present invention, which is bent at a position connected to a nitrogen atom, is more organic than the organic light emitting device using the compound of Comparative Examples 1-1 to 1-3, wherein the position at which the nitrogen atom is connected is linearly different from the present case. It has been confirmed that it has excellent electron suppression ability, shows low voltage and high efficiency, and can be applied to an organic light emitting device.

< Experimental Example  2>

Experimental Example  2-1 to Experimental Example  2-11

In Experimental Example 1, EB 1 (TCTA) was used as the electron blocking layer, and N-([1,1′-biphenyl] -4-yl) -9,9-dimethyl-N- (4- was used as the hole transport layer. (9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluorene-2-amine (N-([1,1'-biphenyl] -4-yl) -9,9-dimethyl-N The same experiment was conducted except that the compounds of Experimental Examples 1-1 to 1-11 were used instead of-(4- (9-phenyl-9H-carbazol-3-yl) phenyl) -9H-fluoren-2-amine). .

Comparative example  2-1

Except that HT 1 was used as the hole transport layer in Experimental Example 2-1 was the same experiment.

[HT 1]

Comparative example  2-2

Except that HT 2 was used as the hole transport layer in Experimental Example 2-1 was the same experiment.

[HT 2]

Comparative example  2-3

Except that HT 3 was used as the hole transport layer in Experimental Example 2-1 was the same experiment.

[HT 3]

When the electric current was applied to the organic light emitting element produced by Experimental Example 2-1 to 2-11 and Comparative Example 2-1 to 2-3, the result of Table 4 was obtained.

compound
(Hole transport layer) Voltage
(V @ 10mA / cm ² ) efficiency
(cd / A @ 10mA / cm ² ) Color coordinates
(x, y) Experimental Example 2-1 Compound 1 3.72 6.35 (0.137, 0.126) Experimental Example 2-2 Compound 3 3.79 6.28 (0.137, 0.126) Experimental Example 2-3 Compound 4 3.75 6.31 (0.137, 0.126) Experimental Example 2-4 Compound 6 3.85 6.24 (0.137, 0.126) Experimental Example 2-5 Compound 7 3.86 6.22 (0.136, 0.126) Experimental Example 2-6 Compound 9 3.84 6.13 (0.136, 0.126) Experimental Example 2-7 Compound 10 3.89 6.11 (0.136, 0.125) Experimental Example 2-8 Compound 12 3.95 6.02 (0.137, 0.125) Experimental Example 2-9 Compound 13 3.93 6.01 (0.137, 0.125) Experimental Example 2-10 Compound 14 3.98 5.92 (0.136, 0.125) Experimental Example 2-11 Compound 15 3.93 5.95 (0.137, 0.125) Comparative Example 2-1 HT 1 4.51 4.72 (0.136, 0.127) Comparative Example 2-2 HT 2 4.64 4.65 (0.137, 0.127) Comparative Example 2-3 HT 3 4.48 4.86 (0.137, 0.125)

As shown in Table 4, it can be seen that the compounds of Experimental Examples 2-1 to 2-11 exhibit characteristics of lower voltage and higher efficiency than Comparative Examples 2-1 to 2-3 in organic light emitting devices.

The compound derivative of the formula according to the present invention in which the position connected to the nitrogen atom is bent than the organic light emitting device using the compound of Comparative Examples 2-1 to 2-3 in which the position connected to the nitrogen atom is linearly different from the present case. It was confirmed that the hole transporting ability is excellent and shows low voltage and high efficiency, and can be applied to the organic light emitting device.

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

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

Claims (12)

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

In Chemical Formula 1,
Ar is hydrogen; heavy hydrogen; Aryl groups having 6 to 20 carbon atoms; Or a fluorenyl group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms,
X is any one of formula B-1 to formula B-4,
Y is any one of formula B-1 to formula B-4,
[Formula B-1]

[Formula B-2]

[Formula B-3]

[Formula B-4]

In Chemical Formulas B-1 to B-4,
R ₁ to R ₁₈ are the same as or different from each other, and each independently hydrogen, or adjacent groups are bonded to each other to form a direct bond,
a, f, o and p are the same as or different from each other, and each independently an integer of 0 to 5,
b, c, e, g, h, j, k, l, m and q are the same as or different from each other, each independently represent an integer of 0 to 4,
d, i, n and r are the same as or different from each other, and each independently an integer of 0 to 3,
When a, b, c, d, e, f, g, h, i, j, k, l, m, n, o, p and r are each two or more, the structures in parentheses are the same or different from each other. The compound of claim 1, wherein X and Y of Formula 1 are the same. The compound of claim 1, wherein X and Y of Formula 1 are different from each other. The method according to claim 1, Ar of Formula 1 is hydrogen; heavy hydrogen; Phenyl group; Biphenyl group; Naphthyl group; A fluorenyl group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; Phenanthrenyl group; Or a triphenylenyl group. The method according to claim 1, Ar of Formula 1 is hydrogen; heavy hydrogen; Or a compound selected from the following structures:

. The compound of claim 1, wherein the compound of Formula 1 is any one selected from the following structures:

. An organic light emitting device comprising a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, wherein at least one layer of the organic layer is any one of claims 1 to 6. An organic light-emitting device comprising a compound according to. The organic light emitting device of claim 7, wherein the organic material layer includes at least one of an electron injection layer and an electron transport layer, and at least one layer of the electron injection layer and the electron transport layer includes the compound. The organic light emitting device of claim 7, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes the compound as a host of the light emitting layer. The method according to claim 7, wherein the organic layer comprises a hole injection layer, a hole transport layer, and at least one layer of the hole injection and hole transport at the same time, wherein one of the layers comprises the compound Organic light emitting device. The organic light emitting device of claim 7, wherein the organic material layer includes an electron blocking layer, and the electronic blocking layer includes the compound. The organic light emitting device of claim 7, wherein the organic material layer includes the compound as a host and another organic compound, a metal, or a metal compound as a dopant.

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