KR20190101902A - Heterocyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention relates to a heterocyclic compound of chemical formula 1 and an organic light emitting device comprising the same. In the chemical formula 1, X and Y are the same as or different from each other, and each independently a substituted or unsubstituted aromatic ring, or a substituted or unsubstituted hetero ring, and A1 and A2 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

Description

Heterocyclic compound and organic light-emitting device including the same TECHNICAL FIELD

This specification claims the benefit of the filing date of Korean Patent Application No. 10-2018-0021859, filed with the Korean Intellectual Property Office on February 23, 2018, the entire contents of which are incorporated herein.

The present specification relates to a heterocyclic compound and an organic light emitting device formed using the heterocyclic compound.

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 and the electrons meet each other. When it falls back to the ground, it glows.

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

US Patent Application Publication No. 2004-0251816

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

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

[Formula 1]

In Chemical Formula 1,

X and Y are the same as or different from each other, and each independently represent a substituted or unsubstituted aromatic ring, or a substituted or unsubstituted hetero ring, and in combination with each other, a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aromatic ring, Or a heterocycle including substituted or unsubstituted substituted or unsubstituted O or S,

A1 and A2 are the same as or different from each other, and each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group,

R1 is hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted alkoxy group , A substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or adjacent substituents may combine with each other to form a substituted or unsubstituted ring,

a is an integer of 0 to 3,

When a is plural, the substituents in parentheses are the same as or different from each other.

In addition, another exemplary embodiment of the present specification includes a first electrode; A second electrode provided to face the first electrode; And at least one organic material layer provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the heterocyclic compound.

The heterocyclic compound according to the exemplary embodiment of the present specification may be used as a material of the organic material layer of the organic light emitting device, and by using the same, the efficiency of the organic light emitting device may be improved, and high color purity may be obtained.

1 illustrates an organic light emitting device according to an exemplary embodiment of the present specification.
2 illustrates an organic light emitting device according to an exemplary embodiment of the present specification.

Hereinafter, this specification is demonstrated in detail.

According to an exemplary embodiment of the present specification provides a heterocyclic compound represented by the formula (1).

In the present specification, when a part "includes" a certain component, this means that it may further include other components, without excluding other components unless specifically stated otherwise.

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

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

As used herein, the term "substituted or unsubstituted" is deuterium; Nitrile group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted aryl group; And it is substituted with one or two or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group, or two or more of the substituents exemplified above are substituted with a substituent, or means that do not have any substituents. For example, "a substituent to which two or more substituents are linked" may be an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heterocyclic group substituted with an aryl group, an aryl group substituted with an alkyl group, or the like.

In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-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-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 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 are not limited thereto. It is not.

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-C30. Specifically, it is preferable that it is C1-C20. More specifically, it is preferable that it is C1-C10. Specifically, methoxy group; Ethoxy group; n-propoxy group; Isopropoxy group; i-propyloxy group; n-butoxy group; Isobutoxy group; tert-butoxy group; sec-butoxy group; n-pentyloxy group; Neopentyloxy group; Isopentyloxy group; n-hexyloxy group; 3,3-dimethylbutyloxy group; 2-ethylbutyloxy group; n-octyloxy group; n-nonyloxy group; n-decyloxy group; Benzyloxy group; p-methylbenzyloxy group and the like, but is not limited thereto.

In the present specification, specifically, the silyl group includes trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, and the like. However, the present invention is not limited thereto.

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

When the aryl group is a monocyclic aryl group, carbon number is not particularly limited, but is preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, etc., but is not limited thereto.

Carbon number is not particularly limited when the aryl group is a polycyclic aryl group. It is preferable that it is C10-30. Specifically, the polycyclic aryl group may be naphthyl group, anthracenyl group, phenanthryl group, triphenyl group, pyrenyl group, penalenyl group, perylenyl group, chrysenyl group, fluorenyl group, etc., but is not limited thereto. no.

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

,

,

,

,

및

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

,

,

,

,

And

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

In the present specification, the amine group may be an arylamine group, and 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. have. 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. For example, the aryl group in the arylamine group may be selected from the examples of the aryl group described above.

In the present specification, the heteroaryl group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S, and the like. Although carbon number is not particularly limited, it is preferably 2 to 30 carbon atoms, the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Zolyl group, acridil group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, pe Nanthrolinyl group (phenanthroline), isooxazolyl group, thiadiazolyl group, phenothiazinyl group and dibenzofuranyl group and the like, but is not limited thereto.

According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by the following Chemical Formula 2 or 3.

[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3, the definitions of A1, A2, R1, and a are the same as those defined in Chemical Formula 1,

R2, R3, R6 and R7 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or adjacent substituents may combine with each other to form a substituted or unsubstituted ring,

Z1 and Z2 are the same as or different from each other, and each independently O or S,

b, c, f and g are integers from 0 to 4,

When b, c, f and g are plural, the substituents in parentheses are the same or different from each other.

According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one selected from the following Chemical Formulas 4 to 6.

[Formula 4]

[Formula 5]

[Formula 6]

In Chemical Formulas 4 to 6, the definitions of A1, A2, R1, and a are the same as those defined in Chemical Formula 1,

Z3 is O or S

R2 to R7 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted Alkoxy group, substituted or unsubstituted aryl group, or substituted or unsubstituted heteroaryl group, or adjacent substituents may combine with each other to form a substituted or unsubstituted ring,

b1 and c1 are each an integer of 0 to 3,

d and e are each an integer of 0 to 8,

When b1, c1, d and e are plural, the substituents in parentheses are the same as or different from each other.

According to an exemplary embodiment of the present specification, the R2, R3, R8 and R9 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl A group, a substituted or unsubstituted amine group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or adjacent substituents combine with each other to form a substituted or unsubstituted ring. Can be formed.

According to an exemplary embodiment of the present specification, the R2, R3, R8 and R9 are the same as or different from each other, and each independently hydrogen; Nitrile group; Halogen group; An aryl group unsubstituted or substituted with a silyl group or an alkyl group; An alkyl group having 1 to 10 carbon atoms; A silyl group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; An alkoxy group having 1 to 10 carbon atoms; An amine group unsubstituted or substituted with an aryl group having 6 to 20 carbon atoms; Or an N, O, or S-containing heteroaryl group having 3 to 10 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, the R2 and R3 are the same as or different from each other, and each independently hydrogen; An alkyl group; Or an alkylsilyl group.

According to an exemplary embodiment of the present specification, the R2 and R3 are the same as or different from each other, and each independently hydrogen; An alkyl group having 1 to 10 carbon atoms; An alkylsilyl group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, the R2 and R3 are the same as or different from each other, and each independently hydrogen; Terbutyl group; Or trimethylsilyl group.

According to an exemplary embodiment of the present specification, R1 is hydrogen; An alkyl group having 1 to 10 carbon atoms; A cycloalkyl group having 3 to 10 carbon atoms; Silyl groups substituted with alkyl groups having 1 to 10 carbon atoms; An amine group unsubstituted or substituted with an aryl group having 6 to 20 carbon atoms; Or a heteroaryl group having 3 to 20 carbon atoms.

According to an exemplary embodiment of the present specification, R1 is hydrogen; An alkyl group having 1 to 10 carbon atoms; A cycloalkyl group having 3 to 10 carbon atoms; Silyl groups substituted with alkyl groups having 1 to 10 carbon atoms; An amine group unsubstituted or substituted with an aryl group having 6 to 20 carbon atoms; Or a heteroaryl group containing N, O, or S having 3 to 20 carbon atoms unsubstituted or substituted with an alkyl group.

According to an exemplary embodiment of the present specification, R1 is hydrogen; Methyl group; Ethyl group; Profile group; Butyl group; Terbutyl group; An amine group unsubstituted or substituted with a phenyl group; Carbazole groups; Cyclohexyl group; Trimethylsilyl group; It is a phenophoto group, a phenothiazine group, or a dimethyldihydroacridine group.

According to an exemplary embodiment of the present specification, R1 is hydrogen; Methyl group; Terbutyl group; An amine group unsubstituted or substituted with a phenyl group; Carbazole groups; Cyclohexyl group; Trimethylsilyl group; It is a phenophoto group, a phenothiazine group, or a dimethyldihydroacridine group.

According to an exemplary embodiment of the present specification, R4 and R5 are the same as or different from each other, and each independently an aryl group having 6 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, R4 and R5 is a phenyl group.

According to an exemplary embodiment of the present specification, R6 and R7 are the same as or different from each other, and each independently hydrogen or an alkyl group.

According to an exemplary embodiment of the present specification, R6 and R7 are the same as or different from each other, and each independently hydrogen or an alkyl group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, R6 and R7 are the same as or different from each other, and each independently hydrogen, methyl group, ethyl group, propyl group, butyl group, pentyl group, or hexyl group.

According to an exemplary embodiment of the present specification, R6 and R7 are the same as or different from each other, and each independently hydrogen or a methyl group.

According to an exemplary embodiment of the present specification, the R8 and R9 are the same as or different from each other, and each independently hydrogen; An alkyl group; Alkylsilyl group; Or an alkoxy group.

According to an exemplary embodiment of the present specification, the R8 and R9 are the same as or different from each other, and each independently hydrogen; An alkyl group having 1 to 10 carbon atoms; An alkylsilyl group having 1 to 10 carbon atoms; Or an alkoxy group having 1 to 10 carbon atoms.

According to an exemplary embodiment of the present specification, the R8 and R9 are the same as or different from each other, and each independently hydrogen; Terbutyl group; Trimethylsilyl group; Or a methoxy group.

According to an exemplary embodiment of the present specification, A1 and A2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

According to an exemplary embodiment of the present specification, A1 and A2 are the same as or different from each other, and each independently contain a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted N, O, or S It is a C3-C20 heteroaryl group.

According to an exemplary embodiment of the present specification, A1 and A2 are the same as or different from each other, and each independently a substituted or unsubstituted monocyclic aryl group having 6 to 20 carbon atoms, a substituted or unsubstituted polycyclic polycyclic group having 6 to 20 carbon atoms Monocyclic heteroaryl group having 3 to 20 carbon atoms containing an aryl group, substituted or unsubstituted N, O, or S, or polycyclic having 3 to 20 carbon atoms containing substituted or unsubstituted N, O, or S Heteroaryl group.

According to an exemplary embodiment of the present specification, A1 and A2 are the same as or different from each other, and each independently a monocyclic having 6 to 20 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms, or an alkylsilyl group having 1 to 10 carbon atoms Aryl group; Or a C6-C20 polycyclic aryl group unsubstituted or substituted with a C1-C10 alkyl group or a C1-C10 alkylsilyl group.

According to an exemplary embodiment of the present specification, A1 and A2 are the same as or different from each other, and each independently a monocyclic or polycyclic aryl group having 6 to 20 carbon atoms, and the monocyclic or polycyclic aryl group having 6 to 20 carbon atoms is a methyl group, Substituted or unsubstituted with one or more substituents selected from the group consisting of ethyl group, propyl group, isopropyl group, butyl group, terbutyl group, pentyl group, hexyl group, and trimethylsilyl group.

According to an exemplary embodiment of the present specification, A1 and A2 are the same as or different from each other, and each independently a phenyl group or a biphenyl group, and the phenyl group or biphenyl group is one selected from the group consisting of a methyl group, a terbutyl group, or a trimethylsilyl group It is substituted by the above substituent.

According to yet an embodiment of the present disclosure, the heterocyclic compound of Formula 1 may be represented by any one of the following structural formula.

In addition, the organic light emitting device according to the present invention comprises a first electrode; A second electrode provided to face the first electrode; And an organic light emitting device including one or two or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include a heterocyclic compound of Chemical Formula 1.

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 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. 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.

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 a first electrode 2, an organic material layer 3, and a second electrode 4 are sequentially stacked on a substrate 1.

2, the first electrode 2, the hole injection layer 5, the hole transport layer 6, the electron blocking layer 7, the light emitting layer 8, the electron transport layer 9, and the electron injection layer The structure of the organic light emitting device in which 10) and the second electrode 4 are sequentially stacked is illustrated.

1 and 2 illustrate an organic light emitting diode and are not limited thereto.

In an exemplary embodiment of the present invention, the organic light emitting device has a structure in which a substrate, a first electrode, an organic material layer, and a second electrode are sequentially stacked.

In an exemplary embodiment of the present invention, the organic light emitting device has a structure in which a substrate, a first electrode, a hole injection layer, an electron blocking layer, a light emitting layer, an electron injection layer, and a second electrode are sequentially stacked.

In an exemplary embodiment of the present invention, the organic light emitting device has a structure in which a substrate, a first electrode, a hole transport layer, an electron blocking layer, a light emitting layer, an electron injection layer, and a second electrode are sequentially stacked.

In an exemplary embodiment of the present invention, the organic light emitting device has a structure in which a substrate, a first electrode, a hole injection layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, and a second electrode are sequentially stacked.

In an exemplary embodiment of the present invention, the organic light emitting device has a structure in which a substrate, a first electrode, a hole injection layer, a hole transport layer, an electron blocking layer, a light emitting layer, an electron transport layer, an electron injection layer, and a second electrode are sequentially stacked. .

In an exemplary embodiment of the present invention, the organic material layer including the heterocyclic compound of Formula 1 may include a light emitting layer, and may include the heterocyclic compound of Formula 1 in the light emitting layer.

In an exemplary embodiment of the present invention, the organic material layer including the heterocyclic compound of Formula 1 may include a light emitting layer, and may include the heterocyclic compound of Formula 1 as a dopant of the light emitting layer.

In an exemplary embodiment of the present invention, the organic material layer includes a light emitting layer, and the light emitting layer includes a host and a dopant in a weight ratio of 99: 1 to 1:99.

In an exemplary embodiment of the present invention, the organic material layer including the heterocyclic compound of Formula 1 includes a light emitting layer, and includes a host and a dopant in a weight ratio of 99: 1 to 50:50 in the light emitting layer.

In an exemplary embodiment of the present invention, the organic material layer including the heterocyclic compound of Formula 1 may include a light emitting layer, and an organic compound may be used as a host of the light emitting layer.

In an exemplary embodiment of the present invention, the organic material layer including the heterocyclic compound of Formula 1 may include a light emitting layer, and an anthracene-based organic compound may be used as a host of the light emitting layer.

In an exemplary embodiment of the present invention, the organic material layer including the heterocyclic compound of Formula 1 includes a hole injection layer, a hole transport layer or an electron blocking layer, and the hole injection layer, the hole transport layer or the electron blocking layer is the heterocyclic ring It may include a compound.

In an exemplary embodiment of the present invention, the organic material layer including the heterocyclic compound of Formula 1 includes an electron injection layer, an electron transport layer or a hole blocking layer, and the electron injection layer, the electron transport layer or the hole blocking layer is the heterocyclic ring. It may include a compound.

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. To form an anode and to form an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an organic material layer containing a heterocyclic compound of the formula (1), and then used as a cathode thereon It can be prepared by depositing. 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.

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); ZnO: Al or SnO 2: Combination of metals and oxides such as 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 light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic containing compound. Specifically, the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and the heterocyclic compounds include heterocyclic compounds, dibenzofuran derivatives, and ladder types. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

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

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

For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking an anode, an organic material layer, and a cathode on a substrate. At this time, the anode is formed by depositing a metal or conductive metal oxide or an alloy thereof on the substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. And an organic material layer including a hole injection layer, a hole transporting layer, a light emitting layer, and an electron transporting layer thereon, and then depositing a material that can be used as a cathode thereon. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

The present specification also provides a method of manufacturing an organic light emitting device formed using the heterocyclic compound.

Specifically, in one embodiment of the present specification, preparing a substrate; Forming a cathode or anode on the substrate; Forming at least one organic layer on the cathode or anode; And forming an anode or a cathode on the organic layer, wherein at least one layer of the organic layer is formed using the heterocyclic compound.

Dopant materials include aromatic heterocyclic compounds, styrylamine compounds, boron complexes, fluoranthene compounds, metal complexes, and the like. Specifically, the aromatic heterocyclic compound is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene and periplanthene having an arylamino group, and a styrylamine compound is substituted or unsubstituted. At least one arylvinyl group is substituted with the substituted arylamine, and one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group are substituted or unsubstituted. Specifically, styrylamine, styryldiamine, styryltriamine, styryltetraamine and the like, but is not limited thereto. In addition, the metal complex includes, but is not limited to, an iridium complex, a platinum complex, and the like.

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

The electron injection layer is a layer that injects electrons from an electrode, has an ability to transport electrons, has an electron injection effect from a cathode, an electron injection effect with respect to a light emitting layer or a light emitting material, and hole injection of excitons generated in the light emitting layer The compound which prevents the movement to a layer and is excellent in thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the like and derivatives thereof, metal Complex compounds and nitrogen-containing five-membered ring derivatives;

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxybenzo [h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtolato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtolato) gallium, It is not limited to this.

The hole blocking layer is a layer for preventing the cathode from reaching the hole, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes, and the like, but are not limited thereto.

The organic light emitting device according to the present specification may be a top emission type, a bottom emission type, or a double side emission type according to a material used.

The preparation method of the heterocyclic compound of Formula 1 and the manufacture of an 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.

 Synthesis Example

Synthesis Example 1 Synthesis of Compound 1

In a three-necked flask, tris (2-bromo-4- (terbutyl) phenyl) amine (20.0 g, 30.8 mmol) and terbutylbenzene in 120 ml t-BuLi 1.7 M in pentane (109 ml) at -40 ° C under nitrogen atmosphere , 184.5 mmol) was added and stirred at room temperature for 1 hour. After cooling to 0 ° C., 7.0 ml of BBr _{3 and} 67.7 mmol) were added 30 ml of terbutylbenzene, followed by stirring at room temperature for 1 hour. Was added. After heating for 15 hours at 160 ℃, phenyl magnesium bromide 1.0M in tetrahydrofuran (THF, 185ml, 184.5mmol) was added at room temperature and stirred for 2 hours. The solvent was concentrated under reduced pressure, and then phosphate buffer was added and extracted with a separating funnel using ethyl toluene and water. The extract was dried over MgSO ₄ , concentrated and the sample was purified by silica gel column chromatography to give compound 1 (0.9 g) through sublimation. (Yield 5%, MS [M + H] < + > 612)

Synthesis Example  2: synthesis of compound 2

In Synthesis Example 1, except that 1.0M in THF of phenyl magnesium bromide was changed to 1.0M in THF of 2-mesitylene magnesium bromide, Compound 2 was obtained by the same preparation method as in the preparation of Compound 1. (MS [M + H] ⁺ = 669)

Synthesis Example  3: Synthesis of Compound 3

Step 1) Synthesis of Compound 3-a

In a three-necked flask, 4- (terbutyl) aniline (10.0g, 67.0mmol) was dissolved in 80ml of a solution containing 1: 1 dichloromethane and MeOH and bromine (9ml, 167.5mmol) was dichloromethane and MeOH 1: It was dissolved in 80 ml of the solution mixed with 1 and slowly added dropwise at room temperature and stirred for 2 hours. After the reaction was completed, the solvent was removed, 150ml of NaOH 20% aqueous solution was added and stirred, and extracted with a separating funnel using diethyl ether. The extract was washed with H ₂ O, dried over MgSO ₄ , concentrated and the sample was purified by silica gel column chromatography to give 17.1 g of compound 3-a. (Yield 83%, MS [M + H] < + > 307)

Step 2) Synthesis of Compound 3-b

Compound 3-a (15.0g, 48.9mmol) and acetic acid 150ml were added to a three neck flask and cooled to 0 ° C. Sodium nitrite (3.7 g, 53.7 mmol) was added dropwise to 30 ml of conc.H ₂ SO _{4 in a} nitrogen atmosphere, and stirred for 4 hours. Subsequently, potassium iodide (56.8g, 342.0mmol) and iodine (11.2g, 44,0mmol) were dissolved in 115ml of H2O and stirred at room temperature for 12 hours. After the reaction was completed, 1800 ml of 15% aqueous NaOH solution was added thereto, and extracted with ethyl acetate. The extract was washed with H ₂ O, dried over MgSO ₄ , concentrated and the sample was purified by silica gel column chromatography to give 17.6 g of compound 3-b. (Yield 86%, MS [M + H] < + > 417)

Step 3) Synthesis of Compound 3-c

In a three-necked flask, compound 3-b (15.0 g, 35.9 mmol) and 10H-spiro [acridin-9,9'-fluorene] (13.1 g, 39.5 mmol) were dissolved in 450 ml of toluene and sodium terbutoxide (5.2 g, 53.8 mmol) and bis (tri-terbutylphosphine) palladium (0) (0.4 g, 0.7 mmol) were added thereto, followed by stirring for 6 hours under reflux condition under argon atmosphere. After the reaction was completed, the mixture was cooled to room temperature, H ₂ O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO ₄ , concentrated and the sample was purified by silica gel column chromatography to give 16.1 g of compound 3-c. (Yield 72%, MS [M + H] < + > 621)

Step 4) Synthesis of Compound 3

Compound 3-c (15.0 g, 24.1 mmol) was dissolved in 225 ml of diethyl ether in a three-necked flask, and then cooled to -78 ° C. 1.7 M terbutyllithium in pentane (71ml, 120.7mmol) was added under nitrogen atmosphere, and it stirred at 0 degreeC for 1 hour. Thereafter, dimethyl mesityldiboronate ester (13.9 g, 72.4 mmol) was dissolved in 45 ml of diethyl ether, and added dropwise at room temperature, followed by stirring for 2 hours under reflux conditions. After the reaction was completed, the mixture was cooled to room temperature, concentrated after passing through celite, and the sample was purified by silica gel column chromatography to obtain 3.6 g of Compound 3 through a sublimation tablet. (Yield 21%, MS [M + H] < + > 719)

Synthesis Example  4: Synthesis of Compound 4

In Synthesis Example 3, 10H-spiro [acridin-9,9'-fluorene] was changed to 2 ', 7'-dimethyl-10H-spiro [acridin-9,9'-fluorene] and used. Except that, the compound was synthesized in the same manner as in the preparation of compound 3 to obtain compound 4. (MS [M + H] ⁺ = 747)

Synthesis Example  5: Synthesis of Compound 5

Preparation of compound 3 in Synthesis Example 3, except that 10H-spiro [acridin-9,9'-fluorene] was changed to 10H-spiro [acridin-9,9'-xanthene] Compound 5 was obtained by synthesis in the same manner as in the preparation. (MS [M + H] ⁺ = 735)

Synthesis Example  6: Synthesis of Compound 6

Step 1) Synthesis of Compound 6-a

In a three-necked flask, 2-bromo-7- (terbutyl) -3-chlorobenzofuran (15.0 g, 58.2 mmol) and aniline (11.9 g, 128.1 mmol) were dissolved in 450 ml of toluene and sodium terbutoxide (11.2 g, 116.5 mmol) and bis (tri-terbutylphosphine) palladium (0) (0.6 g, 1.2 mmol) were added thereto, followed by stirring for 6 hours under reflux conditions under argon atmosphere. After the reaction was completed, the mixture was cooled to room temperature, H ₂ O was added thereto, and the reaction solution was transferred to a separatory funnel for extraction. The extract was dried over MgSO ₄ , concentrated and the sample was purified by silica gel column chromatography to give 21.2 g of compound 6-a. (Yield 72%, MS [M + H] < + > 506)

Step 2) Synthesis of Compound 6

Compound 6-a (15.0 g, 29.6 mmol) was dissolved in 225 ml of diethyl ether in a three neck flask and cooled to -78 ° C. 1.7 M terbutyllithium in pentane (87ml, 148.1mmol) was added under nitrogen atmosphere, and it stirred at 0 degreeC for 1 hour. Thereafter, dimethylmethyldiboronate ester (17.1 g, 88.9 mmol) was dissolved in 45 ml of diethyl ether, and added dropwise at room temperature, followed by stirring for 2 hours under reflux conditions. After the reaction was completed, the mixture was cooled to room temperature, concentrated after passing through celite, and the sample was purified by silica gel column chromatography, and then 3.7 g of Compound 6 was obtained through a sublimation tablet. (Yield 18%, MS [M + H] < + > 693)

[ Example ]

<Example 1>

의 두께로 박막 코팅된 유리기판을 세제에 녹인 증류수에 넣고 초음파로 세척하였다. 이때 세제로는 피셔사(Fischer Co.)의 Decon™ CON705 제품을 사용하였으며, 증류수로는 밀러포어사(Millipore Co.) 제품의 0.22㎛ sterilizing filter로 2차 걸러진 증류수를 사용하였다. ITO를 30분간 세척한 후 증류수로 2회 반복하여 초음파 세척을 10분간 진행하였다. 증류수 세척이 끝난 후, 이소프로필 알코올, 아세톤 및 메탄올의 용제로 각각 10분간 초음파 세척하고, 건조시킨 후 플라즈마 세정기로 수송시켰다. 또한 산소 플라즈마를 이용하여 상기 기판을 5분간 세정한 후, 진공 증착기로 기판을 수송시켰다.Indium Tin Oxide (ITO) 1,400

The glass substrate coated with a thin film was placed in distilled water dissolved in a detergent and washed with ultrasonic waves. Fischer Co. Decon ™ CON705 product was used as a detergent, and distilled water was filtered secondly with a 0.22 μm sterilizing filter from Millerpore Co .. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After the distilled water was washed, ultrasonic washing with a solvent of isopropyl alcohol, acetone and methanol for 10 minutes, dried and then 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 following HI-A and LG-101 were thermally vacuum deposited to a thickness of 650 kPa and 50 kPa, respectively, on the prepared ITO transparent electrode to form a hole injection layer. The following HT-A was vacuum deposited to a thickness of 600 kPa as the hole transport layer, and the following HT-B was thermally vacuum deposited to a thickness of 50 kPa as the electron blocking layer. Subsequently, BH-A and Compound 1 were vacuum deposited in a light emitting layer at a thickness of 200 kPa in a weight ratio of 96: 4. Subsequently, a compound represented by ET and Liq was thermally vacuum deposited to a thickness of 360 kPa in a weight ratio of 1: 1 as the electron transporting layer, and then the compound represented by Liq was vacuum deposited to a thickness of 5 kPa to form an electron injection layer. Magnesium and silver were sequentially deposited on the electron injection layer at a weight ratio of 10: 1 and aluminum was deposited at a thickness of 1000 kW to form a cathode, thereby manufacturing an organic light emitting device.

Example  2 to Example  6, Comparative example  1 and Comparative example  2

The organic light emitting diodes of Examples 2 to 6, Comparative Example 1, and Comparative Example 2 were manufactured by the same method as Example 1, except that the compounds shown in Table 1 were used instead of the dopant materials in Example 1. Each was produced.

The current was applied to the organic light emitting diodes manufactured in Examples 1 to 6 and Comparative Examples 1 to 2, and the voltage, efficiency, and lifetime (T95) were measured, and the results are shown in Table 1 below. Here, voltage and efficiency were measured by applying a current density of 10 mA / cm ² and T95 means the time until the initial luminance drops to 95% at a current density of 20 mA / cm ² .

Dopant @ 10mA / cm ² @ 20mA / cm ² V QE LT95 Example 1 Compound 1 3.92 6.46 40 Example 2 Compound 2 3.88 6.71 35 Example 3 Compound 3 3.93 7.50 60 Example 4 Compound 4 3.96 7.57 65 Example 5 Compound 5 3.85 7.45 60 Example 6 Compound6 3.91 7.38 55 Comparative Example 1 BD-A 4.15 5.30 5 Comparative Example 2 BD-B 4.05 3.02 20

As shown in [Table 1], when the structures of Formula 1 are applied as dopants of the organic light emitting device, the efficiency is high and long life is shown. In particular, in the structure of Formula 1, compounds 3 to 6 in which the X and Y rings are bound through a carbon atom or the X and Y rings are pentagonal rings have a flat structure because the ring is less twisted by a hydrogen atom. It has high luminous efficiency and high molecular stability. In the case of direct coupling such as BD-A, the structure is rather distorted, and a structure connected through boron such as BD-B has a short wavelength of light emission, which decreases efficiency and lifespan. As a result, when the compound of Formula 1 is used as the light emitting layer dopant of the organic light emitting device, a device having high efficiency and long life can be obtained.

1: substrate
2: first electrode
3: organic material layer
4: second electrode
5: hole injection layer
6: hole transport layer
7: electronic jersey
8: light emitting layer
9: electron transport layer
10: electron injection layer

Claims (9)

Heterocyclic compounds represented by the formula (1):
[Formula 1]

In Chemical Formula 1,
X and Y are the same as or different from each other, and each independently represent a substituted or unsubstituted aromatic ring, or a substituted or unsubstituted hetero ring, and in combination with each other, a substituted or unsubstituted aliphatic ring, a substituted or unsubstituted aromatic ring, Or a heterocycle including substituted or unsubstituted O or S,
A1 and A2 are the same as or different from each other, and each independently represent a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group,
R1 is hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted cycloalkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted alkoxy group , A substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or adjacent substituents may combine with each other to form a substituted or unsubstituted ring,
a is an integer of 0 to 3,
When a is plural, the substituents in parentheses are the same as or different from each other. The heterocyclic compound according to claim 1, wherein Formula 1 is represented by Formula 2 or 3 below:
[Formula 2]

[Formula 3]

In Chemical Formulas 2 and 3, the definitions of A1, A2, R1, and a are the same as those defined in Chemical Formula 1,
R2, R3, R8 and R9 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, A substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or adjacent substituents may combine with each other to form a substituted or unsubstituted ring,
Z1 and Z2 are the same as or different from each other, and each independently O or S,
b, c, f and g are each an integer of 0 to 4,
When b, c, f and g are plural, the substituents in parentheses are the same or different from each other. The heterocyclic compound according to claim 1, wherein Formula 1 is represented by any one selected from Formulas 4 to 6.
[Formula 4]

[Formula 5]

[Formula 6]

In Chemical Formulas 4 to 6, the definitions of A1, A2, R1, and a are the same as those defined in Chemical Formula 1,
Z3 is O or S
R2 to R7 are the same as or different from each other, and each independently hydrogen, deuterium, nitrile group, halogen group, substituted or unsubstituted alkyl group, substituted or unsubstituted silyl group, substituted or unsubstituted amine group, substituted or unsubstituted Alkoxy group, substituted or unsubstituted aryl group, or substituted or unsubstituted heteroaryl group, or adjacent substituents may combine with each other to form a substituted or unsubstituted ring,
b1 and c1 are each an integer of 0 to 3,
d and e are each an integer of 0 to 8,
When b1, c1, d and e are plural, the substituents in parentheses are the same as or different from each other. The method of claim 1, wherein R 1 is hydrogen; An alkyl group having 1 to 10 carbon atoms; A cycloalkyl group having 3 to 10 carbon atoms; Silyl groups substituted with alkyl groups having 1 to 10 carbon atoms; An amine group unsubstituted or substituted with an aryl group having 6 to 20 carbon atoms; Or a heterocyclic compound having 3 to 20 carbon atoms. The method of claim 1, wherein A1 and A2 are the same as or different from each other, and each independently a monocyclic aryl group having 6 to 20 carbon atoms substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms or an alkylsilyl group having 1 to 10 carbon atoms; Or a heterocyclic compound having 6 to 20 carbon atoms substituted or unsubstituted with an alkyl group having 1 to 10 carbon atoms or an alkylsilyl group having 1 to 10 carbon atoms. The heterocyclic compound according to claim 1, wherein Formula 1 is any one selected from the following compounds:

A first electrode; A second electrode provided to face the first electrode; And one or two or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include the heterocyclic compound according to any one of claims 1 to 6. Phosphorescent organic light-emitting device. 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 heterocyclic 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 heterocyclic compound as a dopant of the light emitting layer.

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