KR102542201B1 - Compound and organic light emitting device comprising the same - Google Patents

Abstract

The present specification relates to a compound of Formula 1 and an organic light emitting device including the same.

Description

Compound and organic light emitting device including the same {COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME}

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

In general, the organic light emitting phenomenon refers to a phenomenon in which electrical energy is converted 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. Here, the organic material layer is often composed of a multi-layer structure composed of different materials to increase the efficiency and stability of the organic light emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. In the structure of this organic light emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and when the injected holes and electrons meet, excitons are formed. When it falls back to the ground state, it glows.

Development of new materials for the organic light emitting device as described above has been continuously demanded.

US Patent Application Publication No. 2004-0251816

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

The present invention provides a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

L ₁ and L ₂ are the same as or different from each other, and are each independently a substituted or unsubstituted arylene group,

R ₁ to R ₃ are the same as or different from each other, and are each independently hydrogen, heavy hydrogen, a nitrile group, a halogen group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted silyl group. , A substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

Ar ₁ and Ar ₂ are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group;

a is an integer from 0 to 4, and when a is 2 or more, R _a are the same as or different from each other;

b is an integer from 0 to 3, and when b is 2 or more, R _b are the same as or different from each other;

c is an integer from 0 to 4, and when c is 2 or more, R _c are the same as or different from each other;

m and n are the same as or different from each other, and are each independently an integer of 0 to 2;

When m is 2, the L ₁ are the same as or different from each other,

When n is 2, the L ₂ are the same as or different from each other.

In addition, the present invention is 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 at least one of the organic material layers includes the compound.

A compound according to an exemplary embodiment of the present specification may be used as a material of an organic material layer of an organic light emitting device, and by using the same, it is possible to improve efficiency, low driving voltage, and/or lifetime characteristics of the organic light emitting device.

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 will be described in more detail.

The present specification provides a compound represented by Formula 1 above.

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

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

In this specification, the term "substituted or unsubstituted" means deuterium; nitrile group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted aryl group; and a substituted or unsubstituted heterocyclic group, which is substituted with one or two or more substituents selected from the group consisting of two or more substituents among the substituents exemplified above, or a substituent in which two or more substituents are connected. For example, "a substituent in which two or more substituents are connected" 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, and the like.

In the present specification, the alkyl group may be straight or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specifically, it is preferable to have 1 to 20 carbon atoms. More specifically, those having 1 to 10 carbon atoms are preferred. Specific examples include a methyl group; ethyl group; propyl group; n-propyl group; isopropyl group; butyl group; n-butyl group; isobutyl group; tert-butyl group; sec-butyl group; 1-methylbutyl group; 1-ethylbutyl group; pentyl group; n-pentyl group; isopentyl group; neopentyl group; tert-pentyl group; hexyl group; n-hexyl group; 1-methylpentyl group; 2-methylpentyl group; 4-methyl-2-pentyl group; 3,3-dimethylbutyl group; 2-ethylbutyl group; heptyl group; n-heptyl group; 1-methylhexyl group; Cyclopentylmethyl group; cyclohexylmethyl group; octyl group; n-octyl group; tert-octyl group; 1-methylheptyl group; 2-ethylhexyl group; 2-propylpentyl group; n-nonyl group; 2,2-dimethylheptyl group; 1-ethylpropyl group; 1,1-dimethylpropyl group; isohexyl group; 2-methylpentyl group; 4-methylhexyl group; 5-methylhexyl group 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, and more preferably has 3 to 20 carbon atoms. specifically a cyclopropyl group; Cyclobutyl group; cyclopentyl group; 3-methylcyclopentyl group; 2,3-dimethylcyclopentyl group; cyclohexyl group; 3-methylcyclohexyl group; 4-methylcyclohexyl group; 2,3-dimethylcyclohexyl group; 3,4,5-trimethylcyclohexyl group; 4-tert-butylcyclohexyl group; cycloheptyl group; cyclooctyl group, etc., but is not limited thereto.

In the present specification, the alkoxy group may be straight chain, branched chain or cyclic chain. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specifically, it is preferable to have 1 to 20 carbon atoms. More specifically, it is preferable to have 1 to 10 carbon atoms. Specifically, a 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; It may be a p-methylbenzyloxy group or the like, but is not limited thereto.

In the present specification, the amine group is -NH ₂ ; Alkylamine group; N-alkyl arylamine group; Arylamine group; N-arylheteroarylamine group; It may be selected from the group consisting of an N-alkylheteroarylamine group and a heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group; dimethylamine group; ethylamine group; diethylamine group; phenylamine group; naphthylamine group; Biphenylamine group; an anthracenylamine group; 9-methylanthracenylamine group; diphenylamine group; N-phenylnaphthylamine group; ditolylamine group; N-phenyltolylamine group; triphenylamine group; N-phenylbiphenylamine group; N-phenylnaphthylamine group; N-biphenyl naphthylamine group; N-naphthylfluorenylamine group; N-phenylphenanthrenylamine group; N-biphenylphenanthrenylamine group; N-phenylfluorenylamine group; N-phenylterphenylamine group; N-phenanthrenylfluorenylamine group; N-biphenylfluorenylamine group and the like, but are not limited thereto.

In the present specification, the silyl group may be represented by the chemical formula of -SiRaRbRc, wherein Ra, Rb and Rc are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. The silyl group is specifically a trimethylsilyl group; triethylsilyl group; t-butyldimethylsilyl group; a vinyldimethylsilyl group; A propyldimethylsilyl group; triphenylsilyl group; Diphenylsilyl group; phenylsilyl group and the like, but are not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and more preferably has 6 to 20 carbon atoms. The aryl group may be monocyclic or polycyclic. When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 30 carbon atoms. More specifically, those having 6 to 20 carbon atoms are preferred. Specifically, the monocyclic aryl group includes a phenyl group; biphenyl group; It may be a terphenyl group or the like, but is not limited thereto. When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferably 10 to 30 carbon atoms, more specifically preferably 10 to 20 carbon atoms. Specifically, the polycyclic aryl group includes a naphthyl group; Anthracenyl group; phenanthryl group; triphenyl group; pyrenyl group; phenalenyl group; Perylenyl group; Chrysenyl group; It may be a fluorenyl group or the like, but is 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 or a polycyclic aryl group. The arylamine group including two or more aryl groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time. 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 non-carbon atoms, that is, heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S. The number of carbon atoms is not particularly limited, but preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heteroaryl group include a thiophene group; furanyl group; pyrrole group; imidazolyl group; thiazolyl group; oxazolyl group; Oxadiazolyl group; pyridyl group; bipyridyl group; pyrimidyl group; triazinyl group; triazolyl group; acridyl group; pyridazinyl group; pyrazinyl group; quinolinyl group; quinazolinyl group; Quinoxalinyl group; phthalazinyl group; A pyrido pyrimidyl group; A pyrido pyrazinyl group; A pyrazino pyrazinyl group; isoquinolinyl group; indolyl group; carbazolyl group; benzoxazolyl group; benzimidazolyl group; Benzothiazolyl group; Benzocarbazolyl group; Benzothiophene group; Dibenzothiophene group; Benzofuranyl group; phenanthroline; isoxazolyl group; thiadiazolyl group; A phenothiazinyl group and a dibenzofuranyl group, but are not limited thereto.

In one embodiment of the present specification, Formula 1 is represented by Formula 1-1 or 1-2 below.

[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2, R ₁ to R ₃ , L ₁ , L ₂ , Ar ₁ , Ar ₂ , a to c, m and n are as defined in Formula 1 above.

In one embodiment of the present specification, L ₁ and L ₂ are the same as or different from each other, and each independently represents a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In one embodiment of the present specification, L ₁ and L ₂ are the same as or different from each other, and each independently represents a substituted arylene group having 6 to 30 carbon atoms.

In one embodiment of the present specification, L ₁ and L ₂ are the same as or different from each other, and each independently represents an unsubstituted arylene group having 6 to 30 carbon atoms.

In one embodiment of the present specification, L ₁ and L ₂ are the same as or different from each other, and each independently represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted divalent biphenyl group, or a substituted or unsubstituted divalent biphenyl group. A terphenyl group, a substituted or unsubstituted naphthalene group, a substituted or unsubstituted divalent anthracene group, a substituted or unsubstituted divalent phenanthrene group, a substituted or unsubstituted divalent triphenylene group, or a substituted or unsubstituted divalent phenanthrene group. It is a fluorene group.

In one embodiment of the present specification, L ₁ and L ₂ are the same as or different from each other, and each independently represents a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalene group, or a substituted or unsubstituted divalent ratio. is a phenyl group.

In one embodiment of the present specification, L ₁ and L ₂ are the same as or different from each other, and each independently represents a phenylene group, a naphthalene group, or a divalent biphenyl group.

In one embodiment of the present specification, L ₁ and L ₂ are a phenylene group.

In one embodiment of the present specification, L ₁ and L ₂ are naphthalene groups.

In one embodiment of the present specification, L ₁ and L ₂ are a divalent biphenyl group.

In one embodiment of the present specification, L ₁ and L ₂ are different from each other, and are each a phenylene group, a naphthalene group, or a divalent biphenyl group.

In one embodiment of the present specification, Ar ₁ and Ar ₂ are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted hetero group having 3 to 30 carbon atoms. It is an aryl group.

In one embodiment of the present specification, Ar ₁ and Ar ₂ are the same as each other and are substituted or unsubstituted aryl groups having 6 to 20 carbon atoms.

In one embodiment of the present specification, Ar ₁ and Ar ₂ are the same as each other and are substituted aryl groups having 6 to 20 carbon atoms.

In one embodiment of the present specification, Ar ₁ and Ar ₂ are the same as each other and are an unsubstituted aryl group having 6 to 20 carbon atoms.

In one embodiment of the present specification, Ar ₁ and Ar ₂ are the same as each other and are a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

In one embodiment of the present specification, Ar ₁ and Ar ₂ are the same as each other and are substituted heteroaryl groups having 3 to 30 carbon atoms.

In one embodiment of the present specification, Ar ₁ and Ar ₂ are the same as each other and are an unsubstituted heteroaryl group having 3 to 30 carbon atoms.

In one embodiment of the present specification, Ar ₁ and Ar ₂ are the same as each other and are substituted or unsubstituted aryl groups having 6 to 20 carbon atoms.

In an exemplary embodiment of the present specification, Ar ₁ and Ar ₂ are different from each other.

In one embodiment of the present specification, Ar ₁ is a substituted aryl group having 6 to 20 carbon atoms.

In one embodiment of the present specification, Ar ₁ is an aryl group having 6 to 20 carbon atoms.

In one embodiment of the present specification, Ar ₁ is a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

In one embodiment of the present specification, Ar ₁ is a substituted heteroaryl group having 3 to 30 carbon atoms.

In one embodiment of the present specification, Ar ₁ is an unsubstituted heteroaryl group having 3 to 30 carbon atoms.

In one embodiment of the present specification, Ar ₂ is an aryl group having 6 to 20 carbon atoms.

In one embodiment of the present specification, Ar ₂ is a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

In one embodiment of the present specification, Ar ₂ is a substituted heteroaryl group having 3 to 30 carbon atoms.

In one embodiment of the present specification, Ar ₂ is an unsubstituted heteroaryl group having 3 to 30 carbon atoms.

In an exemplary embodiment of the present specification, Ar ₁ and Ar ₂ are the same as or different from each other, and each independently represents any one of the following substituents.

The dotted line is a site that binds to L1 and L2, and Rx is an alkyl group or an aryl group.

In an exemplary embodiment of the present specification, Ar ₁ and Ar ₂ are the same as or different from each other, and each independently selected from a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrene group, a triphenylene group, a fluorene group, and a dibenzo group. A furan group or a dibenzothiophene group,

The phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthrene group, triphenylene group, fluorene group, dibenzofuran group, or dibenzothiophene group is deuterium, a nitrile group, a halogen group, a substituted or unsubstituted alkyl group, It is substituted or unsubstituted with one or more substituents selected from the group consisting of a substituted or unsubstituted aryl group and a substituted or unsubstituted heteroaryl group.

In an exemplary embodiment of the present specification, Ar ₁ and Ar ₂ are the same as or different from each other, and each independently selected from a phenyl group, a biphenyl group, a terphenyl group, a naphthyl group, a phenanthrene group, a triphenylene group, a fluorene group, and a dibenzo group. A furan group or a dibenzothiophene group,

The phenyl group, biphenyl group, terphenyl group, naphthyl group, phenanthrene group, triphenylene group, fluorene group, dibenzofuran group, or dibenzothiophene group is deuterium, nitrile group, halogen group, substituted or unsubstituted carbon number 1 to 10 alkyl groups, substituted or unsubstituted aryl groups having 6 to 20 carbon atoms, and substituted or unsubstituted heteroaryl groups having 3 to 30 carbon atoms.

In an exemplary embodiment of the present specification, R ₁ to R ₃ are the same as or different from each other, and each independently hydrogen, heavy hydrogen, a nitrile group, a halogen group, a nitro group, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, A substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms, a silyl group substituted with an alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms , or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

In an exemplary embodiment of the present specification, R ₁ to R ₃ are the same as or different from each other, and each independently hydrogen; heavy hydrogen; nitrile group; F; Br; Cl; I; nitro group; methyl group; ethyl group; propyl group; isopropyl group; butyl group; terbutyl group; methoxy group; ethoxy group; butoxy group; terbutoxy group; A silyl group substituted with a methyl group, an ethyl group, or a terbutyl group; phenyl group; biphenyl group; naphthyl group; terphenyl group; phenanthrene group; anthracene group; Dibenzofuran group; Dibenzothiophene group; carbazole group; or a trizine group.

In an exemplary embodiment of the present specification, R ₁ to R ₃ are the same as or different from each other, and each independently represents hydrogen.

In one embodiment of the present specification, Formula 1 is any one selected from the following compounds.

In the present specification, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated.

In this specification, when a member is said to be located “on” another member, this includes not only the case where a member is in contact with another member, but also the case where another member exists between the two members.

An organic light emitting device of the present invention includes 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 at least one of the organic material layers may contain the aforementioned compound.

For example, the structure of the organic light emitting device of the present invention may have a structure 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.

1 illustrates an organic light emitting device, but is not limited thereto.

2 shows a first electrode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 8, a hole blocking layer 9 on a substrate 1, electron injection and The structure of the organic light emitting device in which the transport layer 10 and the second electrode 4 are sequentially stacked is illustrated. The compound of the present invention may be used in the hole injection layer, the hole transport layer, the electron suppression layer, the light emitting layer, the hole blocking layer, and the electron injection and transport layer, but is preferably used in the electron suppression layer.

2 illustrates an organic light emitting device, but is not limited thereto.

In one embodiment of the present invention, the organic material layer includes a light emitting layer, and the light emitting layer includes the compound of Formula 1.

In one embodiment of the present invention, the organic material layer may include a hole injection layer, a hole transport layer, or a hole injection and transport layer, and the hole injection layer, the hole transport layer, or the hole injection and transport layer may include the compound of Formula 1. can

In an exemplary embodiment of the present invention, the organic material layer may include an electron injection layer, an electron transport layer, or an electron injection and transport layer, and the electron injection layer, the electron transport layer, or the electron injection and transport layer may include the compound of Formula 1. can

In an exemplary embodiment of the present invention, the organic material layer may include an electron blocking layer, and the electron blocking layer may include the compound of Formula 1.

In one embodiment of the present invention, the organic material layer may include a hole blocking layer, and the hole blocking layer may include the compound of Formula 1.

For example, the organic light emitting device according to the present invention uses a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation to form a metal or conductive metal oxide or an alloy thereof on a substrate. is deposited 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 and an organic material layer including the compound of Formula 1 are formed thereon, and then a material that can be used as a cathode is deposited thereon. It can be produced by In addition to this method, an organic light emitting device may be fabricated 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 high work function is generally preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO:Al or SnO ₂ : A combination of a metal and an oxide such as Sb; Conductive polymers such as poly(3-methyl compound), poly[3,4-(ethylene-1,2-dioxy) compound] (PEDT), polypyrrole, and polyaniline, but are not limited thereto.

The cathode material is preferably a material having a small work function so as to easily inject electrons 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; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

The hole injection material is a material capable of receiving holes well from the anode at a low voltage, and the hole injection material preferably has a highest occupied molecular orbital (HOMO) between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrilehexaazatriphenylene-based organic materials, quinacridone-based organic materials, and perylene-based organic materials. of organic materials, anthraquinone, and polyaniline and conductive polymers of the series, but are not limited thereto.

As the hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer, and a material having high hole mobility is suitable. Specific examples include, but are not limited to, arylamine-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated parts.

The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; Polyfluorene, rubrene, etc., 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 with materials and methods known in the art, except that at least one layer of the organic material layer is formed using the compound.

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

Examples of the dopant material include an aromatic compound, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic compound is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, such as pyrene, anthracene, chrysene, and periplanthene having an arylamino group, and the styrylamine compound is a substituted or unsubstituted A compound in which an arylamine is substituted with at least one arylvinyl group, wherein 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, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, etc., but is not limited thereto. In addition, metal complexes include, but are not limited to, iridium complexes and platinum complexes.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports them to the light emitting layer. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable. do. Specific examples include Al complexes of 8-hydroxyquinoline; complexes including Alq3; 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 according to the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by a layer of aluminum or silver.

The electron injection layer is a layer for injecting electrons from an electrode, has an ability to transport electrons, has an excellent electron injection effect from the cathode, a light emitting layer or a light emitting material, and injects holes of excitons generated in the light emitting layer. A compound that prevents migration to a layer and has excellent thin film forming ability is preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preonylidene methane, anthrone, etc. and their derivatives, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-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)( There are o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium. Not limited to this.

The hole blocking layer is a layer that blocks holes from reaching the cathode, 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.

An 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 depending on materials used.

The organic light emitting device of the present invention may be manufactured by conventional organic light emitting device manufacturing methods and materials, except for forming one or more organic material layers using the above compounds.

The preparation method of the compound of Chemical 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.

In the reaction scheme below, various kinds of intermediates can be synthesized according to the appropriate selection of starting materials known to those skilled in the art for the type and number of substituents. Reaction type and reaction conditions may be used those known in the art.

All of the compounds represented by Chemical Formula 1 described herein can be prepared by appropriately combining the preparation formulas described in the examples herein and the intermediates based on common technical knowledge.

manufacturing example One

After completely dissolving compound A-1 (13.33 g, 24.38 mmol) and compound a1 (6.50 g, 23.90 mmol) in 250 mL of xylene in a 500 mL round bottom flask under a nitrogen atmosphere, NaOtBu (3.44 g, 35.85 mmol) was added. After adding bis(tri-tert-butylphosphine)palladium(0) (0.12 g, 0.24 mmol), the mixture was heated and stirred for 4 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 230 mL of ethyl acetate to prepare Compound 1 (9.47 g, yield: 54%).

MS[M+H] ⁺ = 740

manufacturing example 2

After completely dissolving compound A-1 (12.86 g, 23.51 mmol) and compound a2 (6.50 g, 23.05 mmol) in 220 mL of xylene in a 500 mL round bottom flask under a nitrogen atmosphere, NaOtBu (3.32 g, 34.57 mmol) was added. After adding bis(tri-tert-butylphosphine)palladium(0) (0.12 g, 0.23 mmol), the mixture was heated and stirred for 4 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 230 mL of ethyl acetate to prepare Compound 2 (11.02 g, yield: 64%).

MS[M+H] ⁺ = 750

manufacturing example 3

After completely dissolving compound A-1 (11.77 g, 21.53 mmol) and compound a3 (6.50 g, 21.10 mmol) in 220 mL of xylene in a 500 mL round bottom flask under a nitrogen atmosphere, NaOtBu (3.04 g, 31.66 mmol) was added. After adding bis(tri-tert-butylphosphine)palladium(0) (0.11 g, 0.21 mmol), the mixture was heated and stirred for 4 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 160 mL of ethyl acetate to prepare compound 3 (8.89 g, yield: 54%).

MS[M+H] ⁺ = 776

manufacturing example 4

After completely dissolving compound A-1 (12.86 g, 23.51 mmol) and compound a4 (6.50 g, 23.05 mmol) in 230 mL of xylene in a 500 mL round bottom flask under a nitrogen atmosphere, NaOtBu (3.32 g, 34.57 mmol) was added. After adding bis(tri-tert-butylphosphine)palladium(0) (0.12 g, 0.23 mmol), the mixture was heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 260 mL of ethyl acetate to prepare compound 4 (11.67 g, yield: 68%).

MS[M+H] ⁺ = 750

manufacturing example 5

After completely dissolving compound A-1 (10.73 g, 19.62 mmol) and compound a5 (6.50 g, 19.23 mmol) in 260 mL of xylene in a 500 mL round bottom flask under a nitrogen atmosphere, NaOtBu (2.77 g, 28.85 mmol) was added. After adding bis(tri-tert-butylphosphine)palladium(0) (0.10 g, 0.19 mmol), the mixture was heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 180 mL of ethyl acetate to prepare Compound 5 (8.89 g, yield: 57%).

MS[M+H] ⁺ = 806

manufacturing example 6

After completely dissolving compound A-1 (11.26 g, 20.59 mmol) and compound a6 (6.50 g, 20.19 mmol) in 240 mL of xylene in a 500 mL round bottom flask under a nitrogen atmosphere, NaOtBu (2.91 g, 30.28 mmol) was added. After adding bis(tri-tert-butylphosphine)palladium(0) (0.10 g, 0.20 mmol), the mixture was heated and stirred for 4 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 190 mL of ethyl acetate to prepare Compound 6 (9.36 g, yield: 59%).

MS[M+H] ⁺ = 790

manufacturing example 7

After completely dissolving compound A-1 (14.74 g, 26.95 mmol) and compound a7 (6.50 g, 26.42 mmol) in 220 mL of xylene in a 500 mL round bottom flask under a nitrogen atmosphere, NaOtBu (3.81 g, 39.63 mmol) was added. After adding bis(tri-tert-butylphosphine)palladium(0) (0.14 g, 0.26 mmol), the mixture was heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 210 mL of ethyl acetate to prepare compound 7 (10.19 g, yield: 54%).

MS[M+H] ⁺ = 714

manufacturing example 8

After completely dissolving compound A-1 (13.84 g, 25.31 mmol) and compound a8 (6.50 g, 24.81 mmol) in 250 mL of xylene in a 500 mL round bottom flask under a nitrogen atmosphere, NaOtBu (3.58 g, 37.21 mmol) was added. After adding bis(tri-tert-butylphosphine)palladium(0) (0.13 g, 0.25 mmol), the mixture was heated and stirred for 4 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 230 mL of ethyl acetate to prepare Compound 8 (9.34 g, yield: 52%).

MS[M+H] ⁺ = 730

manufacturing example 9

After completely dissolving compound A-2 (15.46 g, 25.90 mmol) and compound a9 (6.50 g, 25.39 mmol) in 240 mL of xylene in a 500 mL round bottom flask under a nitrogen atmosphere, NaOtBu (3.66 g, 38.09 mmol) was added. After adding bis(tri-tert-butylphosphine)palladium(0) (0.13 g, 0.25 mmol), the mixture was heated and stirred for 4 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 210 mL of toluene to prepare Compound 9 (7.39 g, yield: 38%).

MS[M+H] ⁺ = 674

manufacturing example 10

After completely dissolving compound A-3 (19.21 g, 32.18 mmol) and compound a10 (6.50 g, 31.55 mmol) in 260 mL of xylene in a 500 mL round bottom flask under a nitrogen atmosphere, NaOtBu (4.55 g, 47.33 mmol) was added. After adding bis(tri-tert-butylphosphine)palladium(0) (0.16 g, 0.32 mmol), the mixture was heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 220 mL of ethyl acetate to prepare Compound 10 (11.34 g, yield: 50%).

MS[M+H] ⁺ = 724

manufacturing example 11

After completely dissolving compound A-4 (17.44 g, 26.95 mmol) and compound a11 (6.50 g, 26.42 mmol) in 230 mL of xylene in a 500 mL round bottom flask under a nitrogen atmosphere, NaOtBu (3.81 g, 39.63 mmol) was added. After adding bis(tri-tert-butylphosphine)palladium(0) (0.14 g, 0.26 mmol), the mixture was heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 190 mL of ethyl acetate to prepare Compound 11 (13.46 g, yield: 63%).

MS[M+H] ⁺ = 814

manufacturing example 12

After completely dissolving compound A-5 (13.37 g, 21.53 mmol) and compound a12 (6.50 g, 21.10 mmol) in 240 mL of xylene in a 500 mL round bottom flask under a nitrogen atmosphere, NaOtBu (3.04 g, 31.66 mmol) was added. After adding bis(tri-tert-butylphosphine)palladium(0) (0.11 g, 0.21 mmol), the mixture was heated and stirred for 3 hours. After lowering the temperature to room temperature and filtering to remove the base, xylene was concentrated under reduced pressure and recrystallized with 210 mL of ethyl acetate to prepare Compound 12 (9.56 g, yield: 53%).

MS[M+H] ⁺ = 850

Example 1-1

A glass substrate coated with ITO (indium tin oxide) to a thickness of 1,000 Å was put in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a Fischer Co. product was used as the detergent, and distilled water filtered through a second filter (filtration) of a Millipore Co. product was used as the distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with solvents such as isopropyl alcohol, acetone, and methanol, dried, and transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum deposition machine.

A hole injection layer was formed by thermally vacuum-depositing the following compound HI1 and the following compound HI2 to a thickness of 100 Å in a ratio of 98:2 (molar ratio) on the ITO transparent electrode prepared as described above. A hole transport layer was formed by vacuum depositing a compound (1150 Å) represented by Chemical Formula HT1 on the hole injection layer. Subsequently, an electron blocking layer was formed by vacuum depositing compound 1 on the hole transport layer to a thickness of 50 Å. Subsequently, a compound represented by Chemical Formula BH and a compound represented by Chemical Formula BD were vacuum deposited at a weight ratio of 25:1 to form a light emitting layer on the electron blocking layer to a film thickness of 200 Å. A hole blocking layer was formed on the light emitting layer by vacuum depositing a compound represented by Chemical Formula HB1 to a film thickness of 50 Å. Subsequently, a compound represented by Chemical Formula ET1 and a compound represented by Chemical Formula LiQ were vacuum deposited at a weight ratio of 1:1 on the hole-blocking layer to form an electron injection and transport layer with a thickness of 310 Å. A negative electrode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 12 Å and aluminum to a thickness of 1,000 Å on the electron injection and transport layer.

In the above process, the deposition rate of the organic material was maintained at 0.4 ~ 0.7Å / sec, the deposition rate of lithium fluoride on the cathode was 0.3Å / sec, and the deposition rate of aluminum was 2Å / sec, and the vacuum level during deposition was 2ⅹ10 ^-7 ~ Maintaining 5x10 ^-6 torr, an organic light emitting device was manufactured.

Example 1-2 to Example 1-12

An organic light emitting device was manufactured in the same manner as in Example 1-1, except that the compound shown in Table 1 was used instead of Compound 1.

comparative example 1-1 to 1-4

An organic light emitting device was manufactured in the same manner as in Example 1-1, except that the compound shown in Table 1 was used instead of Compound 1. The compounds of EB2, EB3, EB4 and EB5 used in Table 1 are as follows.

Experimental example One

When current was applied to the organic light emitting devices prepared in Examples and Comparative Examples, voltage, efficiency, color coordinates, and lifetime were measured, and the results are shown in Table 1 below. T95 means the time required for the luminance to decrease from the initial luminance (1600 nit) to 95%.

compound
(electron suppression layer) Voltage
(V@10mA
/cm ² efficiency
(cd/A@10mA
/cm ² ) color coordinates
(x,y) T95
(hr) Example 1-1 compound 1 4.44 6.34 (0.146, 0.046) 270 Example 1-2 compound 2 4.43 6.33 (0.145, 0.045) 270 Example 1-3 compound 3 4.40 6.32 (0.144, 0.044) 265 Example 1-4 compound 4 4.44 6.39 (0.145, 0.047) 270 Example 1-5 compound 5 4.42 6.37 (0.144, 0.046) 265 Example 1-6 compound 6 4.46 6.25 (0.146, 0.045) 265 Examples 1-7 compound 7 4.49 6.26 (0.145, 0.047) 270 Examples 1-8 compound 8 4.41 6.22 (0.144, 0.046) 285 Examples 1-9 compound 9 4.65 6.16 (0.145, 0.045) 240 Examples 1-10 compound 10 4.69 6.17 (0.144, 0.044) 245 Example 1-11 compound 11 4.67 6.16 (0.146, 0.046) 240 Examples 1-12 compound 12 4.68 6.12 (0.145, 0.046) 245 Comparative Example 1-1 EB2 5.26 5.61 (0.142, 0.047 115 Comparative Example 1-2 EB3 4.84 5.06 (0.145, 0.045) 120 Comparative Example 1-3 EB4 5.33 5.31 (0.144, 0.046) 45 Comparative Example 1-4 EB5 6.01 4.21 (0.142, 0.047) 60

As shown in Table 1, the organic light emitting device using the compound of the present invention as an electron blocking layer exhibited excellent characteristics in terms of efficiency, driving voltage and stability of the organic light emitting device.

EB2 using phenylene as a linker between amine and triphenylene, EB4 in which an amine group and a biphenyl group are bonded in a meta form, EB3 in which a triphenylene and an amine are directly bonded, and an additional chain between an amine group and a branched biphenyl group. Compared to the organic light emitting devices of Comparative Examples 1-1 to 1-4 prepared using EB5 materials having a phenyl group, the organic light emitting diodes exhibited characteristics of low voltage, high efficiency, and long lifespan.

Although the preferred embodiment (electron suppression layer) of the present invention has been described above, the present invention is not limited thereto and can be modified and implemented in various ways within the scope of the claims and detailed description of the invention. belongs to the category of invention.

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

Claims (10)

A compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
L ₁ and L ₂ are the same as or different from each other, and are each independently a substituted or unsubstituted arylene group,
R ₁ to R ₃ are the same as or different from each other, and are each independently hydrogen, heavy hydrogen, a nitrile group, a halogen group, a nitro group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted silyl group. , A substituted or unsubstituted alkenyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,
Ar ₁ and Ar ₂ 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;
a is an integer from 0 to 4, and when a is 2 or more, R _a are the same as or different from each other;
b is an integer from 0 to 3, and when b is 2 or more, R _b are the same as or different from each other;
c is an integer from 0 to 4, and when c is 2 or more, R _c are the same as or different from each other;
m and n are the same as or different from each other, and are each independently an integer of 0 to 2;
When m is 2, the L ₁ are the same as or different from each other,
When n is 2, the L ₂ are the same as or different from each other. The compound according to claim 1, wherein Chemical Formula 1 is represented by the following Chemical Formula 1-1 or 1-2:
[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2, R ₁ to R ₃ , L ₁ , L ₂ , Ar ₁ , Ar ₂ , a to c, m and n are as defined in Formula 1 above. The method according to claim 1, wherein the L ₁ and L ₂ are identical to or different from each other, each independently A compound that is a substituted or unsubstituted arylene group having 6 to 20 carbon atoms. The method according to claim 1, wherein Ar ₁ and Ar ₂ are the same as or different from each other, and each independently represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms. compound. The 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 at least one of the organic material layers includes the compound of any one of claims 1 to 5. light emitting element. The organic light emitting device of claim 6, wherein the organic material layer includes a hole injection layer, a hole transport layer, or a hole injection and transport layer, and the hole injection layer, the hole transport layer, or the hole injection and transport layer includes the compound. The organic light emitting device of claim 6, wherein the organic material layer includes an electron injection layer, an electron transport layer, or an electron injection and transport layer, and the electron injection layer, the electron transport layer, or the electron injection and transport layer includes the compound. The organic light emitting device of claim 6, wherein the organic material layer includes an electron blocking layer, and the electron blocking layer includes the compound. The organic light emitting device of claim 6, wherein the organic material layer includes a light emitting layer, and the light emitting layer includes the compound.

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