KR20210062994A - Compound and organic light emitting device comprising the same - Google Patents

Abstract

The present specification provides a compound of chemical formula 1 and an organic light emitting device including the same. The compound according to an exemplary embodiment of the present application is used in the organic light emitting device to increase the luminance of the organic light emitting device, increase a lifespan, lower a driving voltage, improve light efficiency, and improve lifespan characteristics of a device by thermal stability of the compound.

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.

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

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

In order to improve the performance, lifespan or efficiency of the organic light emitting device, the development of a material for the organic thin film is continuously required.

Republic of Korea Patent Publication No. 10-0672536

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

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

[Formula 1]

In Formula 1,

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

L4 is a substituted or unsubstituted alkylene group; a substituted or unsubstituted divalent cycloalkyl group; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

Ar1 and Ar2 are the same as or different from each other, and are each independently a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

X1 to X3 are the same as or different from each other, each independently CH or N,

At least one of X1 to X3 is N,

At least one of Ar1, Ar2 and L4 is an acenaphthyl group unsubstituted or substituted with deuterium, a halogen group, a nitrile group, or an alkyl group; or a divalent acenaphthyl group unsubstituted or substituted with deuterium, a halogen group, a nitrile group, or an alkyl group;

Structures in parentheses are the same as or different from each other.

In addition, the present application is 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 compound described above.

The compound according to an exemplary embodiment of the present application is used in an organic light emitting device to increase the luminance of the organic light emitting device, increase lifespan, lower the driving voltage, improve light efficiency, and improve the lifespan characteristics of the device by thermal stability of the compound can be improved

In the compound of Formula 1, two N-containing monocyclic heterocyclic groups and acenaphthyl groups are properly conjugated to increase electron mobility, thereby improving the efficiency and lifespan of the organic light emitting diode.

1 illustrates an example of an organic light-emitting device in which a substrate 1, an anode 2, an organic material layer 3, and a cathode 4 are sequentially stacked.
2 shows a substrate 1, an anode 2, a hole injection layer 5, a first hole transport layer 6, a second hole transport layer 7, a light emitting layer 8, an electron injection and transport layer 9, and An example of an organic light emitting device in which the cathode 4 is sequentially stacked is shown.

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

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

In this specification, when a member is positioned "on" another member, this includes not only the case where the member is in contact with the other member, but also the case where another member exists between the two members.

In the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless specifically stated to the contrary.

In the entire specification of the present application, the term "combination of these" included in the expression of the Makushi format refers to one or more mixtures or combinations selected from the group consisting of components described in the expression of the Makushi format, and the constituent elements It means to include one or more selected from the group consisting of.

Hereinafter, the substituents of the present specification will be described in detail below, but the present invention is not limited thereto.

As used herein, 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 position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, is not limited, and two or more When substituted, two or more substituents may be the same as or different from each other.

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Nitrile group; Alkyl group; Cycloalkyl group; Alkoxy group; Silyl group; Amine group; Aryl group; And it means substituted or unsubstituted with one or more substituents selected from the group consisting of a heteroaryl group, or substituted or unsubstituted, wherein two or more substituents among the exemplified substituents are connected.

In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group may be a straight chain, branched chain, or cyclic chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-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, 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, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2- propylpentyl, n-nonyl, 2,2-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, is not limited to

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and 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, etc., but are not limited thereto. does not

In the present specification, the alkoxy group may be a straight chain, branched chain, or cyclic chain. Although the number of carbon atoms of the alkoxy group is not particularly limited, it is preferably 1 to 30 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. may be, but is not limited thereto.

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

In the present specification, when the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but preferably 6 to 25 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, a quaterphenyl group, and 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 preferable that it has 10 to 30 carbon atoms. Specifically, the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

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

,

,

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

,

,

, and so on. However, it is not limited thereto.

In the present specification, the heteroaryl group includes one or more atoms other than carbon and one or more heteroatoms, and specifically, the heteroatom 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 is preferably 2 to 30 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heteroaryl group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a pyridine group, a pyrimidine group, a triazine group, a triazole group, a quinolinyl group, a quinazoline group, Carbazole group, benzoxazole group, benzimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuran group, phenanthroline group, isoxazole group, thiadiazole group, and a dibenzofuran group, but is not limited thereto.

In the present specification, the alkylene group means that the alkyl group has two bonding positions, that is, a divalent group. Except that each of these groups is a divalent group, the description of the alkyl group described above may be applied.

In the present specification, an arylene group means that the aryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the aryl group described above may be applied.

In the present specification, the heteroarylene group means that the heteroaryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the aforementioned heteroaryl group may be applied.

In one embodiment of the present specification, the structures in parentheses are different from each other.

In one embodiment of the present specification, the structures in parentheses are the same as each other.

Compounds having the same structure in parentheses of Formula 1 have the effect of increasing electron mobility because symmetry is maintained in forming the organic thin film layer. Accordingly, when compounds having the same structure in parentheses are used for the hole blocking layer, the electron transport layer, or the electron injection and transport layer, the efficiency and lifespan of the organic light emitting device are improved.

In an exemplary embodiment of the present specification, at least one of Ar1 and Ar2 is an acenaphthyl group substituted or unsubstituted with deuterium, a halogen group, a nitrile group, or an alkyl group, or L4 is deuterium, a halogen group, a nitrile group, or It is a divalent acenaphthyl group unsubstituted or substituted with an alkyl group.

In the exemplary embodiment of the present specification, at least one of Ar1 and Ar2 is represented by the following formula (2).

[Formula 2]

In Formula 2,

Any one of R1 to R10 is combined with L1 or L2,

R1 to R10 not bonded to L1 or L2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; or an alkyl group.

In an exemplary embodiment of the present specification, R1 to R10 not bonded to L1 or L2 are the same as or different from each other, and are each independently hydrogen or deuterium.

In an exemplary embodiment of the present specification, L4 is represented by the following formula (3).

[Formula 3]

In Formula 3,

two of R11 to R20 are bonded to two L3s,

R11 to R20 not bonded to L3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; or an alkyl group.

In an exemplary embodiment of the present specification, R11 to R20 not bonded to L3 are the same as or different from each other, and each independently represent hydrogen or deuterium.

In the exemplary embodiment of the present specification, at least one of Ar1 and Ar2 is represented by Formula 2, or L4 is represented by Formula 3 above.

In an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; or an arylene group having 6 to 20 carbon atoms.

In an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently a direct bond; Or a phenylene group.

In an exemplary embodiment of the present specification, L3 is a direct bond; or an arylene group having 6 to 20 carbon atoms.

In an exemplary embodiment of the present specification, L3 is a direct bond; Or a phenylene group.

In an exemplary embodiment of the present specification, L4 is a substituted or unsubstituted C 1 to C 10 alkylene group; a substituted or unsubstituted divalent cycloalkyl group having 1 to 10 carbon atoms; a substituted or unsubstituted arylene group having 6 to 20 carbon atoms; or a substituted or unsubstituted C 2 to C 20 heteroarylene group.

In an exemplary embodiment of the present specification, L4 is an alkyl group, or an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with an aryl group; a divalent cycloalkyl group having 1 to 10 carbon atoms that is unsubstituted or substituted with an alkyl group or an aryl group; an arylene group having 6 to 20 carbon atoms that is unsubstituted or substituted with an alkyl group or an aryl group; Or an alkyl group, or a C 2 to C 20 heteroarylene group unsubstituted or substituted with an aryl group.

In an exemplary embodiment of the present specification, L4 is an alkyl group, or an alkylene group having 1 to 10 carbon atoms unsubstituted or substituted with an aryl group; a divalent cycloalkyl group having 1 to 10 carbon atoms that is unsubstituted or substituted with an alkyl group or an aryl group; an arylene group having 6 to 20 carbon atoms that is unsubstituted or substituted with an alkyl group or an aryl group; or an alkyl group, or a C2 to C20 heteroarylene group including O unsubstituted or substituted with an aryl group.

In an exemplary embodiment of the present specification, L4 is a divalent acenaphthyl group substituted or unsubstituted with an alkyl group; naphthylene group; divalent phenanthrene; a divalent cyclohexyl group; divalent propyl group; biphenylrylene group; a divalent methyl group substituted with an alkyl group or an aryl group; It is a divalent spirofluoro janthene group.

In an exemplary embodiment of the present specification, L4 is a divalent acenaphthyl group substituted or unsubstituted with an alkyl group; naphthylene group; divalent phenanthrene; a divalent cyclohexyl group; divalent iso-propyl group; biphenylrylene group; a divalent methyl group substituted with an aryl group; It is a divalent spirofluoro janthene group.

In an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently an aryl group having 6 to 20 carbon atoms; an alkyl group having 1 to 10 carbon atoms; or a heteroaryl group having 2 to 20 carbon atoms.

In an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently an aryl group having 6 to 20 carbon atoms; an alkyl group having 1 to 10 carbon atoms; or a C 2 to C 20 heteroaryl group including O or S.

In an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently a phenyl group; Biphenyl group; Naphthyl group; Methyl group; thiophene group; or an acenaphthyl group.

In the exemplary embodiment of the present specification, at least one of X1 to X3 is N.

In an exemplary embodiment of the present specification, at least two of X1 to X3 are N.

In an exemplary embodiment of the present specification, X1 to X3 are N.

In an exemplary embodiment of the present specification, the compound of Formula 1 is selected from the following structural formulas.

The compound according to an exemplary embodiment of the present application may be prepared by a manufacturing method described below.

For example, the compound of Formula 1 may be prepared as the compound of Formula 1 as shown in Scheme 1 below. Substituents may be combined by methods known in the art, and the type, position or number of substituents may be changed according to techniques known in the art.

On the other hand, the intermediate of the compound represented by Formula 1 can be prepared by the preparation method as shown in Schemes 1 and 2 below.

[Scheme 1]

[Scheme 2]

The compound represented by Chemical Formula 1 may be prepared by a preparation method as shown in Schemes 3 and 4 below.

[Scheme 3]

[Scheme 4]

In Schemes 1 to 4, Y is a halogen element, and Suzuki coupling reactions are Suzuki coupling reactions, and each reaction is preferably performed in the presence of a palladium catalyst and a base, and the reactor for the Suzuki coupling reaction is a sugar It is subject to change as known in the industry. The manufacturing method may be more specific in Preparation Examples to be described later.

In addition, the present specification provides an organic light-emitting device including the above-described compound.

In an exemplary embodiment of the present application, the 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 compound.

The organic material layer of the organic light emitting device of the present application may have a single-layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, as a representative example of the organic light emitting device of the present invention, the organic light emitting device 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, etc. 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 layers.

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

In an exemplary embodiment of the present application, the organic material layer includes a hole injection layer or a hole transport layer, and the hole injection layer or the hole transport layer includes the compound.

In an exemplary embodiment of the present application, 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.

In an exemplary embodiment of the present application, the organic material layer includes an electron transport layer or an electron injection layer, and the electron transport layer or the electron injection layer includes the compound.

In an exemplary embodiment of the present application, the organic material layer includes a hole blocking layer, an electron injection layer, an electron transport layer or an electron injection and transport layer, and the hole blocking layer, the electron injection layer, the electron transport layer or the electron injection and transport layer is the compound includes

In an exemplary embodiment of the present application, the organic material layer including the compound further includes a metal complex or an organic compound.

In an exemplary embodiment of the present application, the organic material layer including the compound includes a metal complex, and the weight ratio of the compound of Formula 1 to the metal complex is 99:1 to 20:80.

In an exemplary embodiment of the present application, the weight ratio of the compound of Formula 1 and the metal complex is 2:1 to 1:2.

In an exemplary embodiment of the present application, the weight ratio of the compound of Formula 1 and the metal complex is 1:1.

In an exemplary embodiment of the present application, the metal complex is 8-hydroxyquinolinato lithium (LiQ: lithium quinolate), 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)aluminum, tris(8-hydroxyquinolinato)aluminum Nolinato) gallium, bis (10-hydroxybenzo [h] quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chloro Gallium, bis(2-methyl-8-quinolinato)(o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8 -quinolinato) (2-naphtolato) means at least one selected from the group consisting of gallium.

In an exemplary embodiment of the present application, the organic material layer including the compound may further include a compound of Formula 10 below.

[Formula 10]

In the formula (10),

A is hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Hydroxy group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted arylthioxy group; A substituted or unsubstituted alkylsulfoxy group; a substituted or unsubstituted arylsulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, may be bonded to an adjacent substituent to form a substituted or unsubstituted ring, or may be bonded to each other through a single covalent bond with an adjacent group

The curves show the bonds required to form a 5- or 6-membered ring with M; and 2 or 3 atoms, which atoms are unsubstituted or substituted with 1 or 2 or more of the same substituents as defined in A,

M is an alkali metal or alkaline earth metal.

In the exemplary embodiment of the present application, the organic material layer includes the compound of Formula 1 and the compound of Formula 10.

In an exemplary embodiment of the present application, the organic material layer is a hole blocking layer; electron transport layer; or an electron injection and transport layer.

In an exemplary embodiment of the present application, the compound of Formula 10 is included as an n-type dopant.

In an exemplary embodiment of the present application, the organic material layer includes the compound of Formula 1 and the compound of Formula 10, and the compound of Formula 1 and the compound of Formula 10 in a weight ratio of 3:7 to 7:3 .

In an exemplary embodiment of the present application, the organic material layer includes the compound of Formula 1 and the compound of Formula 10 in a weight ratio of 1: 1.

In an exemplary embodiment of the present application, the compound of Formula 10 is a metal complex.

In an exemplary embodiment of the present application, M is lithium, sodium, potassium, rubidium, or cesium.

In the exemplary embodiment of the present application, M is Li.

In the exemplary embodiment of the present application, Chemical Formula 10 is represented by the following Chemical Formula 10-1.

[Formula 10-1]

In Formula 10-1,

M and A are as defined in formula (10), and a is an integer of 0 to 6.

In the exemplary embodiment of the present application, A in Formula 10-1 is hydrogen, and a is 6.

In an exemplary embodiment of the present application, the compound of Formula 10 is lithium quinolate.

In an exemplary embodiment of the present application, the organic light emitting device includes a first electrode; A second electrode provided to face the first electrode; and a light emitting layer provided between the first electrode and the second electrode. and two or more organic material layers provided between the light emitting layer and the first electrode or between the light emitting layer and the second electrode, and at least one of the two or more organic material layers includes the compound. In an exemplary embodiment of the present application, two or more organic material layers may be selected from the group consisting of an electron transport layer, an electron injection layer, an electron injection and transport layer, and a hole blocking layer.

In another exemplary embodiment, the organic light emitting device may be a normal type organic light emitting device in which a first electrode, one or more organic material layers, and a second electrode are sequentially stacked on a substrate.

In another exemplary embodiment, the organic light emitting device may be an inverted type organic light emitting device in which a second electrode, one or more organic material layers, and a first electrode are sequentially stacked on a substrate.

For example, the structure of the organic light emitting device according to an exemplary embodiment of the present specification is illustrated in FIGS. 1 and 2 .

1 illustrates a structure of an organic light emitting device in which a substrate 1, a first electrode 2, an organic material layer 3, and a second electrode 4 are sequentially stacked.

2 shows a substrate 1, an anode 2, a hole injection layer 5, a first hole transport layer 6, a second hole transport layer 7, a light emitting layer 8, an electron injection and transport layer 9, and The structure of the organic light emitting device in which the cathode 4 is sequentially stacked is exemplified, and the compound of Formula 1 may be included in the electron injection and transport layer 9 , but is 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 using materials and methods known in the art, except that at least one layer of the organic material layer includes the compound, that is, the compound represented by Formula 1 above.

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

In addition, the compound of Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

In the exemplary embodiment of the present application, the first electrode is an anode, and the second electrode is a cathode.

In another exemplary embodiment, the first electrode is a cathode, and the second electrode is an anode.

The anode is an electrode for injecting holes, and as the anode material, a material having a large work function is 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, 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; Poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), conductive polymers such as polypyrrole and polyaniline, and the like, but are not limited thereto.

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

The hole injection layer is a layer that facilitates injection of holes from the anode to the light emitting layer. As the hole injection material, holes can be well injected from the anode at a low voltage, and the highest occupied (HOMO) of the hole injection material is The molecular orbital) is preferably between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organic substances, hexanitrile hexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic substances, anthraquinone, polyaniline, and polythiophene-based conductive polymers, but are not limited thereto. The thickness of the hole injection layer may be 1 to 150 nm. When the thickness of the hole injection layer is 1 nm or more, there is an advantage in that the hole injection characteristics can be prevented from being deteriorated, and when it is 150 nm or less, the thickness of the hole injection layer is too thick, so that the driving voltage is increased to improve hole movement There are advantages to avoiding this.

The hole transport layer may serve to facilitate transport of holes. As the hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer is suitable, and a material having high hole mobility is suitable. Specific examples include an arylamine-based organic material, a conductive polymer, and a block copolymer including a conjugated portion and a non-conjugated portion, but are not limited thereto.

An electron blocking layer may be provided between the hole transport layer and the light emitting layer. The electron blocking layer may be a material known in the art.

The emission layer may emit red, green, or blue light, and may be made of a phosphorescent material or a fluorescent material. The light-emitting material is a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, 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 compound; Benzoxazole, benzthiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

Examples of the host material for the light emitting layer include a condensed aromatic ring derivative or a heterocyclic compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

When the emission layer emits red light, the emission dopants include PIQIr(acac)(bis(1-phenylisoquinoline)acetylacetonateiridium), PQIr(acac)(bis(1-phenylquinoline)acetylacetonate iridium), PQIr(tris(1-phenylquinoline)iridium). ), a phosphorescent material such as octaethylporphyrin platinum (PtOEP), or a _{fluorescent material such as Alq 3} (tris(8-hydroxyquinolino)aluminum), but is not limited thereto. When the light-emitting layer emits green light, the light-emitting dopant is a _{phosphor such as Ir(ppy) 3} (fac tris(2-phenylpyridine)iridium), Alq3(tris(8-hydroxyquinolino)aluminum), anthracene-based compound, or pyrene-based compound. A fluorescent material such as a compound or a boron-based compound may be used, but is not limited thereto. When the light emitting layer emits blue light, the light emitting dopant includes a _{phosphorescent material such as (4,6-F2ppy) 2} Irpic, spiro-DPVBi, spiro-6P, distylbenzene (DSB), distrylarylene (DSA), A fluorescent material such as a PFO-based polymer, a PPV-based polymer, an anthracene-based compound, a pyrene-based compound, or a boron-based compound may be used, but is not limited thereto.

The electron transport layer may play a role of facilitating transport of electrons. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high electron mobility is suitable. Specific examples include Al complex of 8-hydroxyquinoline; Complexes containing Alq _3; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The thickness of the electron transport layer may be 1 to 50 nm. If the thickness of the electron transport layer is 1 nm or more, there is an advantage of preventing deterioration of the electron transport characteristics, and if the thickness of the electron transport layer is 50 nm or less, the thickness of the electron transport layer is too thick to prevent an increase in the driving voltage to improve the movement of electrons. There is an advantage to be able to.

The electron injection layer may play a role of smoothly injecting electrons. The electron injection material has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, prevents the movement of excitons generated in the light emitting layer to the hole injection layer, , a compound having excellent thin film forming ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc. Complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

As the metal complex compound, the above-described metal complex may be used, but is not limited thereto.

The hole blocking layer is a layer that blocks the 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, etc., but are not limited thereto.

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

Hereinafter, in order to describe the present specification in detail, examples will be described in detail. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present application is not construed as being limited to the embodiments described below. The embodiments of the present application are provided to more completely describe the present specification to those of ordinary skill in the art.

Manufacturing example 1-1: Preparation of compound E1

In a nitrogen atmosphere, E1-A (20 g, 64.1 mmol) and E1-B (55.8 g, 128.2 mmol) were placed in 400 ml of tetrahydrofuran, stirred and refluxed. Thereafter, potassium carbonate (26.6 g, 192.3 mmol) was dissolved in 27 ml of water, and after sufficient stirring, tetrakistriphenyl-phosphinopalladium (2.2 g, 1.9 mmol) was added. After reaction for 1 hour, after cooling to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again put in chloroform 20 times 986 mL, dissolved, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare a white solid compound E1 (25.6 g, 52%, MS: [M+H] ⁺ = 769).

Manufacturing example 1-2: Preparation of compound E2

In a nitrogen atmosphere, E2-A (20 g, 52.6 mmol) and E2-B (36.2 g, 105.2 mmol) were placed in 400 ml of tetrahydrofuran, stirred and refluxed. After that, potassium carbonate (21.8 g, 157.9 mmol) was dissolved in 22 ml of water, stirred sufficiently, and then tetrakistriphenyl-phosphinopalladium (1.8 g, 1.6 mmol) was added. After the reaction for 3 hours, after cooling to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again put in chloroform 20 times 782 mL to dissolve, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare a white solid compound E2 (23.5 g, 60%, MS: [M+H] ⁺ = 743).

Manufacturing example 1-3: Preparation of compound E3

The E3 compound was prepared in the same manner as in Preparation Example 1-2, except that each starting material was prepared as in the above reaction scheme.

MS: [M+H] ⁺ = 617

Manufacturing example 1-4: Preparation of compound E4

The E4 compound was prepared in the same manner as in Preparation Example 1-2, except that each starting material was prepared as in the above reaction scheme.

MS: [M+H] ⁺ = 911

Manufacturing example 1-5: Preparation of compound E5

In a nitrogen atmosphere, E5-A (20 g, 34 mmol) and E5-B (13.2 g, 34 mmol) were placed in 400 ml of tetrahydrofuran, stirred and refluxed. After that, potassium carbonate (14.1 g, 102.1 mmol) was dissolved in 14 ml of water and thoroughly stirred, and then tetrakistriphenyl-phosphinopalladium (1.2 g, 1 mmol) was added. After reaction for 1 hour, after cooling to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again put in chloroform 20 times 523 mL, dissolved, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to prepare a white solid compound E5 (16 g, 61%, MS: [M+H] ⁺ = 769).

Manufacturing example 1-6: Preparation of compound E6

The E6 compound was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.

MS: [M+H] ⁺ = 767

Manufacturing example 1-7: Preparation of compound E7

The E7 compound was prepared in the same manner as in Preparation Example 1-5, except that each starting material was prepared as in the above reaction scheme.

MS: [M+H] ⁺ = 780

[ Experimental example One]

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

On the thus prepared ITO transparent electrode, the following HI-A compound was thermally vacuum deposited to a thickness of 600 Å to form a hole injection layer. A first hole transport layer and a second hole transport layer were formed by sequentially vacuum-depositing 50 Å of the HAT compound and 60 Å of the HT-A compound on the hole injection layer.

Subsequently, the following BH compound and BD compound were vacuum-deposited at a weight ratio of 25:1 to a thickness of 20 nm on the second hole transport layer to form a light emitting layer.

On the light emitting layer, the compound (E1) of Example 1 and the following LiQ compound were vacuum-deposited at a weight ratio of 1:1 to form an electron injection and transport layer to a thickness of 350 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 10 Å and aluminum to a thickness of 1000 Å on the electron injection and transport layer.

/sec를 유지하였고, 음극의 리튬 플루오라이드는 0.3Å/sec, 알루미늄은 2Å/sec의 증착 속도를 유지하였으며, 증착시 진공도는 1×10^-7 내지 5×10^-5 torr를 유지하여, 유기 발광 소자를 제조하였다.In the above process, the deposition rate of the organic material is 0.4 to 0.9

/sec was maintained, the deposition rate of lithium fluoride of the negative electrode was 0.3Å/sec, and the deposition rate of aluminum was 2Å/sec, and the vacuum degree during deposition was maintained at 1×10 ^-7 to 5×10 ^-5 torr, A light emitting device was manufactured.

Experimental example 2 to 7

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1, except that the compounds (E2 to E7) of the Preparation Examples shown in Table 1 were used instead of the compound (E1) of Experimental Example 1, respectively.

Comparative example 1 to 8

An organic light emitting diode was manufactured in the same manner as in Experimental Example 1, except that the compounds (ET-A to ET-H) in Table 1 below were used instead of the compound (E1) of Experimental Example 1, respectively.

The driving voltage and luminous efficiency were measured at a current density of ^{10 mA/cm 2} for the organic light-emitting devices prepared in the Experimental Examples and Comparative Examples, and the time at which the luminance becomes 90% compared to the initial luminance at a current density of ^{20 mA/cm 2 (T90)} was measured. The results are shown in Table 1 below.

division compound Voltage
(V@10 mA/cm ² ) efficiency
(cd/A@10 mA/cm ² ) Color coordinates
(x, y) Life(h)
T90 at 20 mA/cm ² ) Experimental Example 1 compound E1 4.43 4.73 (0.142, 0.096) 143 Experimental Example 2 compound E2 4.52 4.54 (0.142, 0.096) 172 Experimental Example 3 compound E3 4.47 4.59 (0.142, 0.096) 164 Experimental Example 4 compound E4 4.39 4.82 (0.142, 0.096) 130 Experimental Example 5 compound E5 4.30 4.92 (0.142, 0.096) 123 Experimental Example 6 compound E6 4.25 4.98 (0.142, 0.097) 117 Experimental Example 7 compound E7 4.30 4.97 (0.142, 0.096) 126 Comparative Example 1 Compound ET-A 4.87 3.55 (0.142, 0.096) 89 Comparative Example 2 Compound ET-B 4.97 3.41 (0.142, 0.096) 94 Comparative Example 3 Compound ET-C 4.92 3.44 (0.142, 0.096) 94 Comparative Example 4 Compound ET-D 4.82 3.62 (0.142, 0.096) 81 Comparative Example 5 Compound ET-E 4.73 3.69 (0.142, 0.096) 76 Comparative Example 6 Compound ET-F 4.68 3.73 (0.142, 0.096) 73 Comparative Example 7 Compound ET-G 4.73 3.72 (0.142, 0.097) 78 Comparative Example 8 Compound ET-H 5.06 2.94 (0.142, 0.097) 56

As shown in Table 1, the compound represented by Formula 1 according to the present invention may be used in an organic material layer capable of simultaneously performing electron injection and electron transport of the organic light emitting device.

Comparing Experimental Examples 1 to 7 and Comparative Examples 1 to 7 of Table 1, the compound of Formula 1 according to the present invention has voltage, efficiency, and lifespan of the organic light emitting device compared to the compound in which acenaphthyl is unsubstituted. It was confirmed that the remarkably excellent properties were shown

Comparing Experimental Example 3 and Comparative Example 8 of Table 1, the compound of Formula 1 according to the present invention, compared to the compound in which the arylene group is substituted in the acenaphthyl group, is significantly higher in terms of voltage, efficiency and lifespan of the organic light-emitting device. It was confirmed that excellent characteristics were exhibited.

1: substrate
2: Anode
3: organic layer
4: cathode
5: hole injection layer
6: First hole transport layer
7: second hole transport layer
8: light emitting layer
9: electron injection and transport layer

Claims (10)

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

In Formula 1,
L1 to L3 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group,
L4 is a substituted or unsubstituted alkylene group; a substituted or unsubstituted divalent cycloalkyl group; A substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
Ar1 and Ar2 are the same as or different from each other, and are each independently a substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
X1 to X3 are the same as or different from each other, each independently CH or N,
At least one of X1 to X3 is N,
At least one of Ar1, Ar2 and L4 is an acenaphthyl group unsubstituted or substituted with deuterium, a halogen group, a nitrile group, or an alkyl group; or a divalent acenaphthyl group unsubstituted or substituted with deuterium, a halogen group, a nitrile group, or an alkyl group;
Structures in parentheses are the same as or different from each other. The compound according to claim 1, wherein the structures in parentheses are the same as each other. The compound according to claim 1, wherein at least one of Ar1 and Ar2 is represented by the following formula (2):
[Formula 2]

In Formula 2,
Any one of R1 to R10 is combined with L1 or L2,
R1 to R10 not bonded to L1 or L2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; or an alkyl group. The compound according to claim 1, wherein L4 is represented by the following formula (3):
[Formula 3]

In Formula 3,
two of R11 to R20 are bonded to two L3s,
R11 to R20 not bonded to L3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; or an alkyl group. The compound of claim 1, wherein the compound of Formula 1 is selected from the following structural formulas:

A first electrode; A second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers comprises the compound according to any one of claims 1 to 5. device. The method according to claim 6, wherein the organic layer comprises a hole blocking layer, an electron transport layer, an electron injection layer, or an electron injection and transport layer, the hole blocking layer, the electron transport layer, the electron injection layer, or the electron injection and transport layer contains the compound an organic light emitting device. The organic light emitting device of claim 6 , wherein the organic material layer including the compound further comprises a metal complex or an organic compound. The organic light emitting device according to claim 8, wherein the organic material layer including the compound includes a metal complex, and the weight ratio of the compound of Formula 1 to the metal complex is 99:1 to 20:80. The method according to claim 8, wherein the metal complex is 8-hydroxyquinolinato lithium (LiQ: lithium quinolate), 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-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato) ) (2-naphtolato) an organic light emitting device that is at least one selected from the group consisting of gallium.

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