KR102477810B1 - Organic electroluminescence device and amine compound for organic electroluminescence device - Google Patents

Abstract

The present invention relates to an organic electroluminescent device and an amine compound for an organic electroluminescent device. An amine compound according to an embodiment of the present invention is represented by Formula 1 below.
[Formula 1]

Description

Organic electroluminescent device and amine compound for organic electroluminescent device

The present invention relates to an organic electroluminescent device and an amine compound for an organic electroluminescent device.

As an image display device, organic electroluminescence displays are being actively developed. An organic electroluminescent display device is different from a liquid crystal display device and the like, and realizes display by recombination of holes and electrons injected from the first electrode and the second electrode in the light emitting layer so that a light emitting material, which is an organic compound included in the light emitting layer, emits light. It is a light emitting display device.

Examples of the organic electroluminescent element include a first electrode, a hole transport layer disposed on the first electrode, a light emitting layer disposed on the hole transport layer, an electron transport layer disposed on the light emitting layer, and a second electrode disposed on the electron transport layer. Organized organic elements are known. Holes are injected from the first electrode, and the injected holes move through the hole transport layer and are injected into the light emitting layer. Meanwhile, electrons are injected from the second electrode, and the injected electrons move through the electron transport layer and are injected into the light emitting layer. When holes and electrons injected into the light emitting layer recombine, excitons are generated in the light emitting layer. An organic electroluminescent device emits light using light generated when its excitons fall back to the ground state. In addition, the organic electroluminescent element is not limited to the structure described above, and various changes are possible. In applying the organic light emitting device to a display device, a low driving voltage and a long lifespan of the organic light emitting device are required.

Another object of the present invention is to provide an organic electroluminescent device having low driving voltage, improved lifetime, and high luminous efficiency.

An object of the present invention is to provide an amine compound that can be used in an organic electroluminescent device having low driving voltage, improved lifespan, and high luminous efficiency.

An embodiment of the present invention provides a first electrode, a hole transport region disposed on the first electrode, a light emitting layer disposed on the hole transport region, an electron transport region disposed on the light emitting layer, and a second electrode disposed on the electron transport region. An organic electroluminescent device including an electrode and a hole transport region including an amine compound represented by Chemical Formula 1 is provided.

[Formula 1]

In Formula 1, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aryl group having 6 or more and 30 or less ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 or more and 30 or less ring carbon atoms, and Ar ₃ is a substituted or unsubstituted aryl group having 6 to 20 ring carbon atoms, and when Ar ₃ is substituted, the substituent is at least one of deuterium, a halogen atom, a silyl group, an alkyl group, and an aryl group, and Ar ₁ and Ar ₂ At least one is the above heteroaryl group, or at least one of Ar ₁ and Ar ₂ includes a polycyclic ring, and L ₁ is a substituted or unsubstituted arylene group having 6 or more and 30 or less ring carbon atoms, or a substituted or unsubstituted ring It is a heteroarylene group having 2 or more and 30 or less carbon atoms.

L ₁ may be a substituted or unsubstituted phenylene group, a substituted or unsubstituted divalent biphenyl group, a substituted or unsubstituted dibenzofuranylene group, or a substituted or unsubstituted dibenzothiophenylene group.

Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthylphenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, or a substituted Alternatively, it may be an unsubstituted phenanthryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

At least one of Ar ₁ and Ar ₂ is a substituted or unsubstituted naphthylphenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted It may be a cyclic dibenzothiophenyl group.

Formula 1 may be represented by Formula 1-1 below.

[Formula 1-1]

In Formula 1-1, Ar ₄ is a substituted or unsubstituted aryl group having 6 or more and 20 or less ring carbon atoms, and Ar ₁ , Ar ₃ , and L ₁ are the same as described above.

Formula 1 may be represented by Formula 1-2 below.

[Formula 1-2]

In Formula 1-2, Y ₁ and Y ₂ are each independently a hydrogen atom, a deuterium atom, a halogen atom, an alkyl group, or an aryl group, or may combine with adjacent groups to form a ring, and m1 and m2 are each It is independently an integer of 0 or more and 5 or less, and Ar ₁ and L ₁ are the same as described above.

Chemical Formula 1 may be represented by Chemical Formulas 1-3 below.

[Formula 1-3]

In Formula 1-3, X ₁ is O or S, and Ar ₂ , Ar ₃ , and L ₁ are the same as described above.

Chemical Formula 1 may be represented by Chemical Formulas 1-4 below.

[Formula 1-4]

In Formula 1-4, X ₁ and X ₂ are each independently O or S, and Ar ₃ and L ₁ are the same as described above.

The hole transport region may include a hole injection layer disposed on the first electrode and a hole transport layer disposed on the hole injection layer, and the hole transport layer may include an amine compound represented by Chemical Formula 1. In this case, the hole transport layer may be in contact with the light emitting layer.

The hole transport region includes a hole injection layer disposed on the first electrode, a first hole transport layer disposed on the hole injection layer, and a second hole transport layer disposed on the first hole transport layer and adjacent to the light emitting layer; may include an amine compound represented by Chemical Formula 1.

One embodiment of the present invention provides an amine compound represented by Formula 1 above.

An organic electroluminescent device according to an embodiment of the present invention can implement a low driving voltage, long lifespan, and high luminous efficiency.

An amine compound according to an embodiment of the present invention is included in an organic electroluminescent device, and can contribute to low driving voltage, long life and high efficiency.

1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.
2 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.
3 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.

The above objects, other objects, features and advantages of the present invention will be easily understood through the accompanying drawings and the following preferred embodiments. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosed content will be thorough and complete and the spirit of the present invention will be sufficiently conveyed to those skilled in the art.

Like reference numerals have been used for like elements throughout the description of each figure. In the accompanying drawings, the dimensions of the structures are shown enlarged than actual for clarity of the present invention. Terms such as first and second may be used to describe various components, but the components should not be limited by the terms. These terms are only used for the purpose of distinguishing one component from another. For example, a first element may be termed a second element, and similarly, a second element may be termed a first element, without departing from the scope of the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise.

In this specification, terms such as "include" or "have" are intended to designate that there is a feature, number, step, operation, component, part, or combination thereof described in the specification, but one or more other features It should be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof. In addition, when a part such as a layer, film, region, plate, etc. is said to be "on" another part, this includes not only the case where it is "directly on" the other part, but also the case where another part is present in the middle. Conversely, when a part such as a layer, film, region, plate, etc. is said to be "under" another part, this includes not only the case where it is "directly below" the other part, but also the case where another part is in the middle.

First, an organic electroluminescent device according to an embodiment of the present invention will be described with reference to FIGS. 1 to 3 .

1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention. 2 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention. 3 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.

1 to 3, the organic electroluminescent device 10 according to an embodiment of the present invention includes a first electrode EL1, a hole transport region HTR, a light emitting layer EML, and an electron transport region ETR. and a second electrode EL2.

The hole transport region (HTR) includes an amine compound according to an embodiment of the present invention. However, it is not limited thereto, and at least one of the one or more organic layers disposed between the first electrode EL1 and the second electrode EL2 may include the amine compound according to an embodiment of the present invention. And, for example, the light emitting layer (EML) may include an amine compound according to an embodiment of the present invention.

Hereinafter, after the amine compound according to an embodiment of the present invention is described in detail, each layer of the organic electroluminescent device 10 will be described.

An amine compound according to an embodiment of the present invention is represented by Formula 1 below.

[Formula 1]

In Formula 1, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aryl group having 6 or more and 30 or less ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 or more and 30 or less ring carbon atoms, and Ar ₃ is a substituted or unsubstituted aryl group having 6 to 20 ring carbon atoms, and when Ar ₃ is substituted, the substituent is at least one of deuterium, a halogen atom, a silyl group, an alkyl group, and an aryl group, and L ₁ is a substituted or unsubstituted A cyclic arylene group having 6 or more and 30 or less ring carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 or more and 30 or less ring carbon atoms.

는 연결되는 부위를 의미한다.In this specification,

indicates the connecting part.

In this specification, unless otherwise defined, "substituted or unsubstituted" is deuterium atom, halogen group, cyano group, nitro group, amino group, silyl group, boron group, aryl amine group, phosphine oxide group, phosphine sulfide It may mean that it is substituted or unsubstituted with one or more substituents selected from the group consisting of a group, an alkyl group, an alkenyl group, an aryl group, and a heterocyclic group. In addition, each of the substituents exemplified above may be substituted or unsubstituted. For example, a biphenyl group may be interpreted as an aryl group or a phenyl group substituted with a phenyl group.

In the present specification, “forming a ring by combining with adjacent groups” may mean forming a substituted or unsubstituted hydrocarbon ring or a substituted or unsubstituted heterocycle by combining with adjacent groups. Hydrocarbon rings include aliphatic hydrocarbon rings and aromatic hydrocarbon rings. Heterocycles include aliphatic heterocycles and aromatic heterocycles. Hydrocarbon rings and heterocycles may be monocyclic or polycyclic. In addition, rings formed by combining with each other may be connected to other rings to form a spiro structure.

In this specification, "adjacent group" may refer to a substituent substituted on an atom directly connected to the atom on which the corresponding substituent is substituted, another substituent substituted on the atom on which the corresponding substituent is substituted, or a substituent sterically closest to the corresponding substituent. there is. For example, two methyl groups in 1,2-dimethylbenzene can be interpreted as "adjacent groups" to each other, and 2 methyl groups in 1,1-diethylcyclopentene The two ethyl groups can be interpreted as "adjacent groups" to each other.

In this specification, direct linkage may mean a single linkage.

In this specification, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In this specification, the alkyl group may be straight chain, branched chain or cyclic. The number of carbon atoms of the alkyl group is 1 or more and 30 or less, 1 or more and 20 or less, 1 or more and 15 or less, 1 or more and 10 or less, or 1 or more and 6 or less. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, t-butyl group, i-butyl group, 2-ethylbutyl group, 3,3-dimethylbutyl group , n-pentyl group, i-pentyl group, neopentyl group, t-pentyl group, cyclopentyl group, 1-methylpentyl group, 3-methylpentyl group, 2-ethylpentyl group, 4-methyl-2-pentyl group , n-hexyl group, 1-methylhexyl group, 2-ethylhexyl group, 2-butylhexyl group, cyclohexyl group, 4-methylcyclohexyl group, 4-t-butylcyclohexyl group, n-heptyl group, 1 -Methylheptyl group, 2,2-dimethylheptyl group, 2-ethylheptyl group, 2-butylheptyl group, n-octyl group, t-octyl group, 2-ethyloctyl group, 2-butyloctyl group, 2-hexyl Siloctyl group, 3,7-dimethyloctyl group, cyclooctyl group, n-nonyl group, n-decyl group, adamantyl group, 2-ethyldecyl group, 2-butyldecyl group, 2-hexyldecyl group, 2-ox Tyldecyl group, n-undecyl group, n-dodecyl group, 2-ethyldodecyl group, 2-butyldodecyl group, 2-hexyldodecyl group, 2-octyldodecyl group, n-tridecyl group, n-tetradecyl group, n -Pentadecyl group, n-hexadecyl group, 2-ethylhexadecyl group, 2-butylhexadecyl group, 2-hexylhexadecyl group, 2-octylhexadecyl group, n-heptadecyl group, n-octadecyl group , n- nonadecyl group, n- icosyl group, 2-ethyl icosyl group, 2-butyl icosyl group, 2-hexyl icosyl group, 2-octyl icosyl group, n-henicosyl group, n- docosyl group, n-tricot practical group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, and n-triacontyl group; not limited to these The cyclic alkyl group may also include an adamantyl group.

In this specification, an aryl group means any functional group or substituent derived from an aromatic hydrocarbon ring. The aryl group may be a monocyclic aryl group or a polycyclic aryl group. The number of ring carbon atoms in the aryl group may be 6 or more and 30 or less, 6 or more and 20 or less, or 6 or more and 15 or less. Examples of the aryl group include a phenyl group, a naphthyl group, a fluorenyl group, anthracenyl group, a phenanthryl group, a biphenyl group, a terphenyl group, a quaterphenyl group, a quinquephenyl group, a sexyphenyl group, a triphenylene group, a pyrenyl group, a benzo fluoranthenyl group, Although a chrysenyl group etc. can be illustrated, it is not limited to these.

In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure. For example, the fluorenyl group may be a 9,9'-spirobifluorenyl group.

In the present specification, the heteroaryl group may be a heteroaryl group containing at least one of O, N, P, S, and Si as heterogeneous elements. The heteroaryl group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group. The number of ring carbon atoms in the heteroaryl group is 2 or more and 30 or less, or 2 or more and 20 or less. Examples of the heteroaryl group include a thiophenyl group, a furanyl group, a pyrrolyl group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a triazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, and a triazinyl group. , triazolyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phenoxazyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group , Pyrazino pyrazinyl group, isoquinolinyl group, indolyl group, carbazolyl group, N-arylcarbazolyl group, N-heteroarylcarbazolyl group, N-alkylcarbazolyl group, benzoxazolyl group, benzoimidazolyl group , Benzothiazolyl group, benzocarbazolyl group, benzothiophenyl group, dibenzothiophenyl group, thienothiophenyl group, benzofuranyl group, phenanthroline group (phenanthroline), thiazolyl group, isoxazolyl group, oxadiazolyl group , a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, a dibenzosilolyl group, and a dibenzofuranyl group, but are not limited thereto.

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

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

In this specification, the silyl group includes an alkyl silyl group and an aryl silyl group. Examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, and a phenylsilyl group. Not limited.

In this specification, the boron group includes an alkyl boron group and an aryl boron group. Examples of the boron group include, but are not limited to, trimethylboron, triethylboron, t-butyldimethylboron, triphenylboron, diphenylboron, and phenylboron.

In this specification, an alkenyl group may be straight-chain or branched-chain. The carbon number is not particularly limited, but is 2 or more and 30 or less, 2 or more and 20 or less, or 2 or more and 10 or less. Examples of the alkenyl group include, but are not limited to, a vinyl group, a 1-butenyl group, a 1-pentenyl group, a 1,3-butadienyl aryl group, a styrenyl group, and a styrylvinyl group.

In the present specification, the number of carbon atoms of the amine group is not particularly limited, but may be 1 or more and 30 or less. Amine groups may include alkyl amine groups and aryl amine groups. Examples of the amine group include, but are not limited to, a methylamine group, a dimethylamine group, a phenylamine group, a diphenylamine group, a naphthylamine group, a 9-methyl-anthracenylamine group, and a triphenylamine group.

An amine compound according to an embodiment of the present invention may be a mono amine compound.

At least one of Ar ₁ and Ar ₂ is the heteroaryl group, or at least one of Ar ₁ and Ar ₂ includes a polycyclic ring. “Including a polycyclic ring” may include both cases in which Ar ₁ and/or Ar ₂ themselves are substituents having a multicyclic ring structure and cases in which Ar 1 and/or Ar 2 themselves are substituted with a substituent having a multicyclic ring structure. Examples of the substituent having a polycyclic ring structure include a phenyl group substituted with a naphthyl group, a phenyl group substituted with a biphenyl group, and the like. Examples of substituents having a polycyclic ring structure themselves include a substituted or unsubstituted anthracene group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted fluorenyl group, and a substituted or unsubstituted fluorenyl group. A cyclic dibenzofuran group, a substituted or unsubstituted dibenzothiophene group, etc. are mentioned.

Although not limited thereto, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthylphenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthylphenyl group, or a substituted or unsubstituted terphenyl group. It may be a substituted naphthyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group.

Although not limited thereto, at least one of Ar ₁ and Ar ₂ is a substituted or unsubstituted naphthylphenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted fluorenyl group, or a substituted or unsubstituted dibenzofura It may be a yl group or a substituted or unsubstituted dibenzothiophenyl group.

L ₁ may be a substituted or unsubstituted arylene group having 6 or more and 12 or less ring carbon atoms. L ₁ may be a substituted or unsubstituted phenylene group or a substituted or unsubstituted divalent biphenyl group.

As another example, L ₁ may be a substituted or unsubstituted phenylene group, a substituted or unsubstituted divalent biphenyl group, a substituted or unsubstituted dibenzofuranylene group, or a substituted or unsubstituted dibenzothiophenylene group. .

L ₁ may be represented by Formula 2-1 or 2-2 below.

[Formula 2-1]

[Formula 2-2]

In Formulas 2-1 and 2-2, R ₁ to R ₃ are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted silyl group, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, or a substituted or an unsubstituted aryl group having 6 or more and 30 or less ring carbon atoms, and n ₁ to n ₃ may each independently be an integer of 0 or more and 4 or less. When n ₁ is 0, L ₁ represented by Formula 2-1 may mean that it is not substituted with R ₁ . When n ₁ is an integer of 2 or greater, a plurality of R ₁ may be identical to or different from each other. When n ₂ is 0, L ₁ represented by Formula 2-1 may mean that it is not substituted with R ₂ . When n ₂ is an integer of 2 or greater, a plurality of R ₂ may be identical to or different from each other. When n ₃ is 0, L ₁ represented by Formula 2-1 may mean that it is not substituted with R ₃ . When n ₃ is an integer of 2 or greater, a plurality of R ₃ may be identical to or different from each other.

L ₁ may be represented by any one of Formulas 2-3 to 2-6.

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 2-6]

In Chemical Formulas 2-3 to 2-6, R ₁ to R ₃ , and n ₁ to n ₃ are as described above.

When the amine compound according to an embodiment of the present invention has L ₁ represented by Chemical Formula 2-3 or 2-4, a naphthyl group and an amine at the meta position of at least a part of the substituted or unsubstituted phenylene group of the linker Groups may be connected to each other. When the amine compound according to an embodiment of the present invention has L ₁ represented by Formula 2-5 or 2-6, a naphthyl group and an amine at the para position of a substituted or unsubstituted phenylene group, which is at least a part of the linker Groups may be connected to each other.

Ar ₃ does not include a heteroaryl group. As described above, Ar ₃ is a substituted or unsubstituted aryl group having 6 or more and 20 or less ring carbon atoms, and when substituted, it is substituted with a substituent other than a heteroaryl group. When Ar ₃ is substituted with a heteroaryl group, the effect of stabilizing the relatively unstable heteroaryl group by nitrogen of the aryl amine is low, and thus efficiency may decrease when applied to an organic light emitting device.

Formula 1 may be represented by Formula 1-1 below.

[Formula 1-1]

In Formula 1-1, Ar ₄ is a substituted or unsubstituted aryl group having 6 or more and 20 or less ring carbon atoms, and Ar ₁ , Ar ₃ , and L ₁ are the same as defined in Formula 1.

Formula 1 may be represented by Formula 1-2 below.

[Formula 1-2]

In Formula 1-2, Y ₁ and Y ₂ are each independently a hydrogen atom, a deuterium atom, a halogen atom, an alkyl group, or an aryl group, or may combine with adjacent groups to form a ring, and m1 and m2 are each It is independently an integer of 0 or more and 5 or less, and Ar ₁ and L ₁ are the same as defined in Formula 1.

In Formula 1-2, when m1 is 2 or more, a plurality of Y ₁ are the same as or different from each other, and when m2 is 2 or more, a plurality of Y ₂ are the same or different from each other.

In Formula 1-2, when m1 is 1, Y ₁ may be a substituent other than a hydrogen atom, and when m2 is 1, Y ₂ may be a substituent other than a hydrogen atom.

Chemical Formula 1 may be represented by Chemical Formulas 1-3 below.

[Formula 1-3]

In Formula 1-3, X ₁ is O or S, and Ar ₂ , Ar ₃ , and L ₁ are the same as defined in Formula 1.

Chemical Formula 1 may be represented by Chemical Formulas 1-4 below.

[Formula 1-4]

In Formula 1-4, X ₁ and X ₂ are each independently O or S, and Ar ₃ and L ₁ are the same as defined in Formula 1.

The amine compound represented by Chemical Formula 1 may be any one selected from compounds represented in Compound Group 4 below. However, it is not limited thereto.

[Compound group 4]

The amine compound represented by Chemical Formula 1 may be any one selected from compounds represented in Compound Group 5 below. However, it is not limited thereto.

[Compound group 5]

The amine compound represented by Chemical Formula 1 may be any one selected from compounds represented in Compound Group 1 below. However, it is not limited thereto.

[Compound group 1]

.

.

The amine compound represented by Chemical Formula 1 may be any one selected from compounds represented in Compound Group 2 below. However, it is not limited thereto.

[Compound group 2]

.

.

The amine compound represented by Chemical Formula 1 may be any one selected from compounds represented by Compound Group 3 below. However, it is not limited thereto.

[Compound group 3]

An amine compound according to an embodiment of the present invention includes a naphthyl group in which carbon positions 1 and 8 are substituted. When the amine compound represented by Chemical Formula 1 is applied to an organic electroluminescent device, high luminous efficiency, low driving voltage, and long lifespan can be secured. Since the amine compound containing a naphthyl group having a substitution position at carbons 1 and 8 maintains hole transport properties and improves heat and charge resistance, the organic electroluminescent device using the amine compound has reduced property degradation due to high heat and charge. Implementation of longevity is possible. In addition, since crystallization of the amine compound according to an embodiment of the present invention is suppressed by a large volume of the substituted naphthyl group and film quality can be improved, organic electroluminescent devices using the amine compound can have high efficiency.

Referring again to FIGS. 1 to 3 , an organic electroluminescent device according to an embodiment of the present invention will be described.

Hereinafter, differences from the amine compound according to an embodiment of the present invention described above will be mainly described in detail, and parts not described depend on the amine compound according to an embodiment of the present invention described above.

The first electrode EL1 has conductivity. The first electrode EL1 may be a pixel electrode or an anode. The first electrode EL1 may be a transmissive electrode, a transflective electrode, or a reflective electrode. When the first electrode EL1 is a transmissive electrode, the first electrode EL1 is a transparent metal oxide, for example, indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), or indium ITZO (ITZO). tin zinc oxide) and the like. When the first electrode EL1 is a transflective electrode or a reflective electrode, the first electrode EL1 is Ag, Mg, Cu, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF/Ca, LiF/Al, Mo, Ti, or a compound or mixture thereof (eg, a mixture of Ag and Mg). Alternatively, a plurality of layer structures including a reflective film or semi-transmissive film formed of the above material and a transparent conductive film formed of indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium tin zinc oxide (ITZO), or the like. can be

The hole transport region HTR is disposed on the first electrode EL1. The hole transport region HTR may include at least one of a hole injection layer (HIL), a hole transport layer (HTL), a hole buffer layer, and an electron blocking layer.

The hole transport region HTR may have a single layer structure made of a single material, a single layer made of a plurality of different materials, or a multilayer structure having a plurality of layers made of a plurality of different materials.

For example, as shown in FIG. 2 , the hole transport region HTR may have a structure of a hole injection layer (HIL) or a single layer of a hole transport layer (HTL), and is composed of a hole injection material and a hole transport material. It may have a single layer structure. In addition, the hole transport region HTR has a structure of a single layer made of a plurality of different materials, or a hole injection layer HIL / hole transport layer HTL sequentially stacked from the first electrode EL1, hole injection layer (HIL) / hole transport layer (HTL) / hole buffer layer, hole injection layer (HIL) / hole buffer layer, hole transport layer (HTL) / hole buffer layer or hole injection layer (HIL) / hole transport layer (HTL) / electron blocking layer It may have a structure, but is not limited thereto.

As shown in FIG. 3 , the hole transport region HTR may have a plurality of hole transport layers. The hole transport region HTR may include a first hole transport layer HTL1 and a second hole transport layer HTL2 disposed on the first hole transport layer HTL1. The second hole transport layer HTL2 may be a hole transport layer adjacent to the light emitting layer EML among the plurality of hole transport layers.

The hole transport region (HTR) is formed by various methods such as vacuum deposition method, spin coating method, cast method, LB method (Langmuir-Blodgett), inkjet printing method, laser printing method, laser induced thermal imaging (LITI), and the like. can be formed using

As described above, the hole transport region (HTR) includes an amine compound represented by Chemical Formula 1. The hole transport region (HTR) may include one or two or more amine compounds represented by Chemical Formula 1. The hole transport region (HTR) may include an amine compound according to an embodiment of the present invention described above as a hole transport material. can include The layer including the amine compound according to an embodiment of the present invention described above may be a hole transport layer (HTL). 3 , when the hole transport layer includes the first hole transport layer HTL1 and the second hole transport layer HTL2, the amine compound according to an embodiment of the present invention may be included in the second hole transport layer HTL2. An amine compound according to an embodiment of the present invention may be included in a layer adjacent to the light emitting layer (EML) in the hole transport region (HTR).

When the hole transport layer (HTL) includes an amine compound according to an embodiment of the present invention, the hole injection layer (HIL) may include, for example, a phthalocyanine compound such as copper phthalocyanine; DNTPD (N,N'-diphenyl-N,N'-bis-[4-(phenyl-m-tolyl-amino)-phenyl]-biphenyl-4,4'-diamine), m-MTDATA (4,4' ,4"-tris(3-methylphenylphenylamino)triphenylamine), TDATA(4,4'4"-Tris(N,N-diphenylamino)triphenylamine), 2-TNATA(4,4',4"-tris{N,- (2-naphthyl)-N-phenylamino}-triphenylamine), PEDOT/PSS (Poly(3,4-ethylenedioxythiophene)/Poly(4-styrenesulfonate)), PANI/DBSA (Polyaniline/Dodecylbenzenesulfonic acid), PANI/CSA (Polyaniline /Camphor sulfonicacid), PANI/PSS((Polyaniline)/Poly(4-styrenesulfonate)), NPB(N,N'-di(naphthalene-l-yl)-N,N'-diplienyl-benzidine), triphenylamine Polyether ketone (TPAPEK) containing, 4-Isopropyl-4'-methyldiphenyliodonium Tetrakis (pentafluorophenyl) borate], HAT-CN (1,4,5,8,9,11-Hexaazatriphenylenehexacarbonitrile) and the like may be included.

The hole transport layer (HTL) may further include a known material in addition to the amine compound according to an embodiment of the present invention. The hole transport layer (HTL) may include, for example, carbazole-based derivatives such as N-phenylcarbazole and polyvinylcarbazole, fluorene-based derivatives, TPD (N,N'-bis(3-methylphenyl)-N, Triphenylamine derivatives such as N'-diphenyl-[1,1-biphenyl]-4,4'-diamine), TCTA (4,4',4"-tris(N-carbazolyl)triphenylamine), NPB (N ,N'-di(1-naphthyl)-N,N'-diphenylbenzidine), TAPC(4,4'-Cyclohexylidene bis[N,N-bis(4-methylphenyl)benzenamine]), HMTPD(4,4'- Bis[N,N'-(3-tolyl)amino]-3,3'-dimethylbiphenyl) and the like may be included.

The hole transport region HTR may have a thickness of about 150 Å to about 12000 Å, for example, about 150 Å to about 1500 Å. If the hole transport region (HTR) includes both the hole injection layer (HIL) and the hole transport layer (HTL), the thickness of the hole injection layer (HIL) is about 100 Å to about 10000 Å, for example, about 100 Å to about 1000 Å, The hole transport layer (HTL) may have a thickness of about 50 Å to about 1000 Å. When the thicknesses of the hole transport region HTR, the hole injection layer HIL, and the hole transport layer HTL satisfy the ranges described above, satisfactory hole transport characteristics may be obtained without a substantial increase in driving voltage.

In addition to the aforementioned materials, the hole transport region HTR may further include a charge generating material to improve conductivity. The charge generating material may be uniformly or non-uniformly dispersed within the hole transport region (HTR). The charge generating material may be, for example, a p-dopant. The p-dopant may be one of a quinone derivative, a metal oxide, and a compound containing a cyano group, but is not limited thereto. For example, non-limiting examples of the p-dopant include quinone derivatives such as TCNQ (Tetracyanoquinodimethane) and F4-TCNQ (2,3,5,6-tetrafluoro-tetracyanoquinodimethane), metal oxides such as tungsten oxide and molybdenum oxide, and the like. It may include, but is not limited thereto.

As described above, the hole transport region HTR may further include at least one of a hole buffer layer and an electron blocking layer in addition to the hole injection layer HIL and the hole transport layer HTL. The hole buffer layer may increase light emission efficiency by compensating for a resonance distance according to a wavelength of light emitted from the light emitting layer EML. A material that can be included in the hole transport region (HTR) may be used as a material included in the hole buffer layer. The electron blocking layer is a layer that serves to prevent injection of electrons from the electron transport region ETR to the hole transport region HTR.

The light emitting layer EML is disposed on the hole transport region HTR. The light emitting layer (EML) may be disposed on the hole transport layer (HTL) and contact the hole transport layer (HTL). The thickness of the light emitting layer EML may be, for example, about 100 Å to about 600 Å. The light emitting layer EML may have a single layer structure made of a single material, a single layer made of a plurality of different materials, or a multilayer structure having a plurality of layers made of a plurality of different materials.

The light emitting layer EML may emit one of red light, green light, blue light, white light, yellow light, and cyan light. The light emitting layer EML may include a fluorescent material or a phosphorescent material. In addition, the light emitting layer EML may include a host and a dopant.

As the host material of the light emitting layer (EML), anthracene derivatives, fluoranthene derivatives, pyrene derivatives, arylacetylene derivatives, fluorene derivatives, perylene derivatives, It is selected from chrysene derivatives, phenanthrene derivatives and the like, and preferably includes pyrene derivatives, perylene derivatives, chrysene derivatives, phenanthrene derivatives and anthracene derivatives. For example, as a host material of the light emitting layer (EML), an anthracene derivative represented by Chemical Formula 4 may be used.

[Formula 4]

In Formula 4, Z ₁ to Z ₄ are each independently a hydrogen atom, a deuterium atom, a halogen atom, a substituted or unsubstituted silyl group, a substituted or unsubstituted alkyl group having 1 to 15 carbon atoms, and a substituted or unsubstituted ring. An aryl group having 6 to 30 carbon atoms or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms for ring formation, m ₁ and m ₂ are each independently an integer of 0 to 4, and m ₃ and m ₄ are each independently an integer of 0 or more and 5 or less. In Formula 4, Z ₃ and Z ₄ may independently bond to adjacent groups to form a ring.

Examples of the compound represented by Formula 4 include compounds represented by the following structural formula. However, the compound represented by Formula 4 is not limited to the following.

.

.

The host is not particularly limited as long as it is a commonly used material, but, for example, Alq ₃ (tris (8-hydroxyquinolino) aluminum), CBP (4,4'-bis (N-carbazolyl) -1,1'-biphenyl) , PVK(poly(N-vinylcabazole), ADN(9,10-di(naphthalene-2-yl)anthracene), TCTA(4,4',4''-Tris(carbazol-9-yl)-triphenylamine), TPBi(1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene), TBADN(3-tert-butyl-9,10-di(naphth-2-yl)anthracene), DSA(distyrylarylene), CDBP (4,4′-bis(9-carbazolyl)-2,2′-dimethyl-biphenyl), MADN (2-Methyl-9,10-bis(naphthalen-2-yl)anthracene), and the like can also be used.

The dopant is, for example, a styryl derivative (e.g., 1,4-bis[2-(3-N-ethylcarbazoryl)vinyl]benzene(BCzVB), 4-(di-p-tolylamino)-4'-[ (di-p-tolylamino)styryl]stilbene (DPAVB), N-(4-((E)-2-(6-((E)-4-(diphenylamino)styryl)naphthalen-2-yl)vinyl)phenyl )-N-phenylbenzenamine (N-BDAVBi), perylene and its derivatives (eg 2,5,8,11-Tetra-tert-butylperylene (TBP)), pyrene and its derivatives (eg 1, Dopants such as 1-dipyrene, 1,4-dipyrenylbenzene, and 1,6-Bis(N, N-Diphenylamino)pyrene) may be included.

When the light emitting layer (EML) emits red light, the light emitting layer (EML) is, for example, a fluorescent material containing PBD:Eu(DBM) ₃ (Phen) (tris(dibenzoylmethanato)phenanthoroline europium) or perylene. may further include. When the light emitting layer (EML) emits red light, the dopant included in the light emitting layer (EML) is, for example, PIQIr (acac) (bis (1-phenylisoquinoline) acetylacetonate iridium), PQIr (acac) (bis (1-phenylquinoline) acetylacetonate iridium), metal complexes or organometallic complexes such as tris(1-phenylquinoline)iridium (PQIr) and octaethylporphyrin platinum (PtOEP), rubrene and its derivatives, and 4-dicyano methylene-2-(p-dimethylaminostyryl)-6-methyl-4H-pyran (DCM) and its derivatives.

When the light emitting layer EML emits green light, the light emitting layer EML may further include a fluorescent material including, for example, Alq ₃ (tris(8-hydroxyquinolino)aluminum). When the light emitting layer (EML) emits green light, the dopant included in the light emitting layer (EML) is, for example, a metal complex compound such as Ir(ppy) ₃ (fac-tris(2-phenylpyridine)iridium) or an organic material. It can be selected from organometallic complex and coumarin and its derivatives.

When the light emitting layer (EML) emits blue light, the light emitting layer (EML) is, for example, spiro-DPVBi (spiro-DPVBi), spiro-6P (spiro-6P), DSB (distyryl-benzene), DSA (distyryl- arylene), PFO (Polyfluorene) polymer, and PPV (poly (p-phenylene vinylene) polymer. When the light emitting layer (EML) emits blue light , The dopant included in the light emitting layer (EML) is selected from, for example, a metal complex such as (4,6-F2ppy) ₂ Irpic or an organometallic complex, perylene and derivatives thereof. can

The electron transport region ETR is disposed on the light emitting layer EML. The electron transport region ETR may include at least one of a hole blocking layer, an electron transport layer ETL, and an electron injection layer EIL, but is not limited thereto.

The electron transport region ETR may have a single layer structure made of a single material, a single layer made of a plurality of different materials, or a multilayer structure having a plurality of layers made of a plurality of different materials.

For example, the electron transport region ETR may have a single layer structure of an electron injection layer (EIL) or an electron transport layer (ETL), or may have a single layer structure composed of an electron injection material and an electron transport material. In addition, the electron transport region ETR has a single layer structure made of a plurality of different materials, or an electron transport layer ETL/electron injection layer EIL sequentially stacked from the first electrode EL1, or a hole blocking layer. It may have a layer/electron transport layer (ETL)/electron injection layer (EIL) structure, but is not limited thereto.

As shown in FIG. 3 , the electron transport region ETR may have a plurality of electron transport layers. The electron transport region ETR may include a first electron transport layer ETL1 and a second electron transport layer ETL2 disposed on the first electron transport layer ETL1 .

The electron transport region (ETR) is formed by various methods such as vacuum deposition, spin coating, casting, Langmuir-Blodgett (LB), inkjet printing, laser printing, and laser induced thermal imaging (LITI). can be formed using

When the electron transport region (ETR) includes the electron transport layer (ETL), the electron transport region (ETR) is Alq ₃ (Tris (8-hydroxyquinolinato) aluminum), 1,3,5-tri[(3-pyridyl)- phen-3-yl]benzene, 2,4,6-tris(3'-(pyridin-3-yl)biphenyl-3-yl)-1,3,5-triazine, 2-(4-(N-phenylbenzoimidazolyl -1-ylphenyl)-9,10-dinaphthylanthracene, TPBi(1,3,5-Tri(1-phenyl-1H-benzo[d]imidazol-2-yl)phenyl), BCP(2,9-Dimethyl-4 ,7-diphenyl-1,10-phenanthroline), Bphen(4,7-Diphenyl-1,10-phenanthroline), TAZ(3-(4-Biphenylyl)-4-phenyl-5-tert-butylphenyl-1,2 ,4-triazole), NTAZ(4-(Naphthalen-1-yl)-3,5-diphenyl-4H-1,2,4-triazole), tBu-PBD(2-(4-Biphenylyl)-5-( 4-tert-butylphenyl)-1,3,4-oxadiazole), BAlq (Bis(2-methyl-8-quinolinolato-N1,O8)-(1,1'-Biphenyl-4-olato)aluminum), Bebq ₂ (berylliumbis (benzoquinolin-10-olate), ADN (9,10-di (naphthalene-2-yl) anthracene) and mixtures thereof, but are not limited thereto. The thickness of the electron transport layers (ETLs) is It may be about 100 Å to about 1000 Å, for example, about 150 Å to about 500 A. When the thicknesses of the electron transport layers (ETLs) satisfy the aforementioned range, satisfactory electron transport characteristics may be obtained without a substantial increase in driving voltage. there is.

When the electron transport region ETR includes the electron injection layer EIL, metals such as Al, Ag, Li, Mg, and Ca, and mixtures thereof may be included. However, it is not limited thereto. For example, a lanthanide metal such as LiF, lithium quinolate (LiQ), Li ₂ O, BaO, NaCl, CsF, or Yb, or a metal halide such as RbCl or RbI may be used for the electron injection layer (EIL). It is not limited. The electron injection layer (EIL) may also be made of a mixture of an electron transport material and an insulating organometal salt. The organometallic salt may be a material having an energy band gap of about 4 eV or more. Specifically, for example, the organometallic salt may include metal acetate, metal benzoate, metal acetoacetate, metal acetylacetonate or metal stearate. can The electron injection layers (EIL) may have a thickness of about 10 Å to about 100 Å. When the thickness of the electron injection layers (EIL) satisfies the aforementioned range, satisfactory electron injection characteristics may be obtained without a substantial increase in driving voltage.

As mentioned above, the electron transport region ETR may include a hole blocking layer. The hole blocking layer may include, for example, at least one of BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline) and Bphen (4,7-diphenyl-1,10-phenanthroline). However, it is not limited thereto.

The second electrode EL2 is disposed on the electron transport region ETR. The second electrode EL2 may be a common electrode or a cathode. The second electrode EL2 may be a transmissive electrode, a transflective electrode, or a reflective electrode. When the second electrode EL2 is a transmissive electrode, the second electrode EL2 is a transparent metal oxide, for example, indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), or indium ITZO (indium tin oxide). tin zinc oxide) and the like.

When the second electrode EL2 is a transflective electrode or a reflective electrode, the second electrode EL2 is Ag, Mg, Cu, Al, Pt, Pd, Au, Ni, Nd, Ir, Cr, Li, Ca, LiF/Ca, LiF/Al, Mo, Ti, or a compound or mixture thereof (eg, a mixture of Ag and Mg). Alternatively, a plurality of layer structures including a reflective film or semi-transmissive film formed of the above material and a transparent conductive film formed of indium tin oxide (ITO), indium zinc oxide (IZO), zinc oxide (ZnO), indium tin zinc oxide (ITZO), or the like. can be

Although not shown, the second electrode EL2 may be connected to the auxiliary electrode. When the second electrode EL2 is connected to the auxiliary electrode, resistance of the second electrode EL2 may be reduced.

In the organic electroluminescent device 10, as voltage is applied to the first electrode EL1 and the second electrode EL2, holes injected from the first electrode EL1 form the hole transport region HTR. The electrons injected from the second electrode EL2 are transferred to the light emitting layer EML through the electron transport region ETR. Electrons and holes recombine in the light emitting layer (EML) to generate excitons, and as the excitons fall from an excited state to a ground state, they emit light.

When the organic electroluminescent device 10 is a top emission type, the first electrode EL1 may be a reflective electrode, and the second electrode EL2 may be a transmissive electrode or a transflective electrode. When the organic electroluminescent device 10 is a bottom emission type, the first electrode EL1 may be a transmissive electrode or a transflective electrode, and the second electrode EL2 may be a reflective electrode.

An organic electroluminescent device according to an embodiment of the present invention includes the amine compound represented by Chemical Formula 1 and can secure high luminous efficiency, low driving voltage, and long lifespan. The amine compound according to an embodiment of the present invention is disposed in the hole transport region (HTR) of the organic electroluminescent device, and has high hole transport characteristics while reducing heat and charge loads, resulting in low driving voltage, high luminous efficiency and long lifespan. can be obtained. Specifically, the amine compound represented by Formula 1 is By including a naphthalenyl group having a substitution position at carbons 1 and 8, heat and charge resistance are improved while maintaining hole transport properties, and thus, organic electroluminescent devices to which this is applied reduce degradation of properties due to high heat and electric charges. and can become long-lived. In addition, the crystallization of the amine compound according to an embodiment of the present invention is suppressed by the large volume of the substituted naphthyl group, and the organic electroluminescent device using this as a hole transport layer improves the film quality of the hole transport layer. High efficiency can be achieved.

Hereinafter, the present invention will be described in more detail through specific manufacturing methods, Examples and Comparative Examples. The following examples are merely examples to aid understanding of the present invention, and the scope of the present invention is not limited thereto.

An amine compound according to an embodiment of the present invention may be synthesized as follows, for example. However, it is not limited thereto.

(synthesis example)

1. Synthesis of Compound 5

(Synthesis of Compound A)

THF/water (20%) in which 8.80 g of 1,8-dibromonaphthlene, 4.69 g of Phenylboron acid, 4.89 g of Na ₂ CO ₃ , and 1.07 g of Pd (PPh ₃ ) ₄ were dissolved in a 500 ml three-neck flask under an argon (Ar) atmosphere. 200 mL of the mixed solution was heated and stirred at 80°C for 5 hours. After air cooling, dichloromethane was added to separate the organic layer, and the solvent was evaporated. The obtained product was purified by silica gel column chromatography (hexane/toluene) to obtain 6.27 g (yield 72%) of Compound A as a pale yellow solid. The molecular weight of Compound A measured by FAB-MS was 283.

(Synthesis of Compound B)

Under an argon (Ar) atmosphere, after adding 6.70 g of Compound A and 60 ml of THF solvent to a 200 ml three-necked flask and cooling to -78 ° C, 23.1 mL of a hexane solution (1.6 M) of n-BuLi was added dropwise and stirred for 50 minutes. Thereafter, 5 ml THF solution in which 13.4 g of B(OMe) ₃ was dissolved was added dropwise, stirred at -78°C for 50 minutes, returned to room temperature, and stirred for another 3 hours. Then, a saturated NH ₄ Cl aqueous solution was added, the organic layer was separated, and the solvent was evaporated. The residue obtained in the three-neck flask was washed with hexane to obtain 4.17 g (yield: 71%) of compound B as a white solid. The molecular weight of compound B measured by FAB-MS measurement was 248.

(Synthesis of Compound C)

_THF / _{water ( 20} %) was heated and stirred at 80°C for 5 hours. After air cooling, dichloromethane was added to separate the organic layer, and the solvent was evaporated. The obtained product was purified by silica gel column chromatography (hexane/toluene) to obtain 2.22 g (yield: 27%) of Compound C as a pale yellow solid. The molecular weight of compound C measured by FAB-MS measurement was 359.

(Synthesis of Compound 5)

6.17 g of compound C and N-[1,1"-biphenyl]-4-yl-N-[4-(4,4,5,5-tetramethyl-1,3 3.85 g of ,2-dioxaborolan-2-yl)phenyl]-[1,1?-biphenyl]-4-amine, 1.84 g of K ₃ PO ₄ , and 0.231 g of Pd(PPh ₃ ) ₄ dissolved in THF/water ( 20%) mixed solution (130mL) was heated and stirred at 80° C. for 5 hours. Dichloromethane was added to separate the organic layer, and the solvent was evaporated. The obtained product was purified by silica gel column chromatography (hexane/toluene), and the compound was obtained as a white solid. 3.16 g (yield 70%) of 5 was obtained.The molecular weight of the compound measured by FAB-MS was 676. In addition, the chemical shift value of the compound measured by ¹ H-NMR (CDCl ₃ ) measurement 8.52-8.39 (m, 4H), 8.33 (d, 2H), 8.25 (dd, 4H), 8.10 (d, 2H), 8.02-7.89 (m, 4H), 7.92-7.77 (m, 8H), 7.69- 7.62 (m, 4H), 7.48-7.43 (m, 3H), and 7.18-7.02 (m, 6H) From the above results, it was confirmed that the compound as a white solid was Compound 5.

2. Synthesis of Compound 21

Compound C was obtained in the same manner as in the synthesis method for compound C in the synthesis method of compound 5 described above. Under argon (Ar) atmosphere, compound C 3.70g and 4-(1-naphthalenyl)-N-[4-(1-naphthalenyl)phenyl]-benzenamine 4.21g, Pd(dba) ₂ 0.181g, NaOtBu in a 300ml igu flask 3.69 g and 0.135 g of tBu ₃ P were added, and heating and reflux stirring were performed at 80°C for 6 hours in a mixed solvent of 120 ml toluene. After air cooling, water was added, the organic layer was fractionated, and the solvent was evaporated. The obtained product was purified by silica gel column chromatography (hexane/toluene) to obtain 6.22 g (89% yield) of Compound 21 as a white solid. The molecular weight of the compound measured by FAB-MS measurement was 700. In addition, the chemical shift values of the compounds measured in ¹ H-NMR (CDCl ₃ ) measurement were 8.52-8.39 (m, 4H), 8.33 (d, 2H), 8.25 (dd, 4H), 8.10 (d , 2H), 8.02-7.89 (m, 2H), 7.92-7.77 (m, 8H), 7.69-7.62 (m, 4H), 7.48-7.43 (m, 5H), and 7.18-7.02 (m, 6H). Through the above results, it was confirmed that the compound of white solid was Compound 21.

3. Synthesis of Compound 46

In the synthesis method of compound 21 described above, except for using N-3-dibenzofuranyl-3-Dibenzofuranamine instead of 4-(1-naphthalenyl)-N-[4-(1-naphthalenyl)phenyl]-benzenamine, the synthesis of compound 21 and Compound 46 was synthesized in the same manner. The molecular weight of the compound measured by FAB-MS measurement was 628. In addition, the chemical shift values of the compounds measured in ¹ H-NMR measurement were 8.45-8.39 (m, 4H), 8.31 (d, 2H), 8.25 (dd, 4H), 8.08 (d, 2H), 8.02-7.89 (m, 2H), 7.72-7.60 (m, 4H), 7.50-7.40 (m, 5H), and 7.33-7.26 (m, 6H). Through the above results, it was confirmed that the synthesized compound was Compound 25.

4. Synthesis of Compound 53

Compound D was synthesized in the same manner as in the synthesis of Compound C, except that 1-Bromo-4-iodobenzene was used instead of 1-Bromo-3-iodobenzene in the synthesis method of Compound C described above. Thereafter, in the synthesis method of Compound 21 described above, Compound 53 was synthesized in the same manner as in the synthesis of Compound 21, except that Compound D was used instead of Compound C. The molecular weight of the compound measured by FAB-MS measurement was 700. In addition, the chemical shift values of the compounds measured in ¹ H-NMR measurement were 8.44-8.35 (m, 4H), 8.33 (d, 2H), 8.25 (dd, 4H), 8.20-8.13 (m, 5H) ), 8.10 (d, 2H), 8.02-7.89 (m, 2H), 7.69-7.62 (m, 4H), 7.51-7.45 (m, 8H), 7.28-7.22 (m, 6H) was Through the above results, it was confirmed that the synthesized compound was Compound 53.

5. Synthesis of Compound 4

In the method for synthesizing compound 5 described above, N-[1,1'-biphenyl]-4-yl-N-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2- Except for using B-[4-[(9,9-diphenyl-9H-fluoren-2-yl)phenylamino]phenyl]-boronic acid instead of yl)phenyl]-[1,1'-Biphenyl]-4-amine Compound 4 was synthesized in the same manner as in the synthesis of compound 5. The molecular weight of the compound measured by FAB-MS measurement was 764. In addition, the chemical shift values of the compounds measured by ¹ H-NMR were 8.44-8.37 (m, 4H), 8.31-8.26 (m, 6H), 8.12 (d, 2H), 8.00-7.89 (m, 8H) ), 7.77-7.60 (m, 10H), 7.51-7.40 (m, 5H), and 7.30-7.24 (m, 6H). Through the above results, it was confirmed that the synthesized compound was Compound 4.

6. Synthesis of Compound 59

In the above synthesis method of compound 53, N-[1,1'-biphenyl]-4-yl-4'- instead of 4-(1-naphthalenyl)-N-[4-(1-naphthalenyl)phenyl]-benzenamine Compound 59 was synthesized in the same manner as in the synthesis of compound 53, except that (triphenylsilyl)-benzenamine was used. The molecular weight of the compound measured by FAB-MS measurement was 782. In addition, the chemical shift values of the compounds measured by ¹ H-NMR measurement were 8.38-8.35 (m, 4H), 8.27-8.19 (m, 6H), 8.16 (d, 2H), 8.10-7.89 (m) , 8H), 7.79–7.62 (m, 10H), 7.50–7.35 (m, 5H), and 7.29–7.20 (m, 8H). Through the above results, it was confirmed that the synthesized compound was Compound 59.

7. Synthesis of Compound 66

In the synthesis method of compound 53 described above, except for using N-3-dibenzofuranyl-3-Dibenzofuranamine instead of 4-(1-naphthalenyl)-N-[4-(1-naphthalenyl)phenyl]-benzenamine, Compound 66 was synthesized in the same manner. The molecular weight of the compound measured by FAB-MS measurement was 628. In addition, the chemical shift values of the compounds measured by ¹ H-NMR measurement were 8.40-8.35 (m, 2H), 8.30 (d, 4H), 8.22 (d, 4H), 8.20-8.13 (m, 5H) ), 8.00 (d, 2H), 7.89–7.62 (m, 6H), 7.28–7.22 (m, 2H), and 7.11 (d, 4H). Through the above results, it was confirmed that the synthesized compound was Compound 66.

8. Synthesis of Compound 75

In the synthesis method of compound 59 described above, N-[1,1'-biphenyl]-4-yl-4'-(triphenylsilyl)-benzenamine was replaced with N-[1,1'-biphenyl]-4-yl-3' Compound 75 was synthesized in the same manner as in the synthesis of compound 59, except that -(triphenylsilyl)-benzenamine was used. The molecular weight of the compound measured by FAB-MS measurement was 782. In addition, the chemical shift values of the compounds measured by ¹ H-NMR measurement were 8.41-8.36 (m, 4H), 8.27-8.19 (m, 6H), 8.16 (d, 2H), 8.12-7.99 (m) , 8H), 7.79-7.62 (m, 10H), 7.53-7.41 (m, 4H), and 7.29-7.22 (m, 9H). Through the above results, it was confirmed that the synthesized compound was Compound 75.

9. Synthesis of Compound 81

In the method for synthesizing compound 53 described above, N-[4-(1-naphthalenyl)phenyl]-4-Dibenzothiophenamine was used instead of 4-(1-naphthalenyl)-N-[4-(1-naphthalenyl)phenyl]-benzenamine. Except for the above, compound 81 was synthesized in the same manner as in the synthesis of compound 53. The molecular weight of the compound measured by FAB-MS measurement was 680. In addition, the chemical shift values of the compounds measured by ¹ H-NMR measurement were 8.46-8.37 (m, 4H), 8.33 (dd, 2H), 8.28 (d, 4H), 8.23-8.15 (m, 5H) ), 8.11 (d, 2H), 8.00–7.89 (m, 11H), and 7.47–7.33 (m, 5H). Through the above results, it was confirmed that the synthesized compound was Compound 81.

10. Synthesis of Compound 84

In the above synthesis method of compound 53, N-[4-(1-naphthalenyl)phenyl]-1-Dibenzofuranamine was used instead of 4-(1-naphthalenyl)-N-[4-(1-naphthalenyl)phenyl]-benzenamine. Except for the above, compound 84 was synthesized in the same manner as in the synthesis of compound 53. The molecular weight of the compound measured by FAB-MS measurement was 664. In addition, the chemical shift values of the compounds measured by ¹ H-NMR measurement were 8.42-8.37 (m, 4H), 8.33 (dd, 2H), 8.26 (d, 4H), 8.20-8.14 (m, 5H) ), 8.11 (d, 2H), 7.99–7.89 (m, 6H), and 7.55–7.40 (m, 10H). Through the above results, it was confirmed that the synthesized compound was Compound 84.

11. Synthesis of Compound 92

In the above-described method for synthesizing compound 53, the synthesis of compound 53 and Compound 92 was synthesized in the same manner. The molecular weight of the compound measured by FAB-MS measurement was 660. In addition, the chemical shift values of the compounds measured by ¹ H-NMR measurement were 8.42-8.37 (m, 7H), 8.31 (d, 2H), 8.19 (d, 2H), 7.99 (d, 2H), 7.81-7.60 (m, 6H) and 7.45-7.20 (m, 10H). Through the above results, it was confirmed that the synthesized compound was Compound 92.

12. Synthesis of Compound 105

Compound 105 was synthesized in the same manner as in the synthesis of Compound 81, except that 1-Iodo-3-bromobenzene was used instead of 1-Iodo-4-bromobenzene in the synthesis method of Compound 81 described above. The molecular weight of the compound measured by FAB-MS measurement was 679. In addition, the chemical shift values of the compounds measured by ¹ H-NMR measurement were 8.18-8.11 (m, 1H), 8.07-7.97 (m, 2H), 7.95-7.73 (m, 5H), 7.56-7.29 (m, 14H), 7.23-7.04 (m, 6H), 7.04-6.81 (m, 4H), and 6.73-6.61 (m, 1H). Through the above results, it was confirmed that the synthesized compound was Compound 105.

13. Synthesis of Compound 77

In the synthesis of compound 53, 1-Naphthylboronic acid was used instead of Phenylboronic acid, and N-(4-(naphthalen-1-yl)phenyl)-[ Compound 77 was synthesized in the same manner except for using 1,1'-biphenyl]-4-amine.

The molecular weight of compound 77 determined according to FAB-MS measurement was 699.

The synthesis example described above is an example, and reaction conditions may be changed as needed. In addition, the compound according to one embodiment of the present invention can be synthesized to have various substituents using methods and materials known in the art. By introducing various substituents into the core structure represented by Formula 1, it can have properties suitable for use in organic electroluminescent devices.

(Example of device creation)

Organic electroluminescent devices of Examples 1 to 13 were fabricated using compounds 4, 5, 21, 46, 53, 59, 66, 75, 81, 84, 92, 105 and 77 as materials for the second hole transport layer. .

[Example compound]

Organic electroluminescent devices of Comparative Examples 1 to 7 were manufactured using the following Comparative Examples Compounds X-1 to X-7 as materials for the second hole transport layer.

[Comparative Example Compound]

In the organic electroluminescent devices of Examples 1 to 13 and Comparative Examples 1 to 7, a 150 nm thick first electrode was formed of ITO, a 10 nm thick hole injection layer doped with 2% HIL was formed on HT1, and a 120 nm thick hole injection layer was formed on HT1. A first hole transport layer having a thickness was formed, a second hole transport layer having a thickness of 30 nm was formed using an example compound or a compound of a comparative example, a light emitting layer having a thickness of 30 nm in which BH was doped with BD by 3%, and a thickness of 10 nm was formed with ET1. A first electron transport layer was formed, a 20 nm thick second electron transport layer was formed of ET2, a 1 nm thick electron injection layer was formed of LiF, and a 100 nm thick second electrode was formed of a 10% Ag/Mg alloy. Each layer was formed by vapor deposition in a vacuum atmosphere.

Each material applied to the device is as follows.

(experimental example)

Driving of the organic electroluminescent device prepared with the above-described Example Compounds 4, 5, 21, 46, 53, 59, 66, 75, 81, 84, 92, 105, 77 and Comparative Example Compounds X-1 to X-7 Voltage, lifetime, luminous efficiency, and color coordinates were evaluated. The evaluation results are shown in Table 1 below. The driving voltage of each Example and Comparative Example is a measured value at a current density of 10 mA/cm ² , and the lifespan is a luminance half-life time from an initial luminance of 1000 cd/m ² at a current density of 1.0 mA/cm ² .

Element creation example hole transport layer drive voltage
(V) life span
LT ₅₀ (h) luminous efficiency
(cd/A) color coordinates
CIE(x,y) Example 1 Example compound 4 4.5 182 5.3 0.140, 0.051 Example 2 Example compound 5 4.7 189 5.1 0.142, 0.051 Example 3 Example compound 21 4.7 183 5.4 0.140, 0.052 Example 4 Example compound 46 4.6 193 5.1 0.140, 0.051 Example 5 Example compound 53 4.8 211 4.8 0.140, 0.051 Example 6 Example compound 59 4.7 203 4.9 0.141, 0.050 Example 7 Example compound 66 4.8 209 4.8 0.140, 0.051 Example 8 Example compound 75 4.9 207 4.9 0.140, 0.051 Example 9 Example compound 81 4.8 210 4.9 0.140, 0.051 Example 10 Example compound 84 4.9 196 5.1 0.140, 0.051 Example 11 Example compound 92 4.9 195 5.0 0.140, 0.051 Example 12 Example compound 105 4.8 187 5.1 0.140, 0.051 Example 13 Example compound 77 4.7 218 4.8 0.140, 0.051 Comparative Example 1 Comparative Example Compound X-1 4.9 163 3.9 0.140, 0.052 Comparative Example 2 Comparative Example Compound X-2 4.9 160 3.8 0.141, 0.051 Comparative Example 3 Comparative Example Compound X-3 4.8 164 3.9 0.141, 0.052 Comparative Example 4 Comparative Example Compound X-4 5.1 161 4.0 0.140, 0.051 Comparative Example 5 Comparative Example Compound X-5 4.8 163 4.1 0.140, 0.053 Comparative Example 6 Comparative Example Compound X-6 5.1 160 4.1 0.141, 0.051 Comparative Example 7 Comparative Example Compound X-7 5.0 163 4.0 0.141, 0.051

Referring to the results of Table 1, it can be seen that in Examples 1 to 13, compared to Comparative Examples 1 to 7, driving voltage was reduced and device life and luminous efficiency were improved. Examples 1 to 13 include an amine compound containing a naphthyl group in which the 1st and 8th carbon positions are substituted in the hole transport layer, so that heat and charge resistance are improved while maintaining the characteristics of amine, and thus high heat and Characteristic deterioration due to electric charge is reduced, and long life is achieved. In addition, since crystallization is suppressed by the large volume of the substituted naphthyl group and the film quality of the hole transport layer can be improved, hole transport properties are improved, resulting in low driving voltage and high efficiency.

Examples 1 to 4 and Example 12, including Example Compounds 4, 5, 21, 46, and 105 in which the linker connecting the amine group and the substituted naphthyl group is an m-phenylene group, exhibited a greater improvement in luminous efficiency. This is considered to be because the amine group and the substituted naphthyl group are connected through the m-phenylene group, so that the overall volume of the molecule is increased and the film quality is greatly improved accordingly.

Examples 5 to 11 including Example Compounds 53, 59, 66, 75, 81, 84, 92, and 77 in which the linker connecting the amine group and the substituted naphthyl group is a p-phenylene group, and Examples 11 and 13 have longer device lifetimes. Greatly improved. When connected through the p-phenylene group, the phenyl group substituted with the naphthyl group and the phenylene group as the linker are arranged in the same direction, and thus spatial overlap occurs between the orbitals of the phenyl group and the orbitals of the phenylene group, thereby forming a through-space mutual It is thought that this is because the state of the radical was stabilized by the action.

In Comparative Examples 1 to 3, Comparative Examples Compounds X-1 to X-3 constituting the hole transport layer each contain a naphthyl group, and are connected to an amine group at the 1st carbon position of the naphthyl group through a linker, but an aryl group at the 8th carbon position Since the group is not substituted, the heat and charge resistance is inferior to that of the Example compounds. Accordingly, the driving voltage increases, and the device lifetime and luminous efficiency decrease.

Comparative Example 4 includes a naphthyl group having substitution positions at carbons 1 and 8 of Comparative Example Compound X-4 constituting the hole transport layer, but dibenzofuranyl group, which is a polycyclic heteroaryl group, is substituted at carbon 8 of the naphthyl group. there is. As a result, the volume of the compound becomes very large, decomposition easily occurs, and the hole propagation speed decreases due to the large molecular distance, so the luminous efficiency and device lifespan are lower than those of the embodiment.

Comparative Examples 5 and 6 include a naphthyl group in which the aryl group is substituted in Comparative Example compounds X-5 and X-6 constituting the hole transport layer, but the substitution position of the aryl group in the naphthyl group is not at the 8th carbon position, but at positions 2 and 7 is the number position. Comparative Examples Compounds X-5 and X-6 did not have an aryl group substituted at the position of carbon 8, which is the active point of the naphthyl group, and therefore had poor charge tolerance compared to the compounds of Examples, and thus Comparative Examples 5 and 6 were The luminous efficiency and lifetime of the device are inferior to those of the other devices.

Comparative Examples 4 and 7 use a compound in which a portion corresponding to Ar ₃ in Formula 1 is a heteroaryl group, and is inferior in luminous efficiency and device life compared to Examples 1 to 13. Examples 4 and 7 also use a compound containing a heteroaryl group, but show differences in efficiency due to structural differences. More specifically, in the case of Comparative Examples 4 and 7, relatively unstable heteroaryl groups are separated so as to be located at positions 1 and 8, respectively, with the aryl amine group and naphthalene interposed therebetween, and due to this structure, heteroaryl by nitrogen of the aryl amine group It can be seen that the stabilizing effect of the group is not sufficient, and as a result, the efficiency is lowered.

Although the embodiments of the present invention have been described with reference to the accompanying drawings, those skilled in the art can implement the present invention in other specific forms without changing its technical spirit or essential features. You will understand that there is Therefore, it should be understood that the embodiments described above are illustrative in all respects and not restrictive.

10: organic electroluminescent element EL1: first electrode
HTR: hole transport region EML: light emitting layer
ETR: electron transport region EL2: second electrode
HTL: hole transport layer HTL1: first hole transport layer
HTL2: second hole transport layer

Claims (23)

a first electrode;
a hole transport region disposed on the first electrode;
a light emitting layer disposed on the hole transport region;
an electron transport region disposed on the light emitting layer; and
a second electrode disposed on the electron transport region;
The hole transport region comprises an amine compound represented by Chemical Formula 1:
[Formula 1]

In Formula 1,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aryl group having 6 or more and 30 or less ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 or more and 30 or less ring carbon atoms,
Ar ₃ is a substituted or unsubstituted aryl group having 6 or more and 20 or less ring carbon atoms;
When Ar ₃ is substituted, the substituent is at least one of heavy hydrogen, a halogen atom, a silyl group, an alkyl group, and an aryl group;
At least one of Ar ₁ and Ar ₂ is the heteroaryl group, or at least one of Ar ₁ and Ar ₂ includes a polycyclic ring;
L ₁ is a substituted or unsubstituted arylene group having 6 or more and 30 or less ring carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 or more and 30 or less ring carbon atoms. According to claim 1,
wherein L ₁ is a substituted or unsubstituted phenylene group, a substituted or unsubstituted divalent biphenyl group, a substituted or unsubstituted dibenzofuranylene group, or a substituted or unsubstituted dibenzothiophenylene group. According to claim 1,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthylphenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, A substituted or unsubstituted phenanthryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group. According to claim 1,
At least one of Ar ₁ and Ar ₂ is a substituted or unsubstituted naphthylphenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted An organic electroluminescent device that is a cyclic dibenzothiophenyl group. According to claim 1,
Formula 1 is an organic electroluminescent device represented by Formula 1-1:
[Formula 1-1]

In Formula 1-1,
Ar ₄ is a substituted or unsubstituted aryl group having 6 or more and 20 or less ring carbon atoms;
Ar ₁ , Ar ₃ , and L ₁ are the same as defined in claim 1. According to claim 1,
Formula 1 is an organic electroluminescent device represented by Formula 1-2:
[Formula 1-2]

In Formula 1-2,
Y ₁ and Y ₂ are each independently a hydrogen atom, a deuterium atom, a halogen atom, an alkyl group, or an aryl group, or may combine with adjacent groups to form a ring;
m1 and m2 are each independently an integer of 0 or more and 5 or less,
Ar ₁ and L ₁ are the same as defined in claim 1. According to claim 1,
Formula 1 is an organic electroluminescent device represented by Formula 1-3:
[Formula 1-3]

In Formula 1-3,
X ₁ is O or S;
Ar ₂ , Ar ₃ , and L ₁ are the same as defined in claim 1. According to claim 1,
Chemical Formula 1 is an organic electroluminescent device represented by Chemical Formulas 1-4:
[Formula 1-4]

In Chemical Formulas 1-4,
X ₁ and X ₂ are each independently O or S;
Ar ₃ and L ₁ are the same as defined in claim 1. According to claim 1,
An organic electroluminescent device wherein the amine compound represented by Formula 1 is at least one selected from compounds represented by compound group 4 below:
[Compound group 4]

. According to claim 1,
An organic electroluminescent device wherein the amine compound represented by Formula 1 is at least one selected from compounds represented by compound group 5 below:
[Compound group 5]

. According to claim 1,
The hole transport region is
a hole injection layer disposed on the first electrode; and
A hole transport layer disposed on the hole injection layer;
The hole transport layer is
An organic electroluminescent device comprising the amine compound. According to claim 11,
The hole transport layer is an organic electroluminescent device in contact with the light emitting layer. According to claim 1,
The hole transport region is
a hole injection layer disposed on the first electrode;
a first hole transport layer disposed on the hole injection layer; and
a second hole transport layer disposed on the first hole transport layer and adjacent to the light emitting layer;
The second hole transport layer is
An organic electroluminescent device comprising the amine compound. An amine compound represented by Formula 1 below:
[Formula 1]

In Formula 1,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted aryl group having 6 or more and 30 or less ring carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 or more and 30 or less ring carbon atoms,
Ar ₃ is a substituted or unsubstituted aryl group having 6 to 20 ring carbon atoms;
When Ar ₃ is substituted, the substituent is at least one of heavy hydrogen, a halogen atom, a silyl group, an alkyl group, and an aryl group;
At least one of Ar ₁ and Ar ₂ is the heteroaryl group, or at least one of Ar ₁ and Ar ₂ includes a polycyclic ring;
L ₁ is a substituted or unsubstituted arylene group having 6 or more and 30 or less ring carbon atoms, or a substituted or unsubstituted heteroarylene group having 2 or more and 30 or less ring carbon atoms. According to claim 14,
wherein L ₁ is a substituted or unsubstituted phenylene group, a substituted or unsubstituted divalent biphenyl group, a substituted or unsubstituted dibenzofuranylene group, or a substituted or unsubstituted dibenzothiophenylene group. According to claim 14,
Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthylphenyl group, a substituted or unsubstituted biphenyl group, a substituted or unsubstituted terphenyl group, a substituted or unsubstituted naphthyl group, An amine compound that is a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted dibenzothiophenyl group. According to claim 14,
At least one of Ar ₁ and Ar ₂ is a substituted or unsubstituted naphthylphenyl group, a substituted or unsubstituted phenanthryl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted dibenzofuranyl group, or a substituted or unsubstituted An amine compound that is a cyclic dibenzothiophenyl group. According to claim 14,
Formula 1 is an amine compound represented by the following Formula 1-1:
[Formula 1-1]

In Formula 1-1,
Ar ₄ is a substituted or unsubstituted aryl group having 6 or more and 20 or less ring carbon atoms;
Ar ₁ , Ar ₃ , and L ₁ are the same as defined in claim 14. According to claim 14,
Formula 1 is an amine compound represented by Formula 1-2 below:
[Formula 1-2]

In Formula 1-2,
Y ₁ and Y ₂ are each independently a hydrogen atom, a deuterium atom, a halogen atom, an alkyl group, or an aryl group, or may combine with adjacent groups to form a ring;
m1 and m2 are each independently an integer of 0 or more and 5 or less,
Ar ₁ and L ₁ are the same as defined in claim 14. According to claim 14,
Formula 1 is an amine compound represented by Formula 1-3 below:
[Formula 1-3]

In Formula 1-3,
X ₁ is O or S;
Ar ₂ , Ar ₃ , and L ₁ are the same as defined in claim 14. According to claim 14,
Formula 1 is an amine compound represented by the following Formula 1-4:
[Formula 1-4]

In Chemical Formulas 1-4,
X ₁ and X ₂ are each independently O or S;
Ar ₃ , and L ₁ are the same as defined in claim 14. According to claim 14,
The amine compound represented by Formula 1 is any one selected from the compounds represented by Compound Group 4 below:
[Compound group 4]

. According to claim 14,
The amine compound represented by Formula 1 is any one selected from the compounds represented by compound group 5 below:
[Compound group 5]

.

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