KR102099171B1 - Aryl amine derivatieves and organic electroluminescent device including the same - Google Patents

Abstract

(상기 화학식 1에서 각 치환기들의 정의는 발명의 상세한 설명에서 정의한 바와 같다.)It provides an arylamine derivative that effectively absorbs a high-energy external light source in the UV region and minimizes damage to organic substances inside the organic electroluminescent device, thereby contributing to a substantial improvement in the lifetime of the organic electroluminescent device.
The organic electroluminescent device according to the present invention includes a first electrode and a second electrode; And one or more organic material layers disposed between the first electrode and the second electrode, and the organic material layer includes an arylamine derivative represented by Formula 1 below.
[Formula 1]

(In Formula 1, the definition of each substituent is as defined in the detailed description of the invention.)

Description

Aryl amine derivative and organic electroluminescent device including the same

The present invention relates to an organic light emitting display device including a capping layer having both high refractive index characteristics and ultraviolet absorption characteristics, and more particularly, to an organic electroluminescent device including an aryl amine derivative in an organic material layer or a capping layer.

From the CRT (Cathode Ray Tube), which was the dominant type of the early display industry, to the currently used LCD (Liquid Crystal Display), the display industry has developed remarkably in the past few decades.

Nevertheless, with the recent increase in the size of the display device, there is an increasing demand for a flat display device having a small space occupancy, and the LCD has a disadvantage that a viewing angle is limited and a separate light source is required because it is not a self-emission type. For this reason, OLEDs (Organic Light Emitting Diodes) are attracting attention as a display using a self-luminous phenomenon.

OLED was first attempted by Pope et al. In 1963 to study carrier injection-type electroluminescence (EL) using single crystals of anthracene aromatic hydrocarbons. From these studies, charge injection, recombination, exciton generation, luminescence, etc. from organic materials were attempted. A lot of understanding and research has been started on the basic mechanism and electroluminescence properties of.

In addition, since Tang and Van Slyke reported high-efficiency characteristics using a multilayer thin film structure of an organic electroluminescent device in 1987 [Tang, C. W., Van Slyke, S. A. Appl. Phys. Lett. 51, 913 (1987)], OLED has been in the spotlight as it has excellent characteristics as a next-generation display and has high potential for use in LCD backlight and lighting [Kido, J., Kimura, M., and Nagai, K., Science 267, 1332 (1995)]. In particular, various approaches, such as device structural changes and material development, have been made to increase luminous efficiency [Sun, S., Forrest, S. R., Appl. Phys. Lett. 91, 263503 (2007) / Ken-Tsung Wong, Org. Lett., 7, 2005, 5361-5364].

The basic structure of OLED displays is generally anode, hole injection layer (HIL), hole transporting layer (HTL), emission layer (EML), electron transport layer (ETL) ), And a multilayer structure of a cathode, and an electronic organic multilayer film (organic layer) has a sandwich structure formed between both electrodes.

In general, the organic light emitting phenomenon refers to a phenomenon that converts electrical energy into light energy using organic materials. An organic electroluminescent device using an organic light emitting phenomenon usually has a structure including an anode and a cathode and an organic material layer between them. Here, in order to increase the efficiency and stability of the organic electroluminescent device, the organic material layer is often composed of a multi-layer structure composed of different materials, for example, may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like . When a voltage is applied between two electrodes in the structure of the organic electroluminescent device, holes are injected at the anode and electrons are injected at the cathode into the organic material layer, and excitons are formed when the injected holes meet the electrons. It glows when it falls to the ground. It is known that such an organic electroluminescent device exhibits characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high-speed response.

Materials used as the organic material layer in the organic electroluminescent device may be classified into light emitting materials and charge transport materials, such as hole injection materials, hole transport materials, electron transport materials, and electron injection materials, depending on their function. The light emitting materials include blue, green, and red light emitting materials depending on the light emitting color, and yellow and orange light emitting materials necessary for realizing a better natural color. In addition, a host / dopant system may be used as a light emitting material in order to increase color purity and increase light emission efficiency through energy transfer. The principle is that when a small amount of a dopant having a smaller energy band gap and superior luminous efficiency is mixed with a light emitting layer than a host mainly constituting the light emitting layer, excitons generated from the host are transported to the dopant to emit light with high efficiency. At this time, since the wavelength of the host moves to the wavelength of the dopant, light of a desired wavelength can be obtained according to the type of dopant used.

Recently, materials that form an organic material layer in the device sufficiently to sufficiently exhibit the excellent characteristics of the above-described organic electroluminescent device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc. have been developed. Performance is recognized by commercialized products.

However, as the commercialization of the organic electroluminescent device is achieved and over time, the need for other properties has emerged in addition to the luminescent properties of the organic electroluminescent device itself. In many cases, the organic electroluminescent device is exposed to an external light source for a long time, and as a result, the environment exposed to ultraviolet light having high energy continues to affect the organic materials constituting the organic electroluminescent device. In order to prevent exposure to such a high energy light source, a problem can be solved by applying a capping layer having infrared absorption characteristics.

Additionally, it is generally known that the viewing angle characteristic of an organic electroluminescent device is wide, but from a light source spectrum viewpoint, a considerable deviation occurs depending on the viewing angle, which is the total refractive index and organic electroluminescence of glass substrates, organic materials, electrode materials, etc. constituting the organic electroluminescent device. This is achieved by deviation from the appropriate refractive index value according to the light emission wavelength of the device.

In general, the higher the required refractive index value of blue and the longer the wavelength, the smaller the required refractive index value. Accordingly, it is necessary to develop a material forming a capping layer that satisfies the above-mentioned infrared absorption characteristics and an appropriate refractive index at the same time.

The efficiency of an organic electroluminescent device can be generally divided into internal luminescent efficiency and external luminous efficiency. The internal luminous efficiency is related to how efficiently excitons are formed in the organic layer to perform light conversion, and the external luminous efficiency refers to the efficiency in which light generated in the organic layer is emitted outside the organic electroluminescent element.

In order to improve the overall efficiency, it is necessary to increase the external luminous efficiency as well as the internal luminous efficiency. In order to increase the external luminous efficiency and prevent various problems that may be caused when exposed to daylight for a long time, a new functional capping layer (CPL) compound is to be developed. In particular, we intend to focus on the development of capping layer (CPL) materials that have excellent ability to absorb light in the UV wavelength range among CPL functions.

Republic of Korea Patent Publication No. 2016-0062307 (Name of the invention: an organic light emitting display device including a high refractive index capping layer)

An object of the present invention is to provide a capping layer material for an organic electroluminescent device that can improve luminous efficiency and lifespan and at the same time help to improve viewing angle characteristics.

Another object of the present invention is to provide an organic electroluminescent device using a capping layer using the capping layer material.

An embodiment of the present invention includes a first electrode, an organic material layer disposed on the first electrode, and a second electrode disposed on the organic material layer; And a capping layer disposed on the second electrode, wherein the organic material layer and / or the capping layer provides an organic electroluminescent device including an aryl amine derivative represented by Formula 1 below.

[Formula 1]

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In Chemical Formula 1,
Z ₁ and Z ₂ are each independently O, S or NR ₅ ,
Ar ₁ and Ar ₂ are each independently an alkyl group having 1 to 4 carbon atoms, a deuterium substituted alkyl group, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,
R ₁ , R ₂ , R _3, R ₄ and R ₅ are each independently hydrogen atom, deuterium atom, halogen atom, deuterium substituted alkyl group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted Ring-forming hydrocarbon ring group having 5 to 20 carbon atoms, substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, alkoxy, aryloxy group, cyano group, amino group, substituted or unsubstituted silyl group, alkenyl group, heteroake Nyl group, alkynyl group, unsaturated hydrocarbon ring group, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, acyl group, carbonyl group, carbo group Nilic acid group, carbonyl ester group, nitrile group, isonitrile group, sulfanyl group, sulfinyl group, sulfonyl group, phosphino group, substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, substituted or unsubstituted monovalent ratio - Hyangjok hetero condensed polycyclic group, or, it is possible to form a ring group bonded to or adjacent, n ₁ to n ₄ are each independently an integer of 0 to 4.

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The organic material layer of the organic electroluminescent device includes a hole transport region, a light emitting layer disposed on the hole transport region, and an electron transport region disposed on the light emitting layer.

The organic electroluminescent device including the capping layer according to the present invention exhibits ultraviolet absorption characteristics, and thus the organic electroluminescent field by external light sources Damage to organic substances in the light emitting device can be minimized, and accordingly, the organic electric field The intrinsic efficiency and life span of the light emitting device can be induced to be maintained as much as possible.

In addition, the organic electric field of the present invention The light-emitting device can improve the light efficiency, reduce the half-width of the emission spectrum, and improve the viewing angle characteristics by using a capping layer. It can satisfy various required characteristics of the light emitting device.

1 is an organic electric field according to an embodiment of the present invention It is a sectional view schematically showing a light emitting element.
2 is a graph of light refraction and absorption characteristics when using an arylamine derivative according to an embodiment of the present invention.

The present invention can be applied to various changes and may have various forms, and specific embodiments will be illustrated in the drawings and described in detail in the text. However, this is not intended to limit the present invention to a specific disclosure form, and it should be understood that all modifications, equivalents, and substitutes included in the spirit and scope of the present invention are included.

In describing each drawing, similar reference numerals are used for similar components. In the accompanying drawings, the dimensions of the structures are shown to be enlarged than the 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. The terms are used only for the purpose of distinguishing one component from other components. For example, the first component may be referred to as a second component without departing from the scope of the present invention, and similarly, the second component may be referred to as a first component. Singular expressions include plural expressions unless the context clearly indicates otherwise.

In this application, terms such as “include” or “have” are intended to indicate that a feature, number, step, operation, component, part, or combination thereof described on the specification exists, and that one or more other features are present. It should be understood that the existence or addition possibilities of fields or numbers, steps, actions, components, parts or combinations thereof are not excluded in advance. 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 "directly above" the other part but also another part in the middle.

In the present specification, “substituted or unsubstituted” refers to a deuterium atom, a halogen atom, a cyano group, a nitro group, an amino group, a hydroxy group, a silyl group, a boron group, a phosphine oxide group, a phosphine sulfide group, an alkyl group, an alkoxy group, and an alke. It may mean substituted or unsubstituted with one or more substituents selected from the group consisting of a nil group, an aryl group, a hetero aryl group and a hetero ring group. In addition, each of the exemplified substituents 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, examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.

In the present specification, the alkyl group may be straight chain, branched chain, or cyclic. The alkyl group has 1 to 50 carbon atoms, 1 to 30 carbon atoms, 1 to 20 carbon atoms, 1 to 10 carbon atoms, or 1 to 6 carbon atoms. Examples of the alkyl group are 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-octyl Tildedecyl 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-nonade Real group, n-icosyl group, 2-ethyl isosilyl group, 2-butyl isosilyl group, 2-hexyl isosilyl group, 2-octyl isosilyl group, n-henicosyl group, n-docosyl group, n-tricosyl group, n-tetra A cosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacyl group, and n-triacontyl group, and the like, but is not limited to these. .

As used herein, a hydrocarbon ring group means any functional group or substituent derived from an aliphatic hydrocarbon ring. The hydrocarbon ring group may be a saturated hydrocarbon ring group having 5 to 20 ring carbon atoms.

As used herein, 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 ring-forming carbon number of 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 quarterphenyl group, a quenkyphenyl group, a sexy phenyl group, a triphenylenyl group, a pyrenyl group, a perylene group, a naphtha group Although a enyl group, a pyrenyl group, a benzo fluoranthenyl group, 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 combine with each other to form a spiro structure. In the present specification, the heteroaryl group may be a heteroaryl group including one or more of O, N, P, Si and S as heterogeneous elements. The N and S atoms can be oxidized in some cases, and the N atom (s) can be quaternized in some cases. The number of ring-forming carbon atoms of the heteroaryl group is 2 or more and 30 or less, or 2 or more and 20 or less. The heteroaryl group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group. The polycyclic heteroaryl group may have, for example, a bicyclic or tricyclic structure.

Examples of the heteroaryl group include thiophene group, furan group, pyrrol group, imidazole group, pyrazolyl group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridine group, bipyridine group, pyrimidine group, and triazine group , Tetrazin group, triazole group, tetrazol group, acridil group, pyridazine group, pyrazinyl group, quinoline group, quinazoline group, quinoxaline group, phenoxazine group, phthalazine group, pyrido pyrimidine group, pyrido pyrazino Pyrazine group, isoquinoline group, cinnaoli group, indole group, isoindole group, indazole group, carbazole group, N-aryl carbazole group, N-heteroaryl carbazole group, N-alkyl carbazole group, benzoxazole group, benzoimidazole group , Benzothiazole group, benzocarbazole group, benzothiophene group, benzothiophene group, benzoisothiazolyl, benzoisoxazolyl, dibenzothiophene group, thienothiophene group, benzofuran group, phenanthroline group, phenanthridine group , Thiazole group, isooxazole group, oxadiazole group, thiadiazole group, iso Thiazole group, isoxazole group, phenothiazine group, benzodioxol group, dibenzosilol group and dibenzofuran group, isobenzofuran group, and the like, but is not limited thereto. In addition, there are N-oxide aryl groups corresponding to the monocyclic hetero aryl group or polycyclic hetero aryl group, for example, quaternary salts such as pyridyl N-oxide group, quinolyl N-oxide group, and the like. It is not limited.

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

In the present 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, trimethyl boron group, triethyl boron group, t-butyldimethyl boron group, triphenyl boron group, diphenyl boron group, phenyl boron group, and the like.

In the present specification, the alkenyl group may be straight chain or branched chain. The number of carbon atoms 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, vinyl groups, 1-butenyl groups, 1-pentenyl groups, 1,3-butadienyl aryl groups, styrenyl groups, styryl vinyl groups, and the like.

In the present specification, “adjacent group” may mean a substituent substituted on an atom directly connected to an atom in which the substituent is substituted, another substituent substituted on an atom in which the substituent is substituted, or a substituent that is structurally closest to the substituent. have. For example, two methyl groups in 1,2-dimethylbenzene (1,2-dimethylbenzene) can be interpreted as “adjacent groups”, and 2 in 1,1-diethylcyclopentene (1,1-diethylcyclopentene). Dog ethyl groups can be interpreted as "adjacent groups" to each other.

Hereinafter, embodiments of the present invention will be described with reference to FIGS. 1 and 2.

1 is a cross-sectional view schematically showing an organic electroluminescent device according to an embodiment of the present invention. 1, an organic electric field according to an embodiment The light emitting device includes a first electrode 110 sequentially stacked on a substrate 100, a hole injection layer 210, a hole transport layer 215, a light emitting layer 220, an electron transport layer 230, an electron injection layer 235, The second electrode 120 and the capping layer 300 may be included.

The first electrode 110 and the second electrode 120 are disposed to face each other, and the organic material layer 200 may be disposed between the first electrode 110 and the second electrode 120. The organic material layer 200 may include a hole injection layer 210, a hole transport layer 215, a light emitting layer 220, an electron transport layer 230, and an electron injection layer 235.

On the other hand, the capping layer 300 presented in the present invention is a functional layer deposited on the second electrode 120, and includes a compound according to the formula of the present invention.

In the organic electroluminescent device of the embodiment illustrated in FIG. 1, the first electrode 110 has conductivity. The first electrode 110 may be formed of a metal alloy or a conductive compound. The first electrode 110 is generally an anode, but the function as an electrode is not limited.

The first electrode 110 may be formed by depositing an electrode material on the substrate 100 using an evaporation method, electron beam evaporation, or sputtering method. The material of the first electrode 110 may be selected from materials having a high work function to facilitate injection of holes into the organic EL device.

The capping layer 300 proposed in the present invention is applied when the emission direction of the organic electroluminescent device is front emission, so the first electrode 110 uses a reflective electrode. These materials include Mg (magnesium), Al (aluminum), Al-Li (aluminum-lithium), Ca (calcium), Mg-In (magnesium-indium), Mg-Ag (magnesium-silver), and not oxides. It can also be produced using the same metal. Recently, carbon substrate flexible electrode materials such as CNT (carbon nanotube) and graphene (graphene) may be used.

The organic material layer 200 may be formed of a plurality of layers. When the organic material layer 200 is a plurality of layers, the organic material layer 200 includes a hole transport region 210 to 215 disposed on the first electrode 110, a light emitting layer 220 disposed on the hole transport region, and the light emitting layer The electron transport regions 230 to 235 disposed on the 220 may be included.

The capping layer 300 of one embodiment includes an organic compound represented by Formula 1, which will be described later.

The hole transport regions 210 to 215 are provided on the first electrode 110. The hole transport regions 210 to 215 may include at least one of a hole injection layer 210, a hole transport layer 215, a hole buffer layer, and an electron blocking layer (EBL), and smooth hole injection and transport into the organic electroluminescent device It plays the role of and has a thicker thickness than the electron transport region because hole mobility is generally faster than electron mobility.

The hole transport regions 210 to 215 may have a single layer made of a single material, a single layer made of a plurality of different materials, or a multi-layer structure having a plurality of layers made of a plurality of different materials.

For example, the hole transport regions 210 to 215 may have a single layer structure of the hole injection layer 210 or the hole transport layer 215, or may have a single layer structure made of a hole injection material and a hole transport material. have. In addition, the hole transport regions 210 to 215 have a single layer structure made of a plurality of different materials, or a hole injection layer 210 / a hole transport layer 215 sequentially stacked from the first electrode 110, Hole injection layer 210 / hole transport layer 215 / hole buffer layer, hole injection layer 210 / hole buffer layer, hole transport layer 215 / hole buffer layer, or hole injection layer 210 / hole transport layer 215 / electron Although it may have a structure of a blocking layer (EBL), the embodiment is not limited thereto.

The hole injection layer 210 of the hole transport regions 210 to 215 may be formed by various methods such as a vacuum deposition method, a spin coating method, a cast method, and an LB method over the anode. When the hole injection layer 210 is formed by a vacuum deposition method, the deposition conditions are 100 to 500 depending on the compound used as the hole injection layer 210 material, the structure and thermal properties of the target hole injection layer 210, and the like. The deposition rate can be adjusted at about 1 kPa / s at ℃, and is not limited to specific conditions. When the hole injection layer 210 is formed by the spin coating method, the coating conditions differ depending on the properties between the compound used as the hole injection layer 210 and the layers formed at the interface, but the coating speed and coating for uniform film formation After that, heat treatment for solvent removal is necessary.

The hole transport regions 210 to 215 are, for example, m-MTDATA, TDATA, 2-TNATA, NPB, β-NPB, TPD, Spiro-TPD, Spiro-NPB, methylated-NPB, TAPC, HMTPD, TCTA (4,4 ', 4 "-tris (N-carbazolyl) triphenylamine (4,4', 4" -tris (Ncarbazolyl) triphenylamine)), Pani / DBSA (Polyaniline / Dodecylbenzenesulfonic acid: polyaniline / dodecylbenzene Sulfonic acid), PEDOT / PSS (Poly (3,4-ethylenedioxythiophene) / Poly (4-styrene sulfonate): poly (3,4-ethylenedioxythiophene) / poly (4-styrenesulfonate)), Pani / CSA ( Polyaniline / Camphor sulfonic acid: polyaniline / camphorsulfonic acid), Pani / PSS (Polyaniline) / Poly (4-styrenesulfonate): polyaniline / poly (4-styrenesulfonate), and the like.

The hole transport regions 210 to 215 may have a thickness of about 100 to about 10,000 mm 2, and corresponding organic material layers of each hole transport region 210 to 215 are not limited to the same thickness. For example, when the thickness of the hole injection layer 210 is 50Å, the thickness of the hole transport layer 215 may be 1000Å and the thickness of the electron blocking layer 500Å. The thickness condition of the hole transport regions 210 to 215 may be determined to a degree that satisfies efficiency and life within a range in which the increase in driving voltage of the organic electroluminescent device does not increase. The organic material layer 200 includes a hole injection layer 210, a hole transport layer 215, a functional layer having a hole injection function and a hole transport function at the same time, a buffer layer, an electron blocking layer, a light emitting layer 220, a hole blocking layer, and an electron transport layer ( 230), an electron injection layer 235, and one or more layers selected from the group consisting of a functional layer having an electron transport function and an electron injection function at the same time.

The hole transport regions 210 to 215 may use doping to improve properties, as in the light emitting layer 220, and doping of the charge-generating material into the hole transport regions 210 to 215 improves the electrical properties of the organic EL device. I can do it.

The charge-generating material is generally made of a material having very low HOMO and LUMO, for example, the LUMO of the charge-generating material has a value similar to that of the hole transport layer 215 material. Due to the low LUMO, electrons of the LUMO are easily transferred to the adjacent hole transport layer 215 by using an empty property, thereby improving electrical characteristics.

The charge-generating material can be, for example, a p-dopant. The p-dopant may be one of quinone derivatives, metal oxides, and cyano group-containing compounds, but is not limited thereto. For example, non-limiting examples of the p-dopant include tetracyanoquinone dimethane (TCNQ) and 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinonedimethe Quinone derivatives such as phosphorus (F ₄ -TCNQ); Metal oxides such as tungsten oxide and molybdenum oxide; And cyano group-containing compounds such as the following compounds 3-22 and the like, but are not limited thereto.

The hole transport regions 210 to 215 may further include a charge generating material to improve conductivity, in addition to the aforementioned materials.

The charge generating material may be uniformly or non-uniformly dispersed in the hole transport regions 210 to 215.

The charge generating material can be, for example, a p-dopant. The p-dopant may be one of quinone derivatives, metal oxides, and cyano group-containing compounds, but is not limited thereto. For example, non-limiting examples of p-dopants include metal oxides such as quinone derivatives such as Tetracyanoquinodimethane (TCNQ) and F ₄ -TCNQ (2,3,5,6-tetrafluoro-tetracyanoquinodimethane), tungsten oxide, and molybdenum oxide. And cyano group-containing compounds such as the following compounds 2-22 and the like, but are not limited thereto.

As described above, the hole transport regions 210 to 215 may further include at least one of a hole buffer layer and an electron blocking layer, in addition to the hole injection layer 210 and the hole transport layer 215.

The hole buffer layer may increase the light emission efficiency by compensating the resonance distance according to the wavelength of light emitted from the light emitting layer 220. As a material included in the hole buffer layer, a material that may be included in the hole transport regions 210 to 215 may be used.

The electron blocking layer is a layer that serves to prevent electron injection from the electron transport regions 230 to 235 to the hole transport regions 210 to 215. The electron blocking layer may use a material having a high T1 value to prevent electrons from moving to the hole transport region and to prevent the exciton formed in the light emitting layer 220 from diffusing into the hole transport region 210 to 215. For example, a host or the like of the light emitting layer 220 having a high T1 value may be used as the electron blocking layer material.

The light emitting layer 220 is provided on the hole transport regions 210 to 215. The light emitting layer 220 may have, for example, a thickness of about 100 mm 2 to about 1000 mm 2, or about 100 mm 2 to about 300 mm 2. The light emitting layer 220 may have a single layer made of a single material, a single layer made of a plurality of different materials, or a multi-layer structure having a plurality of layers made of a plurality of different materials.

The light-emitting layer 220 is an area where holes and electrons meet to form excitons. The material forming the light-emitting layer 220 must have an appropriate energy band gap to exhibit high light emission characteristics and a desired light emission color, and generally has two roles: a host and a dopant. It is made of two materials, but is not limited thereto.

The host may include at least one of the following TPBi, TBADN, ADN (also referred to as "DNA"), CBP, CDBP, TCP, mCP, and the material is not limited if the properties are appropriate.

The dopant of the light emitting layer 220 in one embodiment may be an organic metal complex. The content of the general dopant may be selected from 0.01 to 20%, and is not limited thereto.

The electron transport regions 230 to 235 are provided on the emission layer 220. The electron transport regions 230 to 235 may include at least one of a hole blocking layer, an electron transport layer 230, and an electron injection layer 235, but are not limited thereto.

The electron transport regions 230 to 235 may have a single layer made of a single material, a single layer made of a plurality of different materials, or a multi-layer structure having a plurality of layers made of a plurality of different materials.

For example, the electron transport regions 230 to 235 may have a single layer structure of the electron injection layer 235 or the electron transport layer 230, or may have a single layer structure made of an electron injection material and an electron transport material. have. In addition, the electron transport regions 230 to 235 have a single layer structure made of a plurality of different materials, or the electron transport layer 230 / electron injection layer 235 stacked sequentially from the light emitting layer 220, hole blocking The layer / electron transport layer 230 / electron injection layer 235 may have a structure, but is not limited thereto. The thickness of the electron transport regions 230 to 235 may be, for example, about 1000 mm2 to about 1500 mm2.

The electron transport regions 230 to 235 are various such as vacuum evaporation, spin coating, cast, LB (Langmuir-Blodgett), inkjet printing, laser printing, and laser induced thermal imaging (LITI). It can be formed using a method.

When the electron transport regions 230 to 235 include the electron transport layer 230, the electron transport region 230 may include an anthracene-based compound. However, the present invention is not limited thereto, and the electron transport region is, for example, Alq3 (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), Bebq2 (berylliumbis (benzoquinolin-10-olate), ADN (9,10-di (naphthalene-2-yl) anthracene) and mixtures thereof.

Since the electron transport layer 230 is selected as a material having a fast electron mobility or a slow electron mobility according to the structure of the organic electroluminescent device, various materials need to be selected, and the following Liq or Li is sometimes doped.

The thickness of the electron transport layer 230 may be about 100 mm 2 to about 1000 mm 2, for example, about 150 mm 2 to about 500 mm 2. When the thickness of the electron transport layer 230 satisfies the above-described range, a satisfactory electron transport characteristic can be obtained without a substantial increase in driving voltage.

When the electron transport regions 230 to 235 include the electron injection layer 235, the electron transport regions 230 to 235 select a metal material that facilitates injection of electrons, LiF, LiQ (Lithium quinolate), A lanthanide metal such as Li ₂ O, BaO, NaCl, CsF, and Yb, or a halogenated metal such as RbCl or RbI may be used, but is not limited thereto.

The electron injection layer 235 may also be made of a material in which an electron transport material and an insulating organo metal salt are mixed. The organic metal salt may be a material having an energy band gap of approximately 4 eV or more. Specifically, for example, the organic metal salt may include metal acetate, metal benzoate, metal acetoacetate, metal acetylacetonate or metal stearate. You can.

The thickness of the electron injection layer 235 may be about 1 mm2 to about 100 mm2, and about 3 mm2 to about 90 mm2. When the thickness of the electron injection layers 235 satisfies the above-described range, it is possible to obtain a satisfactory electron injection characteristic without substantially increasing the driving voltage.

As described above, the electron transport regions 230 to 235 may include an electron blocking layer. The electron blocking layer includes, for example, at least one of BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), and Balq It can, but is not limited to this.

The second electrode 120 is provided on the electron transport regions 230 to 235. The second electrode 120 may be a common electrode or a cathode. The second electrode 120 may be a transmissive electrode or a semi-transmissive electrode electrode. The second electrode 120 can be used in combination with a metal, an electrically conductive compound, an alloy, and the like having a relatively low work function, unlike the first electrode 110.

The second electrode 120 is a semi-transmissive electrode or a reflective electrode. The second electrode 120 is Li (lithium), Mg (magnesium), Al (aluminum), Al-Li (aluminum-lithium), Ca (calcium), Mg-In (magnesium-indium), Mg-Ag (magnesium) -Silver) or a compound or mixture comprising them (for example, a mixture of Ag and Mg). Or a plurality of layer structure including a reflective 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), etc. Can be

Although not illustrated, the second electrode 120 may be connected to the auxiliary electrode. When the second electrode 120 is connected to the auxiliary electrode, the resistance of the second electrode 120 can be reduced.

An electrode and an organic material layer are formed on the illustrated substrate 100. At this time, the substrate 100 may be made of a hard or soft material. For example, as the hard material, soda lime glass, alkali-free glass, and alumino silicate glass Etc. can be used, and as the soft material, PC (polycarbonate), PES (polyethersulfone), COC (cyclic olefin copolymer), PET (polyethylene terephthalate), PEN (polyethylene naphthalate), etc. can be used. .

In the organic electroluminescent device, holes injected from the first electrode 110 pass through the hole transport regions 210 to 215 as voltages are applied to the first electrode 110 and the second electrode 120, respectively. The electrons injected from the second electrode 120 are moved to the light emitting layer 220 through the electron transport regions 230 to 235. The electrons and holes recombine in the light emitting layer 220 to generate excitons, and the excitons emit light from the excited state to the ground state.

The optical path generated in the light emitting layer 220 may exhibit a very different trend depending on the refractive index of organic and inorganic materials constituting the organic electroluminescent device. Light passing through the second electrode 120 may pass only light transmitted at an angle smaller than the critical angle of the second electrode 120. In addition, the light contacting the second electrode 120 larger than the critical angle is totally reflected or reflected, and thus is not emitted outside the organic electroluminescent device.

If the refractive index of the capping layer 300 is high, it contributes to improving the luminous efficiency by reducing the total reflection or reflection phenomenon, and when it has an appropriate thickness, it also contributes to the improvement of high efficiency and color purity by maximizing the micro-cavity phenomenon. .

The capping layer 300 is positioned on the outermost side of the organic electroluminescent device, and has a great influence on device characteristics without affecting the driving of the device. Therefore, the capping layer 300 is important both in terms of improving the characteristics of the device and at the same time as the internal protective role of the organic EL device.

Organic materials absorb light energy in a specific wavelength region, which depends on the energy band gap. Adjusting this energy band gap for the purpose of absorbing the UV region that can affect the organic materials inside the organic electroluminescent device, the capping layer 300 also includes optical properties to improve the protection of the organic electroluminescent device. Can be used.

Hereinafter, an arylamine derivative compound used in the organic layer and / or the capping layer will be described.

The arylamine derivative compound according to an embodiment of the present invention is represented by the following Chemical Formula 1.

[Formula 1]

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상기 화학식 1에 있어서,
Z₁ 및 Z₂는 각각 독립적으로 O, S 또는 NR₅ 이고,
Ar₁및 Ar₂는 각각 독립적으로 탄소수 1 이상 4 이하의 알킬기, 중수소 치환된 알킬기, 또는 치환 또는 비치환된 고리 형성 탄소수 6 이상 20 이하의 아릴기이고,

In Chemical Formula 1,
Z ₁ and Z ₂ are each independently O, S or NR ₅ ,
Ar ₁ and Ar ₂ are each independently an alkyl group having 1 to 4 carbon atoms, a deuterium substituted alkyl group, or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms,

R ₁ , R ₂ , R _3, R ₄ and R ₅ are each independently hydrogen atom, deuterium atom, halogen atom, deuterium substituted alkyl group, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted Ring-forming hydrocarbon ring group having 5 to 20 carbon atoms, substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, alkoxy, aryloxy group, cyano group, amino group, substituted or unsubstituted silyl group, alkenyl group, heteroake Nyl group, alkynyl group, unsaturated hydrocarbon ring group, substituted or unsubstituted aryl group having 6 to 30 carbon atoms, substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, acyl group, carbonyl group, carbo group Nilic acid group, carbonyl ester group, nitrile group, isonitrile group, sulfanyl group, sulfinyl group, sulfonyl group, phosphino group, substituted or unsubstituted monovalent non-aromatic condensed polycyclic group, substituted or unsubstituted monovalent ratio - It may be an aromatic heterocondensed polycyclic group, or may be combined with an adjacent group to form a ring, and n ₁ to n ₄ are each independently an integer of 0 or more and 4 or less.

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The aryl amine derivative represented by Chemical Formula 1 according to an embodiment of the present invention is selected from compounds represented by Chemical Formula 2, but is not limited thereto.
[Compound Formula 2]

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Hereinafter, an organic electroluminescent device according to an embodiment of the present invention and an aryl amine derivative of an embodiment will be described in detail with reference to Examples and Comparative Examples. In addition, the embodiment shown below is an example to aid the understanding of the present invention, and the scope of the present invention is not limited thereto.

[Example]

Intermediate Synthetic example  1: Synthesis of intermediate (2)

(Synthesis of intermediate (2))

 2-aminophenol (2-aminophenol) 10.0 g (0.092 mol), 4-bromobenzaldehyde (4-Bromobenzaldehyde) 16.9 g (0.092 mol) and ethanol 114 mL was added and stirred at room temperature for 6 hours. After the reaction was completed, the solvent was distilled under reduced pressure and dried to obtain a Crude intermediate (1). The purification process is omitted and the next reaction proceeds.

After dissolving the intermediate (1) in 370 mL of dichloromethane, while stirring at room temperature, 2,3-dichloro-5,6-dicyano-p-benzoquinone (2,3-Dichloro-5,6-dicyano-p- Slowly add 22.8 g (0.101 mol) of benzoquinone, DDQ). After stirring for one day, it is purified by column chromatography (DCM). Solidification with methanol gave 30.5 g (yield: 94.4%) of a white solid compound (Intermediate (2)).

Intermediate Synthetic example  2: Synthesis of intermediate (4)

(Synthesis of intermediate (4))

2-aminobenzothiol (2-aminobenzothiol) 10.0 g (76.88 mmol), 4-bromobenzaldehyde (4-Bromobenzaldehyde) 12.8 g (69.42 mol) and 130 mL of ethanol was added and stirred at room temperature for 6 hours. After the reaction was completed, the solvent was distilled under reduced pressure and dried to obtain a Crude intermediate ( 3 ). The purification process is omitted and the next reaction proceeds.

After dissolving the intermediate (3) in 320 mL of dichloromethane, while stirring at room temperature, 2,3-dichloro-5,6-dicyano-p-benzoquinone (2,3-Dichloro-5,6-dicyano-p- Slowly add 19.9 g (0.088 mol) of benzoquinone, DDQ). After stirring for one day, it is purified by column chromatography (MC). Solidification with methanol gave 26.6 g (yield: 90.2%) of a white solid compound (Intermediate (4)).

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Intermediate Synthesis Example 3: Synthesis of Intermediate (6)

(Synthesis of intermediate (5))

4-Amino-3-bromobenzonitrile 50.0 g (253.76 mmol), 4-bromobenzoyl chloride 55.7 g (253.76 mmol) and pyridine 500 Add mL and stir to reflux for at least 12 hours. After the reaction was completed, the solvent was distilled under reduced pressure. Solidification with diisopropyl ether (IPE) gave 75.6 g (yield: 78.3%) of a pale yellow solid compound (Intermediate (5)).

(Synthesis of intermediate (6))

In a 1-neck 1 L flask, intermediate (5) 75.6 g (251.05 mmol), CuI 2.39 g (12.55 mmol), 1,10-Phenanthroline 4.52 g (25.10 mmol), Cs ₂ CO ₃ 148.7 g (456.56 mmol) and nitrobenzene (Nitrobenzene) 800 mL was stirred under reflux throughout the day. After the reaction was completed, DCM was passed through a pad of celite. After removing the solvent, the solid was dissolved in chloroform, and then purified by column chromatography (CHCl ₃ ). Solidification with methanol gave 42.3 g (yield: 56.3%) of a pale yellow solid compound (Intermediate (6)).

Intermediate Synthesis Example 4: Synthesis of Intermediate (8)

(Synthesis of intermediate (7))

2-Bromo-4-tert-butylaniline 40.0 g (175.34 mmol), 4-bromobenzoyl chloride 38.4 g (175.34 mmol) and THF 360 mL The mixture was stirred at room temperature for 3 hours. After the reaction was completed, the solvent was distilled under reduced pressure. Solidification with diisopropyl ether (IPE) gave 55.8 g (yield: 77.4%) of a pale yellow solid compound (Intermediate (7)).

(Synthesis of intermediate (8))

In a 1-neck 1 L flask, 55.8 g (167.95 mmol) of intermediate (7), 1.60 g (8.40 mmol) of CuI, 3.03 g (16.6 mmol) of 1,10-Phenanthroline, 109.4 g (335.91 mmol) of Cs ₂ CO ₃ and dimethoxy 500 mL of ethane (DME) is stirred at 90 ° C. throughout the day. After the reaction was completed, DCM was passed through a pad of celite. After removing the solvent, the solid was dissolved in chloroform, and then purified by column chromatography (CHCl ₃ ). Solidification with methanol gave 46.8 g (yield: 84.3%) of a pale yellow solid compound (Intermediate (8)).

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Intermediate Synthesis Example 5: Synthesis of Intermediate (11)

(Synthesis of intermediate (9))

1-Aminonaphthalene (1-Aminonaphthalene) 50.0g (349.20 mmol), 4-bromobenzoyl chloride (4-Bromobenzoyl chloride) 76.6 g (349.20 mmol) and THF 500 mL was added and stirred at room temperature for 3 hours. After the reaction was completed, the solvent was distilled under reduced pressure. Solidification with diisopropyl ether (IPE) gave 100.0 g (yield: 87.7%) of a pale yellow solid compound (Intermediate (9)).

(Synthesis of intermediate 10)

100 g (306.57 mmol) of intermediate (9), 136.9 g (367.89 mmol) of Lawesson's reagent and 1,500 mL of toluene were added and refluxed throughout the day. After the reaction is completed, the solvent is distilled under reduced pressure, dissolved in dichlorobenzene (DCM) and passed through a celite pad. The filtrate thus passed was concentrated under reduced pressure to obtain 104.9 g of intermediate (10). The next reaction proceeded without any further purification.

1200 mL of 2M NaOH and 100 mL of ethanol were added dropwise to 104.9 g (306.57 mol) of the intermediate (10), followed by stirring at room temperature for 20 minutes. 1.2MK ₃ [Fe (CN) ₆ ] 970 mL is slowly added dropwise and refluxed throughout the day. After the reaction was completed, the mixture was cooled to room temperature, and the solid produced during the reaction was filtered and washed with water. The solid thus obtained was dissolved in chloroform and subjected to column chromatography (CHCl3: HEX = 1: 1) and solidified with methanol to obtain 38.5 g of a white solid compound (Intermediate (11)) (yield: 38.7%).

Intermediate Synthesis Example 6: Synthesis of Intermediate (15)

(Synthesis of intermediate 12)

9-Bromophenathrene 100.0 g (388.92 mmol), Benzophenone imine 84.5 g (466.70 mmol), Pd (dba) ₂ 11.1 g (19.45 mmol), BINAP 12.1 g (19.45 mmol), Cs ₂ CO _{3 Add} 190.0 g (583.37 mmol) and 1,000 mL of Toluene and stir at reflux throughout the day. After confirming the reaction, impurities are removed using a celite pad.

After removing the solvent, acidified (pH <2) with 100 mL of THF and 50 mL of 2M HCl, and stirred for 1 hour. After confirming the reaction, it was basified with aqueous NaHCO ₃ solution (pH> 8) and stirred for 30 minutes or more. After extraction with EA to remove moisture and solvent, purification was performed by column chromatography (CHCl ₃ ) to obtain 66.8 g (yield: 88.8%) of a pale yellow solid compound (Intermediate (12)).

(Synthesis of intermediate (13))

Intermediate (12) 66.8 g (345.68 mmol), 4-bromobenzoyl chloride (4-Bromobenzoyl chloride) 75.8 g (345.68 mmol) and THF 700 mL were added and stirred at room temperature for 3 hours. After the reaction was completed, the solvent was distilled under reduced pressure. Solidification with diisopropyl ether (IPE) gave 111.0 g (yield: 85.3%) of a pale yellow solid compound (Intermediate (13)).

(Synthesis of intermediate (15))

111 g (295.02 mmol) of intermediate (13), 131.8 g (354.02 mmol) of Lawesson's reagent and 1,500 mL of toluene were added and refluxed throughout the day. After the reaction is completed, the solvent is distilled under reduced pressure, dissolved in dichlorobenzene (DCM) and passed through a celite pad. The filtrate thus passed was concentrated under reduced pressure to obtain 115 g of intermediate (14). The next reaction proceeded without any further purification.

1200 mL of 2M NaOH and 100 mL of ethanol were added dropwise to 115 g (293.13 mol) of the intermediate (14), followed by stirring at room temperature for 20 minutes. 1.2MK ₃ [Fe (CN) ₆ ] 970 mL is slowly added dropwise and refluxed throughout the day. After the reaction was completed, the mixture was cooled to room temperature, and the solid produced during the reaction was filtered and washed with water. The solid thus obtained was dissolved in chloroform and subjected to column chromatography (CHCl ₃ : HEX = 1: 1) and solidified with methanol to obtain 25.8 g of a white solid compound (Intermediate (15)) (yield: 22.5%).

Intermediate Synthesis Example 7: Synthesis of Intermediate (16)

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(Synthesis of intermediate (16))

Intermediate (2) 10.0 g (36.48 mmol), 4-Aminobenzonitrile 6.4 g (54.72 mmol), Pd (dba) ₂ 1.0 g (1.82 mmol), 50% P ( t-Bu) ₃ 1.4 g (3.65 mmol), NaOtBu 7.0 g (72.96 mmol) and Toluene 100 mL were mixed and then refluxed. After the reaction was completed, the mixture was cooled to room temperature, solidified with MeOH, and filtered. After the solid was purified by silica gel column chromatography (MC: HEX), it was solidified with EA and filtered to obtain 7.3 g of a yellow solid compound (Intermediate (16)) (yield: 64.2%).

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Intermediate Synthesis Example 8: Synthesis of Intermediate (17)

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(Synthesis of intermediate (17))

In a 1-neck 250 mL flask, intermediate (6) 10.0 g (33.43 mmol), 4-aminobenzonitrile 5.9 g (50.15 mmol), Pd (dba) ₂ 961 mg (1.67 mmol), 50% P ( t-Bu) ₃ 1.35 g (3.34 mmol), NaOtBu 6.4 g (66.8 mmol) and Toluene 100 mL were mixed and then refluxed. After the reaction was completed, the mixture was cooled to room temperature, solidified with MeOH, and filtered. The solid was purified by silica gel column chromatography (MC: HEX), solidified with EA and filtered to obtain 6.2 g (yield: 55.1%) of a yellow solid compound (Intermediate (17)).

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Intermediate Synthesis Example 9: Synthesis of Intermediate (18)

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(Synthesis of intermediate (18))

In a 1-neck 250 mL flask, 15.0 g (44.09 mmol) of intermediate (11), 5.96 g (132.26 mmol) of ethylamine (132.26 mmol), Pd (dba) ₂ 1.2 g (2.20 mmol), 50% P (t-Bu) ₃ 1.7 g (4.41 mmol), NaOtBu 10.5 g (110.22 mmol) and Toluene 150 mL were mixed and then refluxed. After the reaction was completed, the mixture was cooled to room temperature, solidified with MeOH, and filtered. The solid was purified by silica gel column chromatography (MC: HEX), solidified with EA and filtered to obtain 7.3 g (yield: 54.3%) of a yellow solid compound (Intermediate (18)).

Intermediate Synthesis Example 10: Synthesis of Intermediate 19

(Synthesis of intermediate (19))

In a 1-neck 500 mL flask, intermediate (15) 20.0 g (51.24 mmol), ethylamine (Ethylamine) 6.9 g (153.73 mmol), Pd (dba) ₂ 1.4 g (2.56 mmol), 50% P (t-Bu) ₃ 2.0 g (5.12 mmol), NaOtBu 12.3 g (128.11 mmol) and Toluene 200 mL were mixed and then refluxed. After the reaction was completed, the mixture was cooled to room temperature, solidified with MeOH, and filtered. After the solid was purified by silica gel column chromatography (MC: HEX), it was solidified with EA and filtered to obtain 8.2 g of a yellow solid compound (Intermediate (19)) (yield: 45.1%).

Various arylamine compounds were synthesized as follows using the synthesized intermediate compound.

Example 1: Synthesis of Compound 2-15 (LT17-30-414)

In a 1-neck 100 mL flask, N, N'-diphenyl-p-phenylenediamine (N, N'-Diphenyl-p-phenylenediamine) 2.0 g (7.68 mmol), intermediate (2) 4.4 g (16.13 mmol), Pd (dba) ₂ 441 mg (0.768 mmol), 50% P (t-Bu) ₃ 621 mg (1.54 mmol), NaOtBu 1.8 g (19.21 mmol) and Toluene 20 mL were mixed and then refluxed. After the reaction was completed, the mixture was cooled to room temperature, solidified with MeOH, and filtered. The solid was purified by silica gel column chromatography (MC: HEX), solidified with EA and filtered to obtain 3.2 g (Yield: 64.4%) of a yellowish solid compound 2-15 (LT17-30-414).

Example 2: Synthesis of Compound 2-19 (LT17-35-616)

In a 1-neck 100 mL flask, N, N'-diphenyl-p-phenylenediamine (N, N'-Diphenyl-p-phenylenediamine) 2.0 g (7.68 mmol), intermediate (8) 5.3 g (16.13 mmol), Pd (dba) ₂ 441 mg (0.768 mmol), 50% P (t-Bu) ₃ 621 mg (1.54 mmol), NaOtBu 1.8 g (19.21 mmol) and Toluene 20 mL were mixed and then refluxed. After the reaction was completed, the mixture was cooled to room temperature, solidified with MeOH, and filtered. The solid was purified by silica gel column chromatography (MC: HEX), solidified with EA and filtered to obtain 3.9 g (Yield: 66.8%) of a yellowish solid compound 2-19 (LT17-35-616).

Example 3: Synthesis of Compound 2-22 (LT17-30-593)

In a 1-neck 100 mL flask, N, N'-diphenyl-p-phenylenediamine (N, N'-Diphenyl-p-phenylenediamine) 2.0 g (7.68 mmol), intermediate (6) 4.8 g (16.13 mmol), Pd (dba) ₂ 441 mg (0.768 mmol), 50% P (t-Bu) ₃ 621 mg (1.54 mmol), NaOtBu 1.8 g (19.21 mmol) and Toluene 20 mL were mixed and then refluxed. After the reaction was completed, the mixture was cooled to room temperature, solidified with MeOH, and filtered. The solid was purified by silica gel column chromatography (MC: HEX), solidified with EA and filtered to obtain 2.3 g (Yield: 42.9%) of a yellowish solid compound 2-22 (LT17-30-593).

Example 4: Synthesis of Compound 2-29 (LT17-35-612)

1,4-dibromobenzene (1,4-Dibromobenzene) 2.0 g (8.48 mmol), intermediate (16) 5.5 g (17.80 mmol), Pd (dba) ₂ 487 mg (0.847 mmol) in a 1-neck 100 mL flask , 50% P (t-Bu) ₃ 686 mg (1.70 mmol), NaOtBu 2.0 g (21.20 mmol) and Toluene 50 mL were mixed and then refluxed. After the reaction was completed, the mixture was cooled to room temperature, solidified with MeOH, and filtered. The solid was purified by silica gel column chromatography (MC: HEX), solidified with EA and filtered to obtain 4.1 g (yield: 69.4%) of a yellowish solid compound 2-29 (LT17-35-612).

Example 5: Synthesis of Compound 2-70 (LT17-35-613)

1,4-dibromobenzene (1,4-Dibromobenzene) 1.5 g (6.36 mmol), intermediate (15) 4.7 g (13.35 mmol), Pd (dba) ₂ 365 mg (0.635 mmol) in a 1-neck 100 mL flask , 50% P (t-Bu) ₃ 514 mg (1.27 mmol), NaOtBu 1.5 g (15.9 mmol) and Toluene 40 mL, and then refluxed. After the reaction was completed, the mixture was cooled to room temperature, solidified with MeOH, and filtered. After the solid was purified by silica gel column chromatography (MC: HEX), it was solidified with EA and filtered to obtain 2.4 g (Yield: 48.2%) of a yellowish solid compound 2-70 (LT17-35-613).

Example 6: Synthesis of Compound 2-71 (LT17-30-432)

In a 1-neck 100 mL flask, N, N'-diphenyl-p-phenylenediamine (N, N'-Diphenyl-p-phenylenediamine) 2.0 g (7.68 mmol), intermediate (4) 4.6 g (16.13 mmol), Pd (dba) ₂ 441 mg (0.768 mmol), 50% P (t-Bu) ₃ 621 mg (1.54 mmol), NaOtBu 1.8 g (19.21 mmol) and Toluene 20 mL were mixed and then refluxed. After the reaction was completed, the mixture was cooled to room temperature, solidified with MeOH, and filtered. After the solid was purified by silica gel column chromatography (MC: HEX), it was solidified with EA and filtered to obtain 2.9 g of a yellowish solid compound 2-71 (LT17-30-432) (yield: 55.6%).

Example 7: Synthesis of Compound 2-126 (LT17-35-614)

1.0 g (3.84 mmol), 2- (4-bromophenyl) -N-, N, N'-diphenyl-p-phenylenediamine (N, N'-Diphenyl-p-phenylenediamine) in a 1-neck 100 mL flask Phenylbenzoimidazole (2- (4-Bromophenyl) -N-phenylbenzoimidazole) 2.8 g (8.07 mmol), Pd (dba) ₂ 220 mg (0.384 mmol), 50% P (t-Bu) ₃ 310 mg (0.765 mmol) ), NaOtBu 922 mg (9.60 mmol) and Toluene 20 mL, and then refluxed. After the reaction was completed, the mixture was cooled to room temperature, solidified with MeOH, and filtered. The solid was purified by silica gel column chromatography (MC: HEX), solidified with EA and filtered to obtain 1.9 g (Yield: 62.0%) of a yellowish solid compound 2-126 (LT17-35-614).

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<Test Example 1>

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For the compounds of the present invention, n (refractive index) and k (extinction coefficient) were measured using Filmetrics' F20 instrument.

Device fabrication Test example

In order to measure the optical properties of the produced material, the glass substrate (0.7T) was washed with Ethanol, DI, and Acetone for 10 minutes, respectively, and then a compound of 800Å was deposited on the glass substrate.

Comparative test example: Glass / REF01 ( 80 nm )

The optical characteristic device was fabricated by depositing REF01 (80nm) on glass. Prior to depositing the organic material Glass is 2 × 10 ^- it was for 2 minutes in the oxygen plasma treatment ² Torr to 125 W. Organics are 9 × 10 ^- were deposited at a vacuum degree of ⁷ Torr organic materials were deposited at a rate of 1Å / sec.

<Test Examples 1 to 7>

In the comparative test example, a device was manufactured in the same manner as in the comparative test example, except that each compound shown in Table 1 was used instead of using REF01.

Table 1 shows the properties of the optical properties samples prepared in Comparative Test Examples and Test Examples 1 to 7.

In Table 1, refractive index constants at 420 nm and 620 nm wavelengths and absorption constants at 380 nm wavelength are presented.

division compound n (450nm, 620nm) k (380 nm) Comparative example REF01 2.138, 1.971 0.274 Example 1 2-15
(LT17-30-414) 2.326, 2.018 0.679 Example 2 2-19
(LT17-35-616) 2.263, 1.997 0.598 Example 3 2-22
(LT17-30-593) 2.500, 2.071 0.759 Example 4 2-29
(LT17-35-612) 2.426, 2.108 0.693 Example 5 2-70
(LT17-35-613) 2.362, 2.008 0.532 Example 6 2-71
(LT17-30-432) 2.283, 1.953 0.658 Example 7 2-126
(LT17-35-614) 2.463, 2.118 0.555

As can be seen from Table 1, the n value at 450 nm of the comparative example (REF01) was 2.138, whereas most of the example compounds were found to have a refractive index higher than 2.138. This satisfies the high refractive index value required to ensure a high viewing angle in the blue region.

In addition, k values at 380 nm corresponding to the starting stage of the UV region were also found to be high in most of the example compounds. This may contribute to a substantial improvement in the life of the organic electroluminescent device by effectively absorbing a high energy external light source in the UV region and minimizing damage to organic materials inside the organic light emitting device.

The compound of Formula 1 has surprisingly desirable properties for use as a capping layer in OLEDs.

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

100: substrate, 110: first electrode, 120: second electrode, 200: organic material layer, 210: hole injection layer, 215: hole transport layer, 220: light emitting layer, 230: electron transport layer, 235: electron injection layer, 300: capping layer

Claims (8)

An arylamine derivative for a capping layer of an organic electroluminescent device, represented by the following Chemical Formula 1.
[Formula 1]

(In the above formula 1,
Z ₁ and Z ₂ are each independently O, S,
Ar ₁ and Ar ₂ are each independently a methyl group, ethyl group, isopropyl group, isobutyl group, t-butyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted phenanthrene group, A substituted or unsubstituted dibenzothiophene group, or a substituted or unsubstituted dibenzofuran group.
R ₁ , R ₂ , R ₃ , R ₄ and R ₅ are each independently hydrogen, deuterium, fluorine atom, cyano group, methyl group, ethyl group, isopropyl group, isobutyl group, t-butyl group, trimethylsilyl group, tri Phenylsilyl group, trifluoromethyl group, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted phenanthrene group, substituted or unsubstituted dibenzothiophene group, or substituted or unsubstituted Dibenzofuran group,
n ₁ to n ₄ are each independently an integer of 0 or more and 4 or less.) delete delete According to claim 1,
The formula 1 is any one selected from compounds represented by the following formula 2, an arylamine derivative for a capping layer of an organic electroluminescent device.
[Formula 2]

A first electrode;
An organic layer disposed on the first electrode and composed of a plurality of organic material layers;
A second electrode disposed on the organic layer; And
And a capping layer disposed on the second electrode,
The capping layer is an organic electroluminescent device comprising the arylamine derivative of claim 1 or 4. The method of claim 5,
The organic film is a hole injection layer; Hole transport layer; A light emitting layer; Electron transport layer; And an electron injection layer. delete delete

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