KR102417622B1 - Tertiary amine derivatives and organic electroluminescent device including the same - Google Patents

Abstract

(상기 화학식 1에서 각 치환기들은 발명의 상세한 설명에서 정의한 바와 같다.)Provided is a tertiary amine derivative that effectively absorbs a high-energy external light source in the UV region to minimize damage to organic materials inside the organic EL device, thereby contributing to the improvement of the practical lifespan of the organic EL device.
An organic electroluminescent device according to the present invention, a first electrode; a second electrode; one or more organic material layers disposed between the first electrode and the second electrode; and a capping layer, wherein the capping layer includes a tertiary amine derivative represented by Formula 1 below.
[Formula 1]

(Each substituent in Formula 1 is as defined in the detailed description of the invention.)

Description

Tertiary amine derivatives and organic electroluminescent device including the same

The present invention relates to a tertiary amine derivative and to an organic electroluminescent device including the same, wherein the organic electroluminescent device including a capping layer by the tertiary amine derivative has both high refractive index and ultraviolet absorption characteristics.

OLED (Organic Light Emitting Diodes) is attracting attention as a display using self-luminescence in the display industry.

In OLED, a study of carrier injection electroluminescence (EL) using a single crystal of an anthracene aromatic hydrocarbon was first attempted by Pope et al. in 1963. From these studies, basic mechanisms such as charge injection, recombination, exciton generation, and light emission in organic materials and electroluminescence characteristics have been understood and studied.

In particular, in order to increase the luminous efficiency, various approaches are being made, such as changing the structure of the device and developing materials [Sun, S., Forrest, S. R., Appl. Phys. Lett. 91, 263503 (2007)/Ken-Tsung Wong, Org. Lett., 7, 2005, 5361-5364].

The basic structure of an OLED display is, in general, an anode, a hole injection layer (HIL), a hole transporting layer (HTL), a light emitting layer (Emission Layer, EML), an electron transporting layer (Electron Transporting Layer, ETL), and a multilayer structure of a cathode, and a sandwich structure in which an electron organic multilayer film is formed between two electrodes.

In general, the organic light emitting phenomenon refers to a phenomenon in which electric energy is converted into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon typically has a structure including an anode and a cathode and an organic material layer therebetween. Here, the organic material layer is often formed of a multilayer structure made of different materials in order to increase the efficiency and stability of the organic light emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like.

When a voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It lights up when it falls to the ground state. Such an organic light emitting device is known to have characteristics such as self-luminescence, high luminance, high efficiency, low driving voltage, wide viewing angle, high contrast, and high-speed response.

A material used as an organic material layer in an organic light emitting device may be classified into a light emitting material and a charge transporting material, for example, a hole injection material, a hole transport material, an electron transport material, an electron injection material, and the like, according to functions.

The light-emitting material includes blue, green, and red light-emitting materials depending on the light-emitting color, and yellow and orange light-emitting materials required to realize a better natural color. In addition, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system may be used as a light emitting material. The principle is that when a small amount of a dopant having a smaller energy band gap and superior luminous efficiency than the host constituting the light emitting layer is mixed in the light emitting layer in a small amount, 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 band of the dopant, light having a desired wavelength can be obtained according to the type of dopant used.

In order to sufficiently express the excellent characteristics of the above-described organic light emitting device, materials constituting an organic material layer in the device, such as a hole injection material, a hole transport material, a light emitting material, an electron transport material, an electron injection material, etc. The performance of the organic light emitting device is recognized by the products.

However, as the commercialization of the organic light emitting device is made and time passes, the need for other characteristics in addition to the light emitting characteristic of the organic light emitting device itself is emerging.

Since the organic light emitting diode is exposed to an external light source for a large amount of time, it is in an environment exposed to ultraviolet rays having high energy. Accordingly, there is a problem in that the organic material constituting the organic light emitting device is continuously affected. In order to prevent exposure to such a high energy light source, the problem can be solved by applying a capping layer having ultraviolet absorption characteristics to the organic light emitting diode.

In general, it is known that the viewing angle characteristics of an organic light emitting device are wide, but from the viewpoint of the light source spectrum, a significant deviation occurs depending on the viewing angle. This is due to the occurrence of a deviation between the appropriate refractive indices.

In general, the larger the value of the refractive index required for blue and the longer the wavelength, the smaller the value of the required refractive index. Accordingly, it is necessary to develop a material for forming a capping layer that simultaneously satisfies the above-mentioned ultraviolet absorption characteristics and an appropriate refractive index.

The efficiency of the organic light emitting diode can be generally divided into internal luminescent efficiency and external luminescent efficiency. The internal luminous efficiency is related to the efficiency of the formation of excitons in the organic layer for light conversion to take place.

The external luminous efficiency refers to the efficiency at which light generated in the organic layer is emitted to the outside of the organic light emitting device.

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 external luminous efficiency and prevent various problems that may be caused when exposed to daylight for a long time, the development of a new functional capping layer (CPL) compound is required. In particular, there is a demand for the development of a capping layer (CPL) material having excellent ability to absorb light in the UV wavelength band among CPL functions.

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

SUMMARY OF THE INVENTION It is an object of the present invention to provide a capping layer material for an organic light emitting device, which can improve luminous efficiency and lifespan, and at the same time improve viewing angle characteristics.

An object of the present invention is to provide an organic electroluminescent device with high efficiency and long life, including a capping layer having high refractive index and heat resistance, in particular to improve the light extraction rate of the organic electroluminescent device.

The present invention is a first electrode; an organic material layer disposed on the first electrode; a second electrode disposed on the organic material layer; and a capping layer disposed on the second electrode, wherein the organic material layer or the capping layer provides an organic electroluminescent device including a tertiary amine derivative represented by Formula 1 below.

[Formula 1]

In Formula 1,

Z ₁ is O or S;

n, p and q are each independently 0 or 1,

Ar ₁ and Ar ₂ are the same as each other, and a cyano group; an aryl group substituted with a cyano group; A substituted or unsubstituted dibenzofuran group; a substituted or unsubstituted dibenzothiophene group; a substituted or unsubstituted benzoxazole group; and a substituted or unsubstituted benzthiazole group; any one selected from

The compound described herein may be used as a material for an organic material layer or a capping layer of an organic light emitting device.

The compound according to the present invention can minimize damage to organic materials in the organic light-emitting device by an external light source by exhibiting ultraviolet absorption characteristics, and can improve efficiency, low driving voltage, and/or lifespan characteristics in the organic light-emitting device.

In addition, in an organic light-emitting device using the compound described in the present specification as a capping layer, it is possible to significantly improve luminous efficiency and color purity according to a decrease in the emission spectrum half width.

1 illustrates a first electrode 110, 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 on a substrate 100 according to an embodiment of the present invention. An example of an organic light emitting device in which 235 , the second electrode 120 , and the capping layer 300 are sequentially stacked is shown.
Figure 2 is a graph of the refraction and absorption characteristics of light appearing when using a tertiary amine derivative according to an embodiment of the present invention.

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

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

In describing each figure, like reference numerals have been used for like elements. In the accompanying drawings, the dimensions of the structures are enlarged than the actual size for clarity of the present invention. Terms such as first, second, etc. may be used to describe various elements, but the elements should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component. The singular expression includes the plural expression unless the context clearly dictates otherwise.

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

As used herein, "substituted or unsubstituted" is 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, an alke group It may mean unsubstituted or substituted with one or more substituents selected from the group consisting of a nyl group, an aryl group, a heteroaryl 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, 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 linear, branched or cyclic. Carbon number of an alkyl group is 1 or more and 50 or less, 1 or more and 30 or less, 1 or more and 20 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 group 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-tricho Sil group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, and n-triacontyl group etc. are mentioned, It is not limited to these.

As used herein, the 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, the 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 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, an anthracenyl group, a phenanthryl group, a biphenyl group, a terphenyl group, a quarterphenyl group, a quinkphenyl group, a sexyphenyl group, a triphenylenyl group, a pyrenyl group, a peryleneyl group, a naphtha group Although a cenyl 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 be bonded to each other to form a spiro structure.

In the present specification, the heteroaryl group may be a heteroaryl group including at least one of O, N, P, Si and S as a heterogeneous element. The N and S atoms may optionally be oxidized and the N atom(s) may optionally be quaternized. 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. 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 a thiophene group, a furan group, a pyrrole group, an imidazole group, a pyrazolyl group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridine group, a bipyridine group, a pyrimidine group, a triazine group , tetrazine group, triazole group, tetrazole group, acridyl group, pyridazine group, pyrazinyl group, quinoline group, quinazoline group, quinoxaline group, phenoxazine group, phthalazine group, pyridopyrimidine group, pyridopyrazino group Pyrazine group, isoquinoline group, cinnol group, indole group, isoindole group, indazole group, carbazole group, N-arylcarbazole group, N-heteroarylcarbazole group, N-alkylcarbazole 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, isoxazole group, oxadiazole group, thiadiazole group, isothiazole group, isoxazole group, phenothiazine group, benzodioxol group, dibenzosilol group and dibenzofuran group, isobenzofuran group, etc., It is not limited to these. In addition, there are N-oxide aryl groups corresponding to the monocyclic heteroaryl group or polycyclic heteroaryl group, for example, quaternary salts such as pyridyl N-oxide group, quinolyl N-oxide group, etc., but these not limited

In the present 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, a phenylsilyl group, and the like. 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, a trimethylboron group, a triethylboron group, a t-butyldimethylboron group, a triphenylboron group, a diphenylboron group, and a phenylboron group.

In the present specification, the alkenyl group may be straight-chain or branched. Although carbon number is not specifically limited, 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, a styryl vinyl group, and the like.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group, and may include a polycyclic aryl group or a monocyclic aryl group and a polycyclic aryl group at the same time.

Specific examples of the arylamine group include a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, a 3-methyl-phenylamine group, a 4-methyl-naphthylamine group, and a 2-methyl-biphenylamine group. group, 9-methyl-anthracenylamine group, diphenyl amine group, phenyl naphthylamine group, ditolyl amine group, phenyl tolyl amine group, carbazole and triphenyl amine group, and the like, but are not limited thereto.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroaryl group in the heteroarylamine group may be a monocyclic heterocyclic group or a polycyclic heterocyclic group. The heteroarylamine group including two or more heterocyclic groups may include a monocyclic heterocyclic group, a polycyclic heterocyclic group, or a monocyclic heterocyclic group and a polycyclic heterocyclic group at the same time.

In the present specification, the aryl heteroarylamine group refers to an amine group substituted with an aryl group and a heterocyclic group.

As used herein, “adjacent group” may mean a substituent substituted on an atom directly connected to the atom in which the substituent is substituted, another substituent substituted on the atom in which the substituent is substituted, or a substituent most sterically adjacent to the substituent. have. For example, in 1,2-dimethylbenzene, two methyl groups can be interpreted as “adjacent groups” to each other, and in 1,1-diethylcyclopentene, 2 methyl groups The two ethyl groups can be interpreted as “adjacent groups” to each other.

Hereinafter, the tertiary amine derivative compound used in the organic material layer and/or the capping layer will be described.

The tertiary amine derivative compound according to an embodiment of the present invention is represented by the following formula (1).

[Formula 1]

In Formula 1,

Z ₁ is O or S;

n, p and q are each independently 0 or 1,

Ar ₁ and Ar ₂ are the same as each other, and a cyano group; an aryl group substituted with a cyano group; A substituted or unsubstituted dibenzofuran group; a substituted or unsubstituted dibenzothiophene group; a substituted or unsubstituted benzoxazole group; and a substituted or unsubstituted benzthiazole group; any one selected from

In one embodiment of the present invention, the tertiary amine derivative represented by Formula 1 may be any one selected from compounds represented by Formula 2 below, and the following compounds may be further substituted.

[Formula 2]

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

1 is a cross-sectional view schematically illustrating an organic light emitting diode according to an embodiment of the present invention. Referring to FIG. 1 , in an organic light emitting diode according to an exemplary embodiment, a first electrode 110 , a hole injection layer 210 , a hole transport layer 215 , a light emitting layer 220 , and electrons are sequentially stacked on a substrate 100 . It may include a transport layer 230 , an electron injection layer 235 , a second electrode 120 , and a capping layer 300 .

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 .

Meanwhile, the capping layer 300 presented in the present invention is a functional layer deposited on the second electrode 120 and includes an organic material according to Chemical Formula 1 of the present invention.

In the organic light emitting diode according to the exemplary embodiment shown 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 a deposition method, electron beam evaporation, or sputtering. 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 light emitting device.

The capping layer 300 proposed in the present invention is applied when the emission direction of the organic light emitting device is top emission, and therefore, 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 It can also be manufactured 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 the hole transport regions 210 to 215 disposed on the first electrode 110 , the light emitting layer 220 disposed on the hole transport region, and the light emitting layer. It may include electron transport regions 230 to 235 disposed on 220 .

The capping layer 300 of an embodiment includes an organic compound represented by Chemical Formula 1 to 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). In general, since hole mobility is faster than electron mobility, it has a thicker thickness than the electron transport region.

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 multilayer 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 including 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/hole transport layer 215 stacked sequentially 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 It may have a structure of the blocking layer EBL, but the embodiment is not limited thereto.

The hole injection layer 210 of the hole transport regions 210 to 215 may be formed on the anode by various methods, such as a vacuum deposition method, a spin coating method, a casting method, and an LB method. When the hole injection layer 210 is formed by vacuum deposition, the deposition conditions are 100 to 500 depending on the compound used as the material for the hole injection layer 210, the structure and thermal characteristics of the hole injection layer 210, etc. The deposition rate at ℃ can be freely adjusted to about 1 Å/s, and is not limited to specific conditions. In the case of forming the hole injection layer 210 by the spin coating method, the coating conditions are different depending on the properties between the compound used as the hole injection layer 210 material and the layers formed as the interface, but for an even film formation, the coating speed, coating After that, heat treatment to remove the solvent is required.

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 sulfonicacid: 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 Å, and the 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 50 Å, the thickness of the hole transport layer 215 may be 1000 Å, and the thickness of the electron blocking layer may be 500 Å. The thickness condition of the hole transport regions 210 to 215 may be determined to a degree that satisfies the efficiency and lifespan within a range in which the driving voltage increase of the organic light emitting diode 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, an electron transport layer ( 230), the 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 like the light emitting layer 220 , and doping of a charge-generating material into the hole transport regions 210 to 215 may improve the electrical properties of the organic light emitting device. can

The charge-generating material is generally made of a material having a very low HOMO and LUMO. For example, the LUMO of the charge-generating material has a value similar to the HOMO of the hole transport layer 215 material. Due to the low LUMO, holes are easily transferred to the adjacent hole transport layer 215 by using the electron vacancy characteristic of the LUMO to improve electrical properties.

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 cyano group-containing compound, but is not limited thereto. For example, non-limiting examples of the p-dopant include tetracyanoquinonedimethane (TCNQ) and 2,3,5,6-tetrafluoro-tetracyano-1,4-benzoquinonedimethane quinone derivatives such as phosphorus (F4-TCNQ) and the like; metal oxides such as tungsten oxide and molybdenum oxide; cyano group-containing compounds; and the like, but is 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 may be, for example, a p-dopant. The p-dopant may be one of a quinone derivative, a metal oxide, and a cyano group-containing compound, but is not limited thereto. For example, non-limiting examples of p-dopants include quinone derivatives such as Tetracyanoquinodimethane (TCNQ) and 2,3,5,6-tetrafluoro-tetracyanoquinodimethane (TCNQ), and metal oxides such as tungsten oxide and molybdenum oxide. may be mentioned, but is 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 light emission efficiency by compensating for a resonance distance according to a wavelength of light emitted from the light emitting layer 220 . As a material included in the hole buffer layer, a material capable of being included in the hole transport regions 210 to 215 may be used.

The electron blocking layer serves to prevent electron injection from the electron transport region 230 to 235 to the hole transport region 210 to 215 . The electron blocking layer may use a material having a high T1 value so that excitons formed in the emission layer 220 do not diffuse into the hole transport regions 210 to 215 as well as to block electrons moving to the hole transport region. For example, a host of the light emitting layer 220 having a generally high T ₁ value may be used as the electron blocking layer material.

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

The light emitting layer 220 is a region where holes and electrons meet to form excitons. The material constituting the light emitting layer 220 must have an appropriate energy band gap to exhibit high light emitting characteristics and a desired light emitting color, and generally serve as both a host and a dopant. Eggplant 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, and mCP, and if the properties are appropriate, the material is not limited thereto.

The dopant of the light emitting layer 220 according to an embodiment may be an organometallic complex. The general dopant content may be selected from 0.01 to 20%, but in some cases, it 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 multilayer 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 including 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 and the hole blocking layer that are sequentially stacked from the light emitting layer 220 . It may have a layer/electron transport layer 230/electron injection layer 235 structure, but is not limited thereto. The thickness of the electron transport regions 230 to 235 may be, for example, about 1000 Å to about 1500 Å.

The electron transport regions 230 to 235 may include a vacuum deposition method, a spin coating method, a casting method, a Langmuir-Blodgett (LB) method, an inkjet printing method, a laser printing method, and a laser induced thermal imaging (LITI) method. method can be used.

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 may be included.

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 light emitting device, various materials need to be selected, and in some cases, Liq or Li may be doped.

The thickness of the electron transport layers 230 may be about 100 Å to about 1000 Å, for example, about 150 Å to about 500 Å. When the thickness of the electron transport layers 230 satisfies the above-described range, a satisfactory electron transport characteristic may 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 electron injection, LiF, Lithium quinolate (LiQ), Li ₂ O, BaO, NaCl, CsF, a lanthanide metal such as Yb, or a metal halide 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 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 235 may have a thickness of about 1 Å to about 100 Å, or about 3 Å to about 90 Å. When the thickness of the electron injection layers 235 satisfies the above-described range, a satisfactory electron injection characteristic may be obtained without a substantial increase in driving voltage.

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

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 transflective electrode. Unlike the first electrode 110 , the second electrode 120 may use a combination of a metal, an electrically conductive compound, an alloy, etc. having a relatively low work function.

The second electrode 120 is a transflective electrode or a reflective electrode. The second electrode 120 includes Li (lithium), Mg (magnesium), Al (aluminum), Al-Li (aluminum-lithium), Ca (calcium), Mg-In (magnesium-indium), and Mg-Ag (magnesium). -silver) or a compound or mixture containing them (eg, a mixture of Ag and Mg). Alternatively, a plurality of layer structures 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 shown, 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 may be reduced.

An electrode and an organic material layer are formed on the illustrated substrate 100 . In this case, the substrate 100 may use a rigid or flexible material, for example, soda lime glass, alkali-free glass, aluminosilicate glass as the rigid material. PC (polycarbonate), PES (polyether sulfone), COC (cyclic oliphene copolymer), PET (polyethylene terephthalate), PEN (polyethylene naphthalate), etc. can be used as a soft material. .

In the organic light emitting device, as a voltage is applied to each of the first electrode 110 and the second electrode 120 , holes injected from the first electrode 110 pass through the hole transport regions 210 to 215 to the emission layer The electrons move to 220 , and the electrons injected from the second electrode 120 move to the emission layer 220 through the electron transport regions 230 to 235 . Electrons and holes recombine in the light emitting layer 220 to generate excitons, and the excitons emit light while falling from the excited state to the ground state.

The light path generated by the light emitting layer 220 may exhibit a very different tendency according to the refractive index of the organic/inorganic materials constituting the organic light emitting 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 . Lights contacting the second electrode 120 larger than the other critical angles are totally reflected or reflected, so that they are not emitted to the outside of the organic light emitting diode.

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

The capping layer 300 is located at the outermost part of the organic light emitting device, and has a great influence on device characteristics without affecting the driving of the device at all. Therefore, the capping layer 300 is important both in terms of both an internal protection role of the organic light emitting device and improvement of device characteristics. Organic materials absorb light energy in a specific wavelength region, which depends on the energy bandgap. If this energy bandgap is adjusted for the purpose of absorbing the UV region that can affect the organic materials inside the organic light emitting device, the capping layer 300 can be used for the purpose of protecting the organic light emitting device including improving optical properties. have.

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

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

[Example]

intermediate Synthesis example 1: Synthesis of Intermediate (1)

4-bromodibenzo [b, d] furan (4-bromodibenzo [b, d] furan) 10.0 g (40.5 mmol), benzophenone imine (Benzophenone imine) 8.1 g (44.7 mmol), Pd (dba) ₂ 0.7 g (1.2 mmol), BINAP 1.5 g (2.5 mmol), tert -butoxysodium 11.7 g (121.7 mmol) and toluene 200 mL were stirred at 110 °C all day. The reaction mixture was cooled to room temperature, passed through a celite pad, and distilled under reduced pressure to remove the solvent. The obtained compound was dissolved in 100 mL of tetrahydrofuran, and then slowly acidified (pH<2) with 4N hydrochloric acid, followed by stirring at 50 °C for 4 hours. After cooling to room temperature, tetrahydrofuran was distilled off under reduced pressure, and diethyl ether was added thereto and stirred. The resulting solid was filtered under reduced pressure, the filtered wet body was suspended in 200 mL of water, the acidity was adjusted to 8 or more with saturated sodium carbonate solution, and the mixture was stirred for 1 hour. The resulting solid was filtered, washed with water, and dried under reduced pressure. The obtained compound was purified by column chromatography to obtain 5.0 g (yield: 67%) of the compound (intermediate (1)).

intermediate Synthesis example 2: Synthesis of intermediate (3)

(Synthesis of Intermediate (2))

4-bromo-1-iodobenzene (4-bromo-1-iodobenzene) 10.0 g (35.3 mmol), dibenzofuran-4-ylboronic acid (dibenzofuran-4-ylboronic acid) 8.2 g (38.9 mmol), Pd ( A mixture of 0.2 g (1.1 mmol) of PPh ₃ ) ₄ , 36.0 mL (72.0 mmol) of 2M sodium carbonate solution, 90 mL of toluene and 36 mL of ethanol was stirred under reflux for 12 hours. The reaction mixture was cooled to room temperature, diluted with 100 mL of toluene, and washed with water. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 10.7 g (yield: 93%) of a solid compound (intermediate (2)).

(Synthesis of Intermediate (3))

Intermediate (2) 60.0 g (185.7 mmol), Benzophenone imine 37.0 g (204.2 mmol), Pd (dba) ₂ 5.3 g (9.3 mmol), BINAP 11.5 g (18.5 mmol), tert -butoxysodium A mixture of 44.6 g (464.1 mmol) and 600 mL of toluene was stirred at reflux for 12 hours. The reaction mixture was cooled to room temperature and dissolved in chloroform. The solution was passed through a celite pad and concentrated under reduced pressure. After dissolving the obtained compound in 500 mL of tetrahydrofuran, 80 mL of 6N hydrochloric acid was slowly added thereto, followed by stirring at room temperature overnight. The resulting precipitate was filtered under reduced pressure and washed with chloroform. The filtered wet body was suspended in 600 mL of water, the pH was adjusted to 8 or higher with a saturated sodium carbonate solution, and the layers were separated by extraction with chloroform. The separated chloroform layer was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The concentrated residue was slurried with dichloromethane and n-hexane to obtain 28.0 g (yield: 58%) of the compound (intermediate (3)) as a yellow solid.

intermediate Synthesis example 3: Synthesis of intermediate (4)

1- (2-bromodibenzo [b, d] furan) (1- (2-bromodibenzo [b, d] furan)) 10.0 g (40.5 mmol), Benzophenone imine 8.07 g (44.5 mmol) , Pd(dba) ₂ 0.70 g (1.22 mmol), BINAP 1.51 g (2.43 mmol), tert -butoxysodium 7.78 g (81.0 mmol) and 100 mL of toluene were stirred at reflux for 12 hours. The reaction mixture was cooled to room temperature, diluted with 100 mL of toluene, and washed twice with 200 mL of water. The organic layer was separated, dried over anhydrous sodium sulfate, filtered and concentrated. The concentrated residue was dissolved in 100 mL of tetrahydrofuran, 5 mL of 6N hydrochloric acid was slowly added thereto, and the mixture was stirred at 50 °C for 1 hour. After cooling to room temperature, the obtained solid was filtered under reduced pressure and washed with acetone. The filtered wet body was suspended in 200 mL of water, and the acidity was adjusted to 8 or higher with saturated sodium carbonate solution, followed by stirring for 1 hour. The resulting precipitate was filtered, washed with water, and dried under reduced pressure to obtain 4.09 g (yield: 55%) of intermediate (4).

intermediate Synthesis example 4: Synthesis of intermediate (5)

4-bromodibenzo[b,d]thiophene (4-bromodibenzo[b,d]thiophene) 10.0 g (38.0 mmol), benzophenone imine 6.9 g (38.0 mmol), Pd (dba) ₂ 1.1 g (1.9 mmol), BINAP 2.4 g (3.8 mmol), tert -butoxysodium 7.3 g (76.0 mmol), and a mixture of 190 mL toluene was stirred under reflux for 3 hours. After the reaction mixture was cooled to room temperature, 190 mL of distilled water was added, followed by extraction. After adding 100 mL of 6 N HCl to the organic layer and stirring at room temperature for 3 hours, the resulting solid was filtered under reduced pressure. The filtered wet body was basified (pH>8) with saturated sodium carbonate solution and extracted with 190 mL of dichloromethane. The separated organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by column chromatography to obtain 3.6 g (yield: 47.6 %) of the compound as a pale orange solid (Intermediate (5)).

intermediate Synthesis example 5: Synthesis of intermediate (6)

2-bromodibenzo[b,d]thiophene (2-bromodibenzo[b,d]thiophene) 6.0 g (22.8 mmol), benzophenone imine 4.6 mL (27.4 mmol), Pd ₂ (dba) ₃ A mixture of 1.04 g (1.14 mmol), 1.42 g (2.28 mmol) of BINAP, 22.3 g (68.4 mmol) of cesium carbonate and 110 mL of toluene was stirred at reflux for 12 hours. The reaction mixture was cooled to room temperature, filtered through a pad of Celite, and the filtrate was concentrated under reduced pressure. After dissolving the filtered wet body in 70 mL of tetrahydrofuran, 30 mL of 6N hydrochloric acid was added, followed by stirring for 1 hour. The mixture was basified (pH 7-8) with saturated sodium carbonate solution and then extracted with dichloromethane. The separated organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by column chromatography to obtain 2.72 g (yield: 59.9%) of the compound (intermediate (6)) as a brown solid.

intermediate Synthesis example 6: Synthesis of intermediate (8)

(Synthesis of Intermediate (7))

4-bromo-1-iodobenzene (4-bromo-1-iodobenzene) 10.0 g (35.3 mmol), dibenzofuran-4-ylboronic acid (dibenzofuran-4-ylboronic acid) 8.2 g (38.9 mmol), Pd ( A mixture of 0.2 g (1.1 mmol) of PPh ₃ ) ₄ , 36.0 mL (72.0 mmol) of 2M sodium carbonate solution, 90 mL of toluene and 36 mL of ethanol was stirred under reflux for 12 hours. The reaction mixture was cooled to room temperature, diluted with 100 mL of toluene, and washed with water. The organic layer was separated, dried over anhydrous magnesium sulfate, filtered, and concentrated to obtain 10.7 g (yield: 93%) of a solid compound (intermediate (7)).

(Synthesis of Intermediate (8))

Intermediate (7) 60.0 g (185.7 mmol), Benzophenone imine 37.0 g (204.2 mmol), Pd (dba) ₂ 5.3 g (9.3 mmol), BINAP 11.5 g (18.5 mmol), tert -butoxysodium A mixture of 44.6 g (464.1 mmol) and 600 mL of toluene was stirred at reflux for 12 hours. The reaction mixture was cooled to room temperature and dissolved in chloroform. The solution was passed through a celite pad and concentrated under reduced pressure. After dissolving the obtained compound in 500 mL of tetrahydrofuran, 80 mL of 6N hydrochloric acid was slowly added thereto, followed by stirring at room temperature overnight. The resulting precipitate was filtered under reduced pressure and washed with chloroform. The filtered wet body was suspended in 600 mL of water, the pH was adjusted to 8 or higher with a saturated sodium carbonate solution, and the layers were separated by extraction with chloroform. The separated chloroform layer was dried over anhydrous sodium sulfate, filtered, and concentrated under reduced pressure. The concentrated residue was slurried with dichloromethane and n-hexane to obtain 28.0 g (yield: 58%) of the compound (intermediate (8)) as a yellow solid.

intermediate Synthesis example 7: Synthesis of intermediate (9)

In a 1-neck 250 mL flask, 4.6 g (17.7 mmol) of Intermediate (3), 11.0 g (39.0 mmol) of 1-Bromo-4-iodobenzene, 0.5 g of Pd (dba) ₂ (0.9 mmol), DPPF 1.0 g (1.8 mmol), NaOtBu 5.1 g (53.2 mmol) and toluene 90 mL were added and refluxed and stirred for 4 hours. After cooling to room temperature, impurities were removed through celite filtration. After removing the solvent, it was dissolved in dichloromethane and purified by silica gel column chromatography (DCM:HEX). The obtained solid was filtered with a mixed solution (dichloromethane/acetone) to obtain 6.9 g (yield: 68.6%) of the compound as a white solid (intermediate (9)).

intermediate Synthesis example 8: Synthesis of intermediate (10)

In a 1-neck 500 mL flask, 4.0 g (20.1 mmol) of intermediate (6), 12.5 g (44.2 mmol) of 1-Bromo-4-iodobenzene, 0.6 g of Pd (dba) ₂ (1.0 mmol), DPPF 1.1 g (2.0 mmol), NaOtBu 5.8 g (60.2 mmol) and toluene 100 mL were added, followed by refluxing and stirring for 4 hours. After cooling to room temperature, impurities were removed through celite filtration. After removing the solvent, it was dissolved in dichloromethane and purified by silica gel column chromatography (DCM:HEX). The obtained solid was filtered with a mixed solution (acetone/methanol) to obtain 8.8 g (yield: 86.2%) of a yellow solid compound (intermediate (10)).

intermediate Synthesis example 8: Synthesis of intermediate (11)

10.0 g (59.1 mmol) of 6-hydroxy-2-naphthonitrile was dissolved in 300 mL of dichloromethane (DCM), and 14.0 g (177.3 mmol) of pyridine was added dropwise. The temperature was lowered to 0 °C. 20.0 g (70.9 mmol) of Tf ₂ O was slowly added dropwise, and the temperature was raised to room temperature, followed by reaction for 12 hours. After the reaction was washed with water (500 mL), the separated organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by column chromatography (CHCl ₃ ) to obtain 15.8 g of a yellow solid compound (intermediate (11)) (yield) : 88.7%) was obtained.

intermediate Synthesis example 9: Synthesis of intermediate (13)

(Synthesis of Intermediate (12))

In a 1-neck 1000 mL flask, 1-bromo-4-iodobenzene (1-bromo-4-iodobenzene) 37.2 g (131.5 mmol), dibenzo [b, d] thiophen-4-ylboronic acid (dibenzo [b ,d]thiophen-4-ylboronic acid) 30.0 g (131.5 mmol), Pd(PPh ₃ ) ₄ 4.6 g (3.9 mmol), and toluene 400 mL were added and stirred, followed by stirring. Then, ethanol 200 mL, K ₂ CO ₃ 27.3 g (197.3 mmol) )/200 mL of water was added, and the mixture was heated under reflux and stirred for 8 hours. Upon completion of the reaction, the reaction was cooled to room temperature, the solvent was removed, water was added, and the mixture was extracted with dichloromethane, the organic phase was dried over anhydrous MgSO ₄ , and purified by column chromatography (DCM) to form a slightly yellow solid compound (intermediate (12) )) 29.1 g (yield: 65.3%) was obtained.

(Synthesis of Intermediate (13))

29.1 g (85.8 mmol) of intermediate (12), 17.1 g (94.4 mmol) of benzophenone imine, 16.5 g (171.6 mmol) of NaOtBu, and 500 mL of toluene were added to a 1-neck 1000 mL flask and stirred, followed by Pd (dba) ₂ 1.5 g (2.6 mmol), 3.2 g (5.2 mmol) of BINAP were added, and the mixture was stirred under reflux under heating all day. Upon completion of the reaction, the reaction was cooled to room temperature, the solvent was removed, water was added, and the mixture was extracted with dichloromethane, the organic phase was dried over anhydrous MgSO ₄ , passed through a pad covered with celite with 1000 mL of chloroform, and the solvent was distilled off under reduced pressure. removed. A slightly brown liquid compound was added with 500 mL of tetrahydrofuran and stirred, then adjusted to pH 2 or higher with 4N HCl and stirred at 50° C. for 4 hours. When the reaction was completed, the solvent was blown off, acetone was added to the obtained solid, stirred for 30 minutes, and filtered to obtain a red solid. The solid was adjusted to pH 8 or higher with NaOH, stirred for 30 minutes, extracted with dichloromethane, the solvent was removed, and purified by column chromatography (Hex:CHCl ₃ ) to form a slightly red solid compound (intermediate (13)) 12.6 g ( Yield: 53.4%) was obtained.

Using the synthesized intermediate compound, various tertiary amine derivatives were synthesized as follows.

Example 1: Synthesis of compound 2-4 (LT19-35-308)

Intermediate (4) 2.8 g (15.4 mmol), 2-bromodibenzo [b, d] thiophene (2-bromodibenzo [b, d] thiophene) 8.9 g (33.9 mmol), Pd (dba) ₂ 1.8 g (3.1 mmol), tert -butoxysodium 7.4 g (77.1 mmol), tri- tert -butylphosphine 1.3 g (3.0 mmol, 50wt% toluene solution), and 100 mL of xylene were stirred at 110° C. for 8 hours. The reaction mixture was cooled to room temperature, water was added, and then extracted twice with 300 mL of chloroform. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained mixture was purified by column chromatography to obtain 4.9 g (yield: 58.1%) of compound 2-4 (LT19-35-308).

Example 2: Synthesis of compound 2-5 (LT19-30-224)

Intermediate (4) 1.5 g (8.2 mmol), intermediate (2) 5.3 g (16.4 mmol), Pd(dba) ₂ 0.2 g (0.4 mmol), tert - butoxysodium 2.4 g (24.6 mmol), tri-tert- A mixture of 0.3 g (0.6 mmol, 50wt% toluene solution) of butylphosphine and 23 mL of toluene was stirred under reflux for 3 hours. After the reaction mixture was cooled to room temperature, 115 mL of methanol was added thereto. The resulting semi-solid precipitate was separated and purified by column chromatography to obtain 3.4 g (yield: 62.1%) of yellow solid compound 2-5 (LT19-30-224).

Example 3: Synthesis of compound 2-9 (LT19-30-192)

Intermediate (1) 1.5 g (8.2 mmol), Intermediate (2) 5.3 g (16.4 mmol), Pd(dba) ₂ 0.2 g (1.2 mmol), tri- tert -butylphosphine 0.3 g (0.8 mmol, 50 wt% toluene) solution), 1.6 g (16.4 mmol) of sodium tert -butoxy and 82 mL of toluene was stirred at reflux for 8 hours. The reaction mixture was cooled to room temperature, washed with water, the organic layer was separated, dried over anhydrous sodium sulfate, filtered, and concentrated. The concentrated mixture was purified by column chromatography and recrystallized from dichloromethane and ethyl acetate to obtain 3.9 g (yield: 71.2%) of a white solid compound 2-9 (LT19-30-192).

Example 4: Synthesis of compound 2-13 (LT18-30-239)

Intermediate (4) 1.5 g (8.2 mmol), 2- (4-bromophenyl) benzo [d] oxazole (2- (4-bromophenyl) benzo [d] oxazole) 5.3 g (19.3 mmol), Pd (dba) ) ₂ 483 mg (840.6 μmol), tri- tert -butylphosphine 680 mg (1.7 mmol, 50wt% toluene solution), tert -butoxysodium 4.9 g (50.4mmol), and a mixture of 56 mL xylene at 120 °C was stirred for 12 hours. The reaction mixture was cooled to room temperature, diluted with chloroform, and washed with water. The organic layer was separated, dried over anhydrous sodium sulfate, filtered and concentrated. The obtained mixture was purified by column chromatography to obtain Compound 2-13 (LT18-30-239, 1.8 g (yield: 38.5%) as a yellow solid).

Example 5: Synthesis of compound 2-14 (LT19-30-305)

In a one-necked 250 mL flask, 1.3 g (7.0 mmol) of intermediate (4), 5.1 g (14.7 mmol) of 2-(4-bromophenyl)benzo[d]thiazole, and After adding 100 mL of xylene and stirring at 50 ℃, Pd(dba) ₂ 403.0 mg (0.7 mmol), Sodium tert -butoxide 2.0 g (21.0 mmol) and tri- tert -butylphospine (50wt% in Toluene) 567.2 mg ( 1.4 mmol) was added, and the mixture was stirred at 125-130 °C all day. After completion of the reaction, it was cooled to room temperature, and the reactant was passed through a celite pad with CHCl ₃ and distilled under reduced pressure to remove the solvent. The obtained compound was solidified with hexane to obtain a yellow solid, dissolved by heating in 800 mL of CHCl ₃ , and then charcoal was added and stirred for 30 minutes. Using a hot mixed solvent (Hot CHCl ₃ :EA=20:1), it was passed through a pad of Celite and SiO ₂ , and then the solvent was removed by distillation under reduced pressure. The obtained compound was purified by SiO ₂ column chromatography (EA:CHCl ₃ :HEX=1:1:5). It was slurryed with DCM and Hexane to obtain 3.1 g (yield: 73.5%) of compound 2-14 (LT19-35-305) as a yellow solid.

Example 6: Synthesis of compound 2-21 (LT19-30-312)

1.7 g (6.5 mmol) of intermediate (8), 4.6 g (14.4 mmol) of intermediate (2), sodium tert -butoxy 1.9 g (19.6 mmol), Pd(dba) ₂ 0.2 g (0.4 mmol), tri- tert -butylphosphine A mixture of 0.2 g (0.5 mmol, 50wt % toluene solution) and 150 mL of xylene was stirred under reflux throughout the day. The reaction mixture was cooled to room temperature, diluted with 500 mL of chloroform, and filtered through a pad of Celite. After the filtrate was concentrated, the residue was purified by column chromatography to obtain 2.9 g (yield: 60.7%) of compound 2-21 (LT19-35-312) as a yellow solid.

Example 7: Synthesis of compound 2-27 (LT19-30-286)

Intermediate (3) 4.0 g (15.4 mmol), 4-bromobenzonitrile (4-bromobenzonitrile) 8.4 g (46.3 mmol), Pd (dba) ₂ 1.8 g (3.1 mmol), tri- tert -butylphosphine 3.0 mL A mixture of (6.2 mmol, 50wt% toluene solution), 5.9 g (61.7 mmol) of tert -butoxysodium and 154 mL of toluene was stirred under reflux for 16 hours. The reaction mixture was cooled to room temperature, washed with water, the organic layer was separated, dried over anhydrous sodium sulfate, filtered, and concentrated. The concentrated mixture was purified by column chromatography and recrystallized from ethyl acetate to obtain 1.3 g (yield: 18.3%) of compound 2-27 (LT19-30-286) of ivory color.

Example 8: Synthesis of compound 2-29 (LT19-30-259)

Intermediate (3) 4.0 g (15.4 mmol), 2-bromodibenzo [b, d] thiophene (2-bromodibenzo [b, d] thiophene) 8.9 g (33.9 mmol), Pd (dba) ₂ 1.8 g (3.1 mmol), tert -butoxysodium 7.4 g (77.1 mmol), tri- tert -butylphosphine 1.3 g (3.0 mmol, 50wt% toluene solution), and 100 mL of xylene were stirred at 110° C. for 8 hours. The reaction mixture was cooled to room temperature, water was added, and then extracted twice with 300 mL of chloroform. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained mixture was purified by column chromatography to obtain 1.7 g (yield: 17.7%) of compound 2-29 (LT19-30-259).

Example 9: Synthesis of compound 2-36 (LT19-30-278)

Intermediate (6) 2.5 g (12.5 mmol), 4-bromobenzonitrile (4-bromobenzonitrile) 4.8 g (26.3 mmol), Pd (dba) ₂ 1.4 g (2.5 mmol), tert -butoxysodium 6.0 g (62.7) mmol), tri- tert -butylphosphine 1.0 g (2.5 mmol, 50wt% toluene solution), and 100 mL of xylene were stirred at 110° C. for 8 hours. The reaction mixture was cooled to room temperature, water was added, and then extracted twice with 300 mL of chloroform. The organic layer was dried over anhydrous magnesium sulfate, filtered, and concentrated under reduced pressure. The obtained compound was purified by column chromatography to obtain 1.4 g (yield: 27.9%) of compound 2-36 (LT19-30-278).

Example 10: Synthesis of compound 2-40 (LT19-30-218)

1.3 g (6.5 mmol) of intermediate (6), 4.6 g (14.4 mmol) of intermediate (2), sodium tert -butoxy 1.9 g (19.6 mmol), Pd(dba) ₂ 0.2 g (0.4 mmol), tri- tert -butylphosphine A mixture of 0.2 g (0.5 mmol, 50wt% toluene solution) and 150 mL of xylene was stirred at reflux throughout the day. The reaction mixture was cooled to room temperature, diluted with 500 mL of chloroform, and filtered through a pad of Celite. After the filtrate was concentrated, the residue was purified by column chromatography to obtain 2.7 g (yield: 60.7%) of compound 2-40 (LT19-30-218) as a yellow solid.

Example 11: Synthesis of compound 2-44 (LT19-30-199)

Intermediate (5) 2.0 g (10.0 mmol), Intermediate (2) 6.5 g (20.1 mmol), Pd(dba) ₂ 0.6 g (1.0 mmol), tri- tert -butylphosphine 1.0 mL (2.0 mmol, 50 wt% toluene) solution), 3.9 g (40.2 mmol) of sodium tert -butoxy and 100 mL of toluene were stirred under reflux for 8 hours. The reaction mixture was cooled to room temperature, washed with water, the organic layer was separated, dried over Na ₂ SO ₄ , filtered, and concentrated. The concentrated mixture was purified by column chromatography and recrystallized from dichloromethane and MeOH to obtain 1.5 g (yield: 21.9%) of white solid compound 2-44 (LT19-30-199).

Example 12: Synthesis of compound 2-48 (LT18-30-263)

Intermediate (6) 1.6 g (8.0 mmol), 2- (4-bromophenyl) benzo [d] oxazole (2- (4-bromophenyl) benzo [d] oxazole) 5.5 g (20.1 mmol), Pd (dba) ) ₂ 0.92 g (1.61 mmol), tri- tert -butylphosphine 1.3 g (3.2 mmol, 50wt% toluene solution), tert -butoxysodium 3.1 g (32.1 mmol), and a mixture of 54 mL of xylene were refluxed throughout the day. stirred. The reaction mixture was cooled to room temperature, filtered through a pad of Celite, and distilled under reduced pressure to remove the solvent. The obtained mixture was purified by column chromatography to obtain 3.1 g (yield: 66.2%) of compound 2-48 (LT18-30-263) as a brown solid.

Example 13: Synthesis of compound 2-87 (LT20-30-070)

In a 1-neck 250 mL flask, 2.8 g (15.3 mmol) of intermediate (4), 4'-bromo-[1.1'-biphenyl]-4-carbonitrile (4'-bromo-[1.1'-biphenyl]-4- carbonitrile) 8.7 g (33.6 mmol), NaO t Bu 4.4 g (45.8 mmol), and xylene 150 mL were added, stirred, and then Pd(dba) ₂ 0.5 g (0.9 mmol), P( t -Bu) ₃ 0.3 mL (1.2) mmol) and stirred under reflux under heating all day. Upon completion of the reaction, the reaction is cooled to room temperature, the solvent is blown off, and 500 mL of chloroform is passed through a celite pad, and then the solvent is removed by distillation under reduced pressure. It was purified by column chromatography (Hex:CHCl ₃ ) to obtain 2.5 g (yield: 30.4%) of compound 2-87 (LT20-30-070) as a yellow solid.

Example 14: Synthesis of compound 2-114 (LT20-30-068)

In a 1-neck 250 mL flask, 4.7 g (8.3 mmol) of Intermediate (9), 3.6 g (24.8 mmol) of 4-Cyanophenylboronic acid, 0.5 g (0.8 mmol) of Pd(dba) ₂ , XPhos 0.8 g (1.7 mmol), 2M K ₃ PO ₄ 16 mL (33.0 mmol) and 1,4-dioxane 40 mL were added and stirred at 85° C. for 2 hours. After cooling to room temperature, the resulting solid was filtered and washed with ethanol. The solid was boiled with chloroform (200 mL) and purified through silica gel column chromatography (CHCl ₃ :HEX). The obtained solid was filtered with dichloromethane and washed with acetone to obtain 2.9 g (yield: 58.3%) of compound 2-114 (LT20-30-068) as a yellow solid.

Example 15: Synthesis of compound 2-117 (LT20-30-260)

In a one-necked 250 mL flask, 5.0 g (19.3 mmol) of Intermediate (3), 12.2 g (40.5 mmol) of Intermediate (11), 1.1 mg (1.9 mmol) of Pd(dba) ₂ , 1.6 g of 50% t-Bu ₃ P ( 3.9 mmol), NaOtBu 5.6 g (57.9 mmol), and 80 mL of Xylene were added and mixed, followed by reaction at 120° C. for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, added with water, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained compound was purified by silica gel column chromatography (Hex:EA), dissolved in acetone, and then solidified while slowly adding methanol dropwise to obtain 1.5 g (yield: 13.8%) of compound 2-117 (LT20-30-260) as a yellow solid. got it

Example 16: Synthesis of compound 2-123 (LT20-30-051)

Intermediate (10) 4.6 g (9.0 mmol), 4-Cyanophenylboronic acid 4.0 g (27.1 mmol), Pd(dba) ₂ 0.5 g (0.9 mmol), XPhos in a 1-neck 250 mL flask 0.9 g (1.8 mmol), 2M K ₃ PO ₄ 18 mL (36.1 mmol) and 1,4-dioxane 45 mL were added and stirred at 85° C. for 2 hours. After cooling to room temperature, the resulting solid was filtered and washed with ethanol. After boiling the solid with chloroform, it was purified by silica gel column chromatography (CHCl ₃ :HEX). The obtained solid was boiled with dichloromethane, cooled, filtered and washed with acetone to obtain 3.4 g (yield: 68.7%) of compound 2-123 (LT20-30-051) as a yellow solid.

Example 17: Synthesis of compound 2-153 (LT20-35-365)

In a one-necked 250 mL flask, 5.0 g (18.2 mmol) of Intermediate (13), 11.5 g (38.1 mmol) of Intermediate (11), 1.0 mg (1.8 mmol) of Pd(dba) ₂ , 1.5 g of 50% t-Bu ₃ P ( 3.6 mmol), NaOtBu 5.2 g (54.5 mmol) and Xylene 80 mL were added and mixed, followed by reaction at 120° C. for 12 hours. After completion of the reaction, the mixture was cooled to room temperature, added with water, extracted with chloroform, and the solvent was removed under reduced pressure. The obtained compound was purified by silica gel column chromatography (Hex:EA), dissolved in acetone, and then solidified while slowly adding methanol dropwise to obtain 1.1 g of compound 2-153 (LT20-35-365) as a yellow solid (yield: 10.5%) got it

<Test Example>

For the compounds of the present invention J.A. Measure n (refractive index) and k (extinction coefficient) of a single film for optical property evaluation using WOOLLAM's Ellipsometer device.

Fabrication of single film for evaluation of optical properties:

To measure the optical properties of the compound, the glass substrate (0.7T) was washed with Ethanol, DI Water, and Acetone for 10 minutes each, and then treated with oxygen plasma on the glass substrate at 2×10 ^{- 2} Torr at 125 W for 2 minutes and then with 9× A single film is fabricated by depositing 800 Å of the compound on a glass substrate at a rate of 1 Å/sec in a vacuum of 10 ^{- 7} Torr.

Comparative test example:

REF01 was used as a compound in the production of the single film for evaluation of optical properties.

< Test Examples 1 to 17 >

In the comparative test example, a single membrane 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 optical properties of the compounds according to the Comparative Test Examples and Test Examples 1 to 17.

The optical properties are the refractive index constants at 450 nm and 620 nm wavelengths and the absorption coefficient constants at 380 nm wavelengths.

division compound n (450 nm, 620 nm) k (380 nm) Comparative test example REF01 2.000, 1.846 0.193 Test Example 1 2-4
(LT19-35-308) 2.020, 1.884 0.253 Test Example 2 2-5
(LT19-30-224) 2.076, 1.922 0.557 Test Example 3 2-9
(LT19-30-192) 2.081,1.853 0.456 Test Example 4 2-13
(LT18-30-239) 2.241, 1.941 0.864 Test Example 5 2-14
(LT19-35-305) 2.282, 1.983 0.592 Test Example 6 2-21
(LT19-35-312) 2.123, 1.921 0.321 Test Example 7 2-27
(LT19-30-286) 2.111, 1.888 0.532 Test Example 8 2-29
(LT19-30-259) 2.041, 1.899 0.421 Test Example 9 2-36
(LT19-30-278) 2.123, 1.921 0.321 Test Example 10 2-40
(LT19-30-218) 2.086, 1.929 0.539 Test Example 11 2-44
(LT19-30-199) 2.020, 1.884 0.253 Test Example 12 2-48
(LT18-30-263) 2.283, 1.968 0.920 Test Example 13 2-87
(LT20-30-070) 2.253, 1.973 0.809 Test Example 14 2-114
(LT20-30-068) 2.302, 2.015 0.936 Test Example 15 2-117
(LT20-30-260) 2.294, 2.014 0.672 Test Example 16 2-123
(LT20-30-051) 2.265, 1.986 0.758 Test Example 17 2-153
(LT20-35-365) 2.284, 2.019 0.714

As can be seen from Table 1, n values in the blue region (450 nm) and the red region (620 nm) of Comparative Test Example (REF01) were 2.000 and 1.846, respectively, whereas most of the compounds according to the present invention were generally As a result, it was confirmed to have a higher refractive index than that of Comparative Test Example compound (REF01) in the blue region, the green region and the red region. This satisfies the high refractive index value required to secure a high viewing angle in the blue region.

In addition, it was confirmed that the k value at 380 nm corresponding to the starting stage of the UV region was also high for most of the example compounds. This will effectively absorb a high energy external light source in the UV region to minimize damage to organic materials inside the organic light emitting device, thereby contributing to the substantial improvement of the lifespan of the organic light emitting device.

<Example>

device fabrication

For device fabrication, ITO, a transparent electrode, was used as the anode layer, 2-TNATA for the hole injection layer, NPB for the hole transport layer, αβ-ADN for the host of the emission layer, Pyene-CN for the blue fluorescent dopant, and Liq for the electron injection layer. , Mg:Ag was used as the negative electrode. The structures of these compounds are as follows.

Comparative Example: ITO / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN: 10% Pyrene-CN (30 nm) / Alq ₃ (30 nm) / Liq (2 nm) / Mg: Ag (1:9, 10 nm) / REF01 (60 nm)

Blue fluorescence organic light emitting diode ITO (180 nm) / 2-TNATA (60 nm) / NPB (20 nm) / αβ-ADN:Pyrene-CN 10% (30 nm) / Alq ₃ (30 nm) / Liq (2 nm) / Mg:Ag (1:9, 10 nm) / REF (60 nm) by deposition in the order to fabricate a device. Before depositing the organic material, the ITO electrode was subjected to oxygen plasma treatment at 2 × 10 ^{- 2} Torr at 125 W for 2 minutes. Organic materials were deposited at a vacuum degree of 9 × 10 ^{- 7} Torr, Liq was 0.1 Å/sec, αβ-ADN was 0.18 Å/sec, and Pyrene-CN was simultaneously deposited at 0.02 Å/sec, and the remaining organic materials were all 1 Deposited at a rate of Å/sec. The capping layer material used in the experiment was selected as REF01. After the device was manufactured, it was encapsulated in a glove box filled with nitrogen gas to prevent the device from contacting air and moisture. After forming the barrier with 3M's adhesive tape, barium oxide, a moisture absorbent that can remove moisture, was added and a glass plate was attached.

< Examples 1 to 17 >

In the comparative example, a device was manufactured in the same manner as in the comparative example, except that each compound shown in Table 2 was used instead of REF01.

Table 2 shows the electroluminescence characteristics of the organic light emitting devices prepared in Comparative Examples and Examples 1 to 17.

division compound Driving voltage [V] Efficiency [cd/A] life span(%) Comparative Example REF01 4.50 5.10 88.92 Example 1 2-4
(LT19-35-308) 4.42 6.11 97.54 Example 2 2-5
(LT19-30-224) 4.47 6.52 98.13 Example 3 2-9
(LT19-30-192) 4.45 6.13 97.45 Example 4 2-13
(LT18-30-239) 4.38 6.23 97.40 Example 5 2-14
(LT19-35-305) 4.40 6.10 97.32 Example 6 2-21
(LT19-35-312) 4.41 6.23 97.55 Example 7 2-27
(LT19-30-286) 4.42 6.00 98.00 Example 8 2-29
(LT19-30-259) 4.49 5.99 95.61 Example 9 2-36
(LT19-30-278) 4.40 6.22 98.11 Example 10 2-40
(LT19-30-218) 4.42 6.11 97.54 Example 11 2-44
(LT19-30-199) 4.40 6.25 97.42 Example 12 2-48
(LT18-30-263) 4.41 6.23 97.55 Example 13 2-87
(LT20-30-070) 4.45 6.12 97.35 Example 14 2-114
(LT20-30-068) 4.45 6.21 97.91 Example 15 2-117
(LT20-30-260) 4.43 6.11 97.56 Example 16 2-123
(LT20-30-051) 4.45 6.22 97.00 Example 17 2-153
(LT20-35-365) 4.44 6.15 97.49

From the results of Table 2 above, a specific tertiary amine derivative compound according to the present invention can be used as a material for a capping layer of an organic electronic device including an organic light emitting device, and an organic electronic device including an organic light emitting device using the same has efficiency, It can be seen that it exhibits excellent characteristics such as driving voltage and stability. In particular, the compound according to the present invention exhibited high efficiency characteristics due to excellent micro-cavity ability.

The compound of Formula 1 has unexpectedly desirable properties for use as a capping layer in an OLED.

The compound of the present invention can be applied to industrial organic electronic device products due to these properties.

However, the above-described synthesis example is an example, and the reaction conditions may be changed as needed. 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 into the core structure represented by Formula 1, it may have properties suitable for use in an organic electroluminescent device.

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 (3)

A tertiary amine derivative for a capping layer of an organic electroluminescent device, represented by the following formula (1).
[Formula 1]

Z ₁ is O or S;
n, p and q are each independently 0 or 1,
Ar ₁ and Ar ₂ are the same as each other, and a cyano group; an aryl group substituted with a cyano group; a substituted or unsubstituted benzoxazole group; and a substituted or unsubstituted benzthiazole group; any one selected from The method of claim 1,
Formula 1 is a tertiary amine derivative for a capping layer of an organic electroluminescent device selected from compounds represented by Formula 2 below.
[Formula 2]

a first electrode;
an organic material layer formed of a plurality of organic material layers disposed on the first electrode;
a second electrode disposed on the organic material layer; and
a capping layer disposed on the second electrode; and
The capping layer is an organic electroluminescent device comprising the tertiary amine derivative of claim 1 or 2.

Images