KR20230131993A - Carbazole derivatives and organic electroluminescent device including the same - Google Patents

Abstract

Provided is a high-refractive carbazole derivative that contributes to substantially improving the lifespan of organic electroluminescent devices by effectively absorbing high-energy external light sources in the UV region and minimizing damage to organic substances inside organic electroluminescent devices.
The organic electroluminescent device according to the present invention includes a first electrode; second electrode; One or more organic layers disposed between the first electrode and the second electrode; and a capping layer, wherein the capping layer includes a high refractive index carbazole derivative represented by the following formula (1).
[Formula 1]

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

Description

Carbazole derivatives and organic electroluminescent device including the same}

The present invention relates to a carbazole derivative and an organic electroluminescent device containing the same. The present invention relates to a carbazole derivative that allows an organic electroluminescent device including a capping layer to have both a high refractive index characteristic and an ultraviolet ray absorption characteristic.

In the display industry, OLED (Organic Light Emitting Diodes) is attracting attention as a display that uses the self-luminescence phenomenon.

In OLED, research on carrier injection-type electroluminescence (EL) using a single crystal of anthracene aromatic hydrocarbon was first attempted by Pope et al. in 1963. From these studies, the basic mechanisms and electroluminescence properties of charge injection, recombination, exciton generation, and luminescence in organic materials have been understood and studied.

In particular, various approaches, such as changing the structure of the device and developing materials, are being used 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 an OLED display is generally an anode, a hole injection layer (HIL), a hole transport layer (HTL), an emission layer (EML), and an electron transport layer. It consists of a multilayer structure of ETL) and a cathode, and has a sandwich structure in which an electro-organic multilayer film is formed between the two electrodes.

In general, organic luminescence refers to a phenomenon that converts electrical energy into light energy using organic materials. Organic light-emitting devices that utilize the organic light-emitting phenomenon usually have a structure including an anode, a cathode, and an organic material layer between them. Here, the organic material layer is often composed of a multi-layer structure made of different materials to increase the efficiency and stability of the organic light-emitting device, and may include, for example, a hole injection layer, a hole transport layer, a light-emitting layer, an electron transport layer, and an electron injection layer.

In the structure of this organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode into the organic material layer, and when the injected holes and electrons meet, an exciton is formed, and this exciton When it falls to the ground state, it glows. These organic light-emitting devices are known to have characteristics such as self-luminescence, high brightness, high efficiency, low driving voltage, wide viewing angle, high contrast, and high-speed response.

Materials used as organic layers in organic light-emitting devices can 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.

Depending on the color of the light, there are blue, green, and red light emitting materials, as well as yellow and orange light emitting materials needed to achieve better natural colors. Additionally, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system can be used as a luminescent material. The principle is that when a small amount of a dopant, which has a smaller energy band gap and higher luminous efficiency than the host that mainly constitutes the light-emitting layer, is mixed into the light-emitting layer, the exciton generated in the host is transported to the dopant and emits light with high efficiency. At this time, since the wavelength of the host moves to the wavelength of the dopant, light of the desired wavelength can be obtained depending on the type of dopant used.

In order to fully express the excellent characteristics of the above-described organic light-emitting device, materials forming the organic material layer within the device, such as hole injection materials, hole transport materials, light-emitting materials, electron transport materials, and electron injection materials, have been developed and commercialized. The performance of organic light emitting devices is being recognized by products.

However, as organic light-emitting devices are commercialized and time passes, the need for other characteristics in addition to the light-emitting characteristics of the organic light-emitting devices themselves is emerging.

Since organic light-emitting devices are often exposed to external light sources for a long time, they are in an environment where they are exposed to high-energy ultraviolet rays. Accordingly, there is a problem in that the organic materials that make up the organic light emitting device are continuously affected. To prevent exposure to such high-energy light sources, the problem can be solved by applying a capping layer with ultraviolet absorbing properties to the organic light-emitting device.

It is generally known that the viewing angle characteristics of organic light-emitting devices are wide, but in terms of the light source spectrum, significant deviations occur depending on the viewing angle, which depends on the overall refractive index of the glass substrate, organic materials, and electrode materials that make up the organic light-emitting device and the emission wavelength of the organic light-emitting device. This is due to the deviation occurring between the appropriate refractive indices.

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

The efficiency of organic light emitting devices can generally be divided into internal luminescent efficiency and external luminescent efficiency. Internal luminescence efficiency is related to the efficiency of formation of excitons in the organic layer for photoconversion to occur.

External light-emitting efficiency refers to the efficiency with which light generated in the organic layer is emitted outside the organic light-emitting device.

In order to improve overall efficiency, it is necessary to increase not only internal luminous efficiency but also external luminous efficiency, and therefore, the development of a capping layer (CPL, luminous efficiency improvement layer) material with excellent ability to increase external luminous efficiency is required.

Meanwhile, compared to the top device structure of the resonance structure and the bottom device structure of the non-resonance structure, the formed light is reflected by the anode, which is a reflective film, and comes out toward the cathode, resulting in optical energy loss due to SPP (Surface Plasmon Polariton). big.

Therefore, one of the important methods to improve the shape and efficiency of the EL spectrum is to use a light efficiency improvement layer (capping layer) on the top cathode.

In general, four types of metals, Al, Pt, Ag, and Au, are mainly used for electron emission in SPP, and surface plasmons are generated on the surface of the metal electrode. For example, when Ag is used as the cathode, the emitted light is quenched by SPP (light energy loss due to Ag), reducing efficiency.

On the other hand, when a capping layer (light efficiency improvement layer) is used, SPP occurs at the interface between the MgAg electrode and the organic material. In this case, if the organic material has a high refractive index (for example, n>1.69 @620), TE (Transverse Electric) polarized light is extinguished in the vertical direction on the capping layer surface (luminous efficiency improvement layer surface) by an evanescent wave, and TM (transverse magnetic) polarized light moving along the cathode and capping layer causes surface plasma resonance. Amplification of the wavelength occurs due to plasma resonance, which increases the intensity of the peak, enabling high efficiency and effective color purity control.

However, there is still a need to develop materials and structures necessary to improve various characteristics in a balanced manner along with improving efficiency and color purity in organic light-emitting devices.

Republic of Korea Patent Publication No. 2016-0062307 (Title of invention: Organic light emitting display device including high refractive index capping layer) Republic of Korea Patent Publication No. 10-2170558 (Title of invention: Organic light-emitting compound and organic light-emitting device containing the same) Republic of Korea Patent Publication No. 10-2080737 (Title of invention: Organic light-emitting compound and organic light-emitting device containing the same) Republic of Korea Patent Publication No. 10-2251836 (Title of invention: Organic light-emitting compound and organic light-emitting device containing the same)

An object of the present invention is 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.

The purpose of the present invention is to provide a high-efficiency and long-life organic electroluminescent device including a capping layer with high refractive index and heat resistance in order to improve the light extraction rate of the organic electroluminescent device.

In order to achieve the above object, the present inventors conducted an example study as shown below.

That is, materials with greatly improved refractive index were selected by introducing cyano groups and benzazole groups as functional groups with high refractive index characteristics into the carbazole parent core structure with excellent thermal stability. Then, an organic light-emitting device was manufactured using this material as a capping layer, and the characteristics of the device were evaluated as an example.

The present invention relates to a first electrode; An organic material layer disposed on the first electrode; a second electrode disposed on the organic layer; and a capping layer disposed on the second electrode, wherein the organic layer or capping layer includes a carbazole derivative represented by the following formula (1).

[Formula 1]

In Formula 1,

a, b and c are each independently integers from 0 to 2,

L ₁ , L ₂ and L ₃ are each independently a phenylene group with a substituted or unsubstituted cyano group; A naphthylene group with a substituted or unsubstituted cyano group; And a cyano group substituted or unsubstituted pyridylene group; is selected from,

x, y and z are each independently integers from 0 to 3,

Ar _{1 ,} Ar ₂ and Ar ₃ are each independently a phenyl group; naphthyl group; phenanthrene group; triphenylene group; triazine group; benzofuran group; benzothiophene group; carbazole group; Dibenzofuran group; Dibenzothiophene group; fluorene group; benzoxazole group and benzothiazole group; is selected from among

The compounds described in this specification can be used as a material for the organic layer of an organic light-emitting device.

The compound according to at least one embodiment exhibits ultraviolet ray absorption characteristics, can minimize damage to organic matter in an organic light-emitting device by an external light source, and can improve efficiency, low driving voltage, and/or lifespan characteristics in the organic light-emitting device. there is.

In addition, in organic light-emitting devices using the compounds described in this specification as a capping layer, color purity can be significantly improved by improving luminous efficiency and reducing the half-width of the emission spectrum.

The compound according to the present invention exhibits an unexpectedly high refractive index by introducing a cyano group and a benzazole group into a conventional compound. As a result, the carbazole compound with a high refractive index improves the viewing angle and luminous efficiency of light extracted into the air. It can be used as a material for a capping layer (light efficiency improvement layer).

1 shows 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. (235) shows an example of an organic light emitting device in which the second electrode 120 and the capping layer 300 are sequentially stacked.
Figure 2 is a graph of light refraction and absorption characteristics when using a carbazole derivative according to an embodiment of the present invention.

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

Since the present invention can be subject to various changes and have various forms, 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 disclosed form, and should be understood to include all changes, equivalents, and substitutes included in the spirit and technical scope of the present invention.

While describing each drawing, similar reference numerals are used for similar components. In the attached drawings, the dimensions of the structures are enlarged from the actual size for clarity of the present invention. Terms such as first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, a first component may be named a second component, and similarly, the second component may also be named a first component without departing from the scope of the present invention. Singular expressions include plural expressions unless the context clearly dictates otherwise.

In this application, terms such as “comprise” or “have” are intended to designate the presence of features, numbers, steps, operations, components, parts, or combinations thereof described in the specification, but are not intended to indicate the presence of one or more other features. It should be understood that this does not exclude in advance the possibility of the existence or addition of elements, numbers, steps, operations, components, parts, or combinations thereof. Additionally, when a part of a layer, membrane, region, plate, etc. is said to be “on” another part, this includes not only being “directly above” the other part, but also cases where there is another part in between.

In this 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 alkenyl group. , may mean substituted or unsubstituted with one or more substituents selected from the group consisting of an aryl group, heteroaryl group, and heterocyclic group. Additionally, each of the above-exemplified substituents may be substituted or unsubstituted. For example, a biphenyl group may be interpreted as an aryl group, or as a phenyl group substituted with a phenyl group.

In this specification, examples of halogen atoms include fluorine atom, chlorine atom, bromine atom, or iodine atom.

As used herein, alkyl groups may be straight chain, branched chain, or cyclic. The carbon number of the alkyl group is 1 to 50, 1 to 30, 1 to 20, 1 to 10, or 1 to 6. Examples of alkyl groups 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, and 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-octyl group 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-tricosyl group Examples include syl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, n-heptacosyl group, n-octacosyl group, n-nonacosyl group, and n-triacontyl group, It is not limited to these.

As used herein, hydrocarbon ring group refers to 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 refers to 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 to 30, 6 to 20, or 6 to 15. Examples of aryl groups include phenyl group, naphthyl group, fluorenyl group, anthracenyl group, phenanthryl group, biphenyl group, terphenyl group, quarterphenyl group, quincphenyl group, sexiphenyl group, triphenylenyl group, pyrenyl group, perylenyl group, naphtha. Examples include cenyl group, pyrenyl group, benzofluoranthenyl group, chrysenyl group, etc., but are not limited to these.

In the present specification, the fluorenyl group may be substituted, and two substituents may be combined with each other to form a spiro structure.

In the present specification, the heteroaryl group may be a heteroaryl group containing one or more of O, N, P, Si, and S as heterogeneous elements. The N and S atoms may optionally be oxidized, and the N atom(s) may optionally be quaternized. The number of ring-forming carbon atoms of the heteroaryl group is 2 to 30 or 2 to 20. The heteroaryl group may be a monocyclic heteroaryl group or a polycyclic heteroaryl group. For example, the polycyclic heteroaryl group may have a 2- or 3-ring structure.

Examples of heteroaryl groups include thiophene group, furan group, pyrrole group, imidazole group, pyrazolyl group, thiazole group, oxazole group, oxadiazole group, triazole group, pyridine group, bipyridine group, pyrimidine group, and triazine group. , tetrazine group, triazole group, tetrazole group, acridyl group, pyridazine group, pyrazinyl group, quinoline group, quinazoline group, quinoxaline group, phenoxazine group, phthalazine group, pyrido pyrimidine group, pyrido pyrazino Pyrazine group, isoquinoline group, cinol group, indole group, isoindole group, indazole group, carbazole group, N-arylcarbazole group, N-heteroarylcarbazole group, N-alkylcarbazole group, benzoxazole group, benzimidazole 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, benzodioxole group, dibenzosilol group, dibenzofuran group, isobenzofuran group, etc. It is not limited to these. In addition, there are quaternary salts such as N-oxide aryl groups corresponding to the monocyclic heteroaryl group or polycyclic heteroaryl group, for example, pyridyl N-oxide group, quinolyl N-oxide group, etc. It is not limited.

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

As used herein, boron groups include alkyl boron groups and aryl boron groups. Examples of boron groups include, but are not limited to, trimethyl boron group, triethyl boron group, t-butyldimethyl boron group, triphenyl boron group, diphenyl boron group, and phenyl boron group.

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

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 simultaneously.

Specific examples of aryl amine groups include phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 3-methyl-phenylamine group, 4-methyl-naphthylamine group, and 2-methyl-biphenylamine. group, 9-methyl-anthracenylamine group, diphenyl amine group, phenyl naphthylamine group, ditolyl amine group, phenyl tolyl amine group, carbazole and triphenyl amine group, etc., but is not limited thereto.

In the present specification, examples of heteroarylamine groups 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 containing 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 simultaneously.

In the present specification, an arylheteroarylamine 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 on which the substituent is substituted, another substituent substituted on the atom on which the substituent is substituted, or a substituent that is sterically closest to the substituent. there is. For example, in 1,2-dimethylbenzene, the two methyl groups can be interpreted as “adjacent groups,” and in 1,1-diethylcyclopentene, the two methyl groups can be interpreted as “adjacent groups.” The ethyl groups can be interpreted as “adjacent groups”.

Hereinafter, carbazole derivative compounds used in the organic layer and/or capping layer will be described.

A carbazole derivative compound according to an embodiment of the present invention is represented by the following formula (1).

[Formula 1]

In Formula 1,

a, b and c are each independently integers from 0 to 2,

L ₁ , L ₂ and L ₃ are each independently a phenylene group with a substituted or unsubstituted cyano group; A naphthylene group with a substituted or unsubstituted cyano group; And a cyano group substituted or unsubstituted pyridylene group; is selected from,

x, y and z are each independently integers from 0 to 3,

Ar _{1 ,} Ar ₂ and Ar ₃ are each independently a phenyl group; naphthyl group; phenanthrene group; triphenylene group; triazine group; benzofuran group; benzothiophene group; carbazole group; Dibenzofuran group; Dibenzothiophene group; fluorene group; benzoxazole group and benzothiazole group; is selected from among

In the present invention, the carbazole derivative represented by Formula 1 is represented by Formulas 2 to 5 below.

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 2 to 5,

Z _1, Z ₂ , Z ₃ and Z ₄ are each independently selected from O, S and NR ₁ (where R ₁ is a phenyl group),

Q ₁ and Q ₂ are each independently CH or N,

L ₁ , L ₂ , L ₃ , Ar ₁ , a, b, c, x, y and z are as defined in Formula 1 above.

In one embodiment of the present invention, the carbazole derivative represented by Formula 1 may be any one selected from compounds represented by Formula 6 below, and the following compounds may be further substituted.

[Formula 6]

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

1 is a cross-sectional view schematically showing an organic light-emitting device according to an embodiment of the present invention. Referring to FIG. 1, the organic light emitting device according to one embodiment includes a first electrode 110, a hole injection layer 210, a hole transport layer 215, a light emitting layer 220, and an electron layer 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 an 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 device of one embodiment shown in FIG. 1, the first electrode 110 is conductive. The first electrode 110 may be formed of a metal alloy or a conductive compound. The first electrode 110 is generally an anode, but its function as an electrode is not limited.

The first electrode 110 may be formed on the substrate 100 using an electrode material deposition method, electron beam evaporation, or sputtering method. The material of the first electrode 110 may be selected from materials with 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 light 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), and Mg-Ag (magnesium-silver), which are not oxides. It can also be manufactured using the same metal. Recently, carbon substrate flexible electrode materials such as CNT (carbon nanotube) and graphene may be used.

The organic material layer 200 may be formed of multiple 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. It may include an electron transport region (230-235) disposed on (220).

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

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 may provide smooth hole injection and transport into the organic light emitting device. It has a thicker thickness than the electron transport area 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 composed of a hole injection material and a hole transport material. there is. 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 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 It may have an blocking layer (EBL) structure, 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 vacuum deposition, spin coating, casting, and LB method. When forming the hole injection layer 210 by vacuum deposition, the deposition conditions are 100 to 500 Å depending on the compound used as the hole injection layer 210 material, the structure and thermal characteristics of the target hole injection layer 210, etc. The deposition rate can be freely adjusted to around 1Å/s and is not limited to specific conditions. When forming the hole injection layer 210 by spin coating, the coating conditions vary depending on the properties between the compound used as the hole injection layer 210 material and the layers formed at the interface, but the coating speed and coating are adjusted for uniform film formation. Afterwards, heat treatment to remove the solvent is required.

The hole transport region (210-215) is, for example, m-MTDATA, TDATA, 2-TNATA, NPB, β-NPB, TPD, Spiro-TPD, Spiro-NPB, methylated-NPB, TAPC, HMTPD, TCTA (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: May include polyaniline/camphor sulfonic acid), PANI/PSS (Polyaniline)/Poly(4-styrenesulfonate):polyaniline)/poly(4-styrenesulfonate)), etc.

The hole transport regions 210 to 215 may have a thickness of about 100 to about 10,000 Å, and the corresponding organic material layers in each hole transport region 210 to 215 are not limited to the same thickness. For example, if the hole injection layer 210 has a thickness of 50 Å, the hole transport layer 215 can have a thickness of 1000 Å, and the electron blocking layer can have a thickness of 500 Å. The thickness conditions of the hole transport regions 210 to 215 can be set to satisfy efficiency and lifespan within a range that does not increase the driving voltage of the organic light-emitting device. The organic material layer 200 includes a hole injection layer 210, a hole transport layer 215, a functional layer having both a hole injection function and a hole transport function, 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 a functional layer having both an electron transport function and an electron injection function.

The hole transport regions 210 to 215, like the light emitting layer 220, can be doped to improve the properties, and doping of a charge-generating material into these hole transport regions 210 to 215 can improve the electrical characteristics of the organic light emitting device. You can.

The charge-generating material is generally made of a material with very low HOMO and LUMO. For example, the LUMO of the charge-generating material has a similar value to the HOMO of the hole transport layer 215 material. Due to this low LUMO, holes are easily transferred to the adjacent hole transport layer 215 using the electron-empty characteristic of LUMO, thereby improving electrical characteristics.

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); metal oxides such as tungsten oxide and molybdenum oxide; and cyano group-containing compounds, but are not limited thereto.

In addition to the previously mentioned materials, the hole transport regions 210 to 215 may further include a charge generating material to improve conductivity.

The charge generating material may be uniformly or non-uniformly dispersed within the hole transport 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 TCNQ (Tetracyanoquinodimethane) and F4-TCNQ (2,3,5,6-tetrafluoro-tetracyanoquinodimethane), metal oxides such as tungsten oxide and molybdenum oxide, etc. Examples include, but are not limited to.

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 can increase light emission efficiency by compensating for the resonance distance according to the wavelength of light emitted from the light emitting layer 220. Materials included in the hole buffer layer may be materials that can be included in the hole transport regions 210 to 215.

The electron blocking layer is a layer that serves to prevent electron injection from the electron transport regions 230 to 235 into the hole transport regions 210 to 215. The electron blocking layer not only blocks electrons moving to the hole transport region, but also can be made of a material with a high T1 value to prevent excitons formed in the light-emitting layer 220 from diffusing into the hole transport region 210 to 215. For example, the host of the light emitting layer 220, which generally has a high T ₁ value, can be used as the electron blocking layer material.

The light emitting layer 220 is provided on the hole transport regions 210 to 215. For example, the light emitting layer 220 may have a thickness of 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 multi-layer 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 forming the light-emitting layer 220 must have an appropriate energy band gap to exhibit high light-emitting characteristics and the desired light-emitting color, and generally plays two roles as a host and a dopant. It is made of two materials, but is not limited to these.

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

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

Electron transport regions 230 to 235 are provided on the light emitting 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 composed of an electron injection material and an electron transport material. there is. In addition, the electron transport regions 230 to 235 have a single-layer structure made of a plurality of different materials, or have an electron transport layer 230/electron injection layer 235 or a hole blocking layer sequentially stacked from the light emitting layer 220. It may have a structure of layer/electron transport layer 230/electron injection layer 235, 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 are formed using various methods such as vacuum deposition, spin coating, casting, LB (Langmuir-Blodgett), inkjet printing, laser printing, and laser induced thermal imaging (LITI) methods. 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, it is not limited to this, 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), It may include ADN (9,10-di(naphthalene-2-yl)anthracene) and mixtures thereof.

The electron transport layer 230 is selected from a material with fast or slow electron mobility depending on the structure of the organic light emitting device, so it is necessary to select a variety of materials, and in some cases, it is doped with Liq or Li as shown below.

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

When the electron transport region 230 to 235 includes the electron injection layer 235, the electron transport region 230 to 235 is selected from a metal material that facilitates injection of electrons, such as LiF, LiQ (Lithium quinolate), Lanthanide metals such as Li ₂ O, BaO, NaCl, CsF, and Yb, or halogenated metals such as RbCl and RbI may be used, but are not limited thereto.

The electron injection layer 235 may also be made of a material that is a mixture of an electron transport material and an insulating organo metal salt. Organic metal salts can be materials with an energy band gap of approximately 4 eV or more. Specifically, for example, the organometallic salt may include metal acetate, metal benzoate, metal acetoacetate, metal acetylacetonate, or metal stearate. You can. The thickness of the electron injection layers 235 may be about 1Å to about 100Å, or about 3Å to about 90Å. When the thickness of the electron injection layers 235 satisfies the range described above, satisfactory electron injection characteristics can be obtained without a substantial increase in driving voltage.

As mentioned 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 BCP (2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline), Bphen (4,7-diphenyl-1,10-phenanthroline), and Balq. It can be done, but it 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. Unlike the first electrode 110, the second electrode 120 may be used in combination with metals, electrically conductive compounds, alloys, 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 these (for example, a mixture of Ag and Mg). Or a plurality of layer structure including a reflective film or semi-transmissive film formed of the above materials and a transparent conductive film formed of ITO (indium tin oxide), IZO (indium zinc oxide), ZnO (zinc oxide), ITZO (indium tin zinc oxide), etc. It can be.

Although not shown, the second electrode 120 may be connected to an 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 material may be a hard or soft material. For example, hard materials include soda lime glass, alkali-free glass, and alumino silicate. Glass, etc. can be used, and soft materials such as PC (polycarbonate), PES (polyether sulfone), COC (cyclic olipencopolymer), PET (polyethylene terephthalate), and PEN (polyethylene naphthalate) can be used. there is.

In an organic light emitting device, as voltage is applied to 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 and then pass through the light emitting layer. 220, and the electrons injected from the second electrode 120 move to the light emitting 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 as they fall from the excited state to the ground state.

The optical path generated in the light emitting layer 220 may exhibit very different trends depending on the refractive index of the organic and inorganic materials that make up the organic light emitting device. Light passing through the second electrode 120 can only pass through at an angle smaller than the critical angle of the second electrode 120. Other lights that contact the second electrode 120 at a angle greater than the critical angle are totally reflected or reflected and are not emitted outside the organic light emitting device.

If the capping layer 300 has a high refractive index, it contributes to improving luminous efficiency by reducing total reflection or reflection phenomenon, and if it has an appropriate thickness, it maximizes the micro-cavity phenomenon and contributes to high efficiency and color purity. .

The capping layer 300 is located on the outermost side of the organic light emitting device and has a significant influence on the device characteristics without affecting the operation of the device at all. Therefore, the capping layer 300 serves to protect the interior of the organic light-emitting device and at the same time helps the light generated in the organic light-emitting layer 220 to be efficiently emitted to the outside. Organic materials absorb light energy in a specific wavelength range and this depends on the energy band gap. By adjusting this energy band gap for the purpose of absorbing the UV region, which 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. there is. And the capping layer 300 containing this tertiary amine compound has a large refractive index of 1.9 or more. For example, the capping layer may have a refractive index ranging from 1.9 to 3.0. When the refractive index of the capping layer 300 is high, light may be reflected at the interface of the capping layer 300, thereby causing light resonance.

The organic light emitting device according to the present specification may be a front emitting type, a back emitting type, or a double-sided emitting type depending on the material used.

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

[Example]

intermediate Synthesis example 1: Synthesis of intermediate (3)

(Synthesis of intermediate (1))

In one 2000 mL flask, 50.0 g (235.8 mmol) of 4-bromo-3-methoxybenzonitrile, 4-chloro-2-fluorophenylboronic acid (4-chloro-2) -fluorophenylboronic acid) 45.2 g (259.4 mmol), Pd(PPh ₃ ) ₄ After mixing and stirring 8.2 g (7.1 mmol) and 800 mL of toluene, 400 mL of ethanol, 65.2 g (471.6 mmol) of K ₂ CO ₃ and 400 mL of distilled water were added and stirred under heating and reflux all day. After confirming the completion of the reaction, it was cooled to room temperature and the solvent was removed. The organic layer separated by extraction with ethyl acetate and distilled water was distilled under reduced pressure to remove the solvent. It was purified by column chromatography (Hex:CHCl ₃ ) to obtain 43.2 g (yield: 70.0%) of the compound (Intermediate (1)) as a yellow solid.

(Synthesis of intermediate (2))

In a one-neck 2000 mL flask, mix and stir 43.2 g (165.1 mmol) of intermediate (1) and 850 mL of dichloromethane, then slowly add 23.9 mL (247.6 mmol) of boron tribromide (BBr ₃ ) dropwise at 0°C. Afterwards, the temperature was raised to room temperature and stirred for 5 days. After confirming the completion of the reaction, distilled water was slowly added dropwise at 0°C and extracted with dichloromethane. The separated organic layer was dried over MgSO ₄ and purified by column chromatography (DCM) to obtain 27.2 g (yield: 66.5%) of a red solid compound (Intermediate (2)).

(Synthesis of intermediate (3))

In a 1-neck 500 mL flask, mix 27.2 g (109.8 mmol) of intermediate (2), 45.5 g (329.5 mmol) of K ₂ CO ₃ , and 300 mL of N,N-dimethylformamide (DMF), then stir at 105°C for one day. It was stirred. After confirming the completion of the reaction, it was cooled to room temperature, distilled water was added, and the resulting solid was filtered. Methanol and hexane were added to the resulting reaction mixture, stirred at room temperature for 1 hour, and filtered to obtain 15.8 g (yield: 63.3%) of a red solid compound (Intermediate (3)).

intermediate Synthesis example 2: Synthesis of intermediate (6)

(Synthesis of intermediate (4))

Dissolve 30.0 g (177.3 mmol) of 6-hydroxy-2-naphthonitrile in 700 mL of dichloromethane, add 42.9 mL (531.9 mmol) of pyridine, and cool to 0°C. The temperature was lowered. After slowly adding 35.7 mL (212.8 mmol) of Tf ₂ O dropwise, the temperature was raised to room temperature and reacted for 12 hours. After washing the reaction product with 500 mL of distilled water, the separated organic layer was dried over anhydrous sodium sulfate, filtered, concentrated, and purified by column chromatography (CHCl ₃ ) to yield 53.0 g of the compound (Intermediate (4)) as a yellow solid (yield: 99.2). %) was obtained.

(Synthesis of intermediate (5))

In a 1-neck 2 L flask, 53.0 g (175.9 mmol) of intermediate (4), 67.0 g (263.9 mmol) of pinacolatodiboron (Bis(pinacolato)diboron), and 2.9 g (3.5 g) of Pd(dppf)Cl ₂ -CH ₂ Cl ₂ mmol), 51.8 g (527.8 mmol) of KOAc, and 800 mL of 1,4-dioxane were mixed and stirred at 100°C for 12 hours. After the reaction was completed, it was cooled to room temperature, the reactant was passed through a Celite pad, and then concentrated under reduced pressure. The reaction mixture was purified by silica gel column chromatography (CHCl ₃ ) and solidified with a mixed solvent (DCM/MeOH) to obtain 38.0 g (yield: 77.4%) of the compound (Intermediate (5)) as a white solid.

(Synthesis of intermediate (6))

In a one-neck 250mL flask, 4.3 g (15.4 mmol) of intermediate (5), 21.8 g (77.0 mmol) of 1-bromo-4-iodobenzene, and 0.5 g of Pd (PPh ₃ ) ₄ (0.5 mmol), 15.4 mL (30.8 mmol) of 2M aqueous solution K ₂ CO ₃ , 102 mL of toluene, and 51 mL of ethanol were mixed and stirred at 80°C for 3 hours. After confirming the completion of the reaction, it was cooled to room temperature, and distilled water was added dropwise. The reactant was extracted with dichloromethane, the separated organic layer was dried over anhydrous sodium sulfate, and the solvent was removed under reduced pressure. The obtained reaction product was purified by silica gel column chromatography (Hexanes/DCM) to obtain 3.4 g (yield: 72.3%) of a white solid compound (Intermediate (6)).

intermediate Synthesis example 3: Synthesis of intermediate (7)

In one 500 mL flask, 2,7-dibromo-9H-carbazole 15.0 g (46.2 mmol), 4-cyanophenylboronic acid 14.9 g(101.5 mmol), Pd(PPh ₃ ) ₄ After mixing and stirring 3.2 g (2.8 mmol) and 200 mL of toluene, 100 mL of ethanol, 19.1 g (138.5 mmol) of K ₂ CO ₃ and 100 mL of distilled water were added, and the mixture was stirred under heating and reflux all day. When the reaction was completed, the mixture was cooled to room temperature, the solvent was removed, distilled water was added, the organic layer was separated with dichloromethane, the solvent in the organic layer was removed, methanol was added, and the mixture was stirred for 30 minutes. The formed solid was filtered, washed with distilled water and methanol, and dried to obtain 7.3 g (yield: 43.1%) of a brown solid compound (Intermediate (7)).

intermediate Synthesis example 4: Synthesis of intermediate (8)

In one 500 mL flask, 2,7-dibromo-9H-carbazole 15.0 g (46.2 mmol), 3-cyanophenylboronic acid 14.9 g(101.5 mmol), Pd(PPh ₃ ) ₄ After mixing and stirring 3.2 g (2.8 mmol) and 200 mL of toluene, 100 mL of ethanol, 19.1 g (138.5 mmol) of K ₂ CO ₃ and 100 mL of distilled water were added, and the mixture was stirred under heating and reflux all day. When the reaction was completed, the mixture was cooled to room temperature, the solvent was removed, distilled water was added, the organic layer was separated with dichloromethane, the solvent in the organic layer was removed, methanol was added, and the mixture was stirred for 30 minutes. The formed solid was filtered, washed with distilled water and methanol, and dried to obtain 7.3 g (yield: 43.1%) of a brown solid compound (Intermediate (8)).

intermediate Synthesis example 5: Synthesis of intermediate (9)

In one 500 mL flask, 8.0 g (24.6 mmol) of 2,7-dibromo-9H-carbazole, naphthalen-2-ylboronic acid ) 10.1 g (59.0 mmol), 1.7 g (1.5 mmol) of Pd (PPh ₃ ) ₄ , 62.0 mL (124.0 mmol) of 2M K ₂ CO ₃ aqueous solution, 82 mL of toluene, and 41 mL of ethanol (EtOH) were mixed. It was refluxed and stirred for the next 4 hours. After the reaction was completed, the resulting solid was filtered, washed with methanol, and dried. After refluxing in monochlorobenzene, it was filtered through Celite and silica gel. Monochlorobenzene was distilled under reduced pressure and solidified with chloroform to obtain 6.2 g (yield: 60.2%) of a white solid compound (Intermediate (9)).

intermediate Synthesis example 6: Synthesis of intermediate (10)

1-Bromo-4-iodobenzene 23.4 g (84.3 mmol), benzo[b]thiophen-2-ylboronic acid 10.0 g (56.2 mmol) ), 1.9 g (0.7 mmol) of Pd(PPh ₃ ) ₄ , 84.3 mL (168.6 mmol) of 2M K ₂ CO ₃ aqueous solution, 187 mL of toluene, and 94 mL of ethanol were mixed and stirred under reflux for 2 hours. After confirming the completion of the reaction, it was cooled to room temperature and the organic layer was separated. The separated organic layer was filtered through silica and celite pads and washed with toluene. The filtrate was concentrated under reduced pressure and slurried with a mixed solution (DCM/HEX) to obtain 10.0 g (yield: 61.7%) of a white solid compound (Intermediate (10)).

intermediate Synthesis example 7: Synthesis of intermediate (12)

In a 2-neck 1 L flask, 5.0 g (15.4 mmol) of 2,7-dibromo-9 H -carbazole, 10.3 g (36.9 mmol) of intermediate (5), and Pd ( 1.1 g (923.1 μmol) of PPh ₃ ) ₄ , 10.6 g (76.9 mmol) of K ₂ CO ₃ , 80 mL of toluene, 20 mL of ethanol, and 20 mL of distilled water were mixed and stirred at 90°C for one day. When the reaction was completed, it was cooled to room temperature, distilled water was added to the reactant, stirred, filtered, and washed with distilled water, methanol, and ethyl acetate. The obtained solid compound was filtered on a silica gel pad (THF/Hex), suspended in THF, stirred, and filtered to obtain 5.8 g (yield: 80.3%) of a yellow solid compound (Intermediate (12)).

intermediate Synthesis example 8: Synthesis of intermediate (14)

(Synthesis of intermediate (13))

Intermediate (3) 20.0 g (87.9 mmol), Bis(pinacolato)diboron) 33.5 g (131.8 mmol), Pd ₂ (dba) ₃ 4.0 g (4.4 mmol), X-Phos 4.2 g (8.8 mmol) ), 25.9 g (263.6 mmol) of KOAc, and 350 mL of xylene were mixed, and then refluxed and stirred for 12 hours. After the reaction was completed, it was cooled to room temperature, the reactant was passed through a silica pad (CHCl ₃ ), and then concentrated under reduced pressure. The reaction mixture was solidified with a mixed solvent (DCM/MeOH) to obtain 24.9 g (yield: 88.8%) of a white solid compound (Intermediate (13)).

(Synthesis of intermediate (14))

In a 1 L flask, 31.2 g (162.9 mmol) of 1-bromo-4-chlorobenzene, 40.0 g (125.3 mmol) of intermediate (13), 7.2 g of Pd (PPh ₃ ) ₄ (6.3 mmol), 43.3 g (313.3 mmol) of K ₂ CO ₃ , 280 mL of toluene, 60 mL of ethanol, and 80 mL of distilled water were mixed and stirred under reflux for 12 hours. After the reaction was completed, the solid was filtered, washed with distilled water, methanol, and ethyl acetate, and dried to obtain 32.0 g (yield: 84.1%) of a white solid compound (Intermediate (14)).

intermediate Synthesis example 9: Synthesis of intermediate (15)

In a 1-neck 2 L flask, 50.0 g (274.7 mmol) of 3-bromobenzonitrile, 45.1 g (288.4 mmol) of 4-chlorophenylboronic acid, and Pd (PPh ₃ ) ) ₄ 15.9 g (13.7 mmol), K ₂ CO ₃ 94.9 g (686.7 mmol), toluene 500 mL), ethanol 150 mL, and distilled water 150 mL were mixed and then refluxed and stirred for 12 hours. After the reaction was completed, distilled water was added, extracted with ethyl acetate, and concentrated under reduced pressure. After passing through a silica pad (CHCl ₃ ), it was concentrated under reduced pressure and solidified with methanol to obtain 47.3 g (yield: 80.6%) of the compound (Intermediate (15)) as a white solid.

intermediate Synthesis example 10: Synthesis of intermediate (16)

In one 500 mL flask, 10.0 g (30.8 mmol) of 2,7-dibromo-9H-carbazole, benzothiophen-2-ylboronic acid (benzo[b]thiophen- 2-ylboronic acid) 22.2 g (123.0 mmol), Pd(PPh ₃ ) ₄ 3.6 g (3.1 mmol), Na ₂ CO ₃ 19.6 g (184.6 mmol), dioxane 90 mL and distilled water 30 mL were mixed and then left for 12 hours. It was refluxed and stirred. After the reaction was completed, the solid was filtered, washed with distilled water and methanol, dried, and solidified with a mixed solvent (CHCl ₃ /MeOH) to obtain 13.8 g (yield: 100%) of a white solid compound (Intermediate (16)).

intermediate Synthesis example 11: Synthesis of intermediate (18)

(Synthesis of intermediate (17))

In a 1-neck 500 mL flask, 5-bromoisophthalonitrile (5-bromoisophthalonitrile) 10.0 g (48.3 mmol), bis(pinacolato)diboron} 14.7 g (58.0 mmol), Pd(dppf) ) 1.6 g (1.9 mmol) of Cl ₂ , 9.5 g (96.6 mmol) of potassium acetate (KOAc), and 300 mL of dioxane were added together and refluxed at 100°C under nitrogen all day. When the reaction was completed, the solvent was removed, water was added, and extracted with chloroform. The separated organic layer was dried over anhydrous MgSO ₄ and purified by column chromatography (Hex:CHCl ₃ ) to obtain 7.6 g of a white solid compound (Intermediate (17)). (yield: 62.1%) was obtained.

(Synthesis of intermediate (18))

In one 500 mL flask, 7.6 g (30.0 mmol) of intermediate (17), 8.5 g (30.0 mmol) of 1-bromo-4-iodobenzene, Pd (PPh ₃ ) ₄ 1.0 g (0.9 mmol) and 150 mL of toluene were added together and stirred, then 80 mL of ethanol, 8.3 g (59.8 mmol) of K ₂ CO ₃ and 80 mL of distilled water were added, and the mixture was stirred under heating and reflux all day. When the reaction was completed, it was cooled to room temperature, the solvent was removed, distilled water was added, extracted with dichloromethane, and the separated organic layer was dried over anhydrous MgSO ₄ and purified by column chromatography (Hex:CHCl ₃ ) to obtain a pale yellow solid compound. (Intermediate (18)) 2.9 g (yield: 34.1%) was obtained.

intermediate Synthesis example 12: Synthesis of intermediate (20)

(Synthesis of intermediate (19))

In a 2-neck 1 L flask, 10.0 g (30.8 mmol) of 2,7-dibromo-9 H -carbazole, 23.4 g of Bis(pinacolato)diboron) (92.3 mmol), Pd(dppf)Cl ₂ ·CH ₂ Cl ₂ 1.5 g (1.8 mmol), KOAc 153.8 g (15.1 mmol) and 150 mL of 1,4-dioxane were mixed, then reacted at 110°C for one day. did. When the reaction is completed, it is cooled to room temperature, filtered through a Celite pad, the mixture is dissolved in toluene and filtered through a silica gel pad (Hex: THF), and the resulting mixture is solidified with methanol to obtain 11.3 g of a white solid compound (Intermediate (19)). (yield: 87.6%) was obtained.

(Synthesis of intermediate (20))

In a 2-neck 1 L flask, 11.3 g (27.0 mmol ) of intermediate (19), 18.3 g (107.8 mmol) of 2-chlorobenzo[ d ] thiazole, 1.9 g of Pd(PPh ₃ ) ₄ (1.6 mmol), 14.3 g (134.8 mmol) of K ₂ CO ₃ , 135 mL of toluene, 35 mL of ethanol, and 35 mL of distilled water were mixed and stirred at 90°C for one day. When the reaction was completed, it was cooled to room temperature, distilled water was added to the reactant, stirred, filtered, and washed with distilled water, methanol, and chloroform. The obtained solid compound was dried to obtain 11.6 g (yield: 99.2%) of a yellow solid compound (Intermediate (20)).

intermediate Synthesis example 13: Synthesis of intermediate (22)

(Synthesis of intermediate (21))

In one 500 mL flask, 10.0 g (36.5 mmol) of 2-(4-bromophenyl)benzo[d]oxazole, 10.2 g (40.1 mmol) of Bis(pinacolato)diboron , 1.2 g (1.5 mmol) of Pd(dppf)Cl ₂ ·CH ₂ Cl ₂ , 7.2 g (73.0 mmol) of potassium acetate (KOAc), and 300 mL of dioxane were added together, and the mixture was refluxed and stirred at 100°C all day. . When the reaction was completed, the solvent was removed, and the obtained compound was purified by silica gel column chromatography to obtain 8.6 g (yield: 73.4%) of a slightly white solid compound (Intermediate (21)).

(Synthesis of intermediate (22))

In a 1-neck 500 mL flask, 4.0 g (12.3 mmol) of 2,7-dibromo-9H-carbazole, 8.6 g (26.7 mmol) of intermediate (21), and Pd(PPh) ₃ ) ₄ After mixing and stirring 1.4 g (1.2 mmol) and 40 mL of toluene, 20 mL of ethanol, 6.8 g (49.2 mmol) of K ₂ CO ₃ and 20 mL of distilled water were added, and the mixture was stirred under heating and reflux all day. After the reaction was completed, the resulting solid was filtered, washed with methanol, and dried. After refluxing in monochlorobenzene, it was filtered through Celite and silica gel. Monochlorobenzene was distilled under reduced pressure and solidified with chloroform to obtain 4.1 g (yield: 60.2%) of a white solid compound (Intermediate (22)).

intermediate Synthesis example 14: Synthesis of intermediate (23)

In a two-neck 1 L flask, 11.3 g (27.0 mmol ) of intermediate (19), 16.5 g (107.8 mmol) of 2-chlorobenzo[ d ]oxazole, 1.9 g of Pd(PPh ₃ ) ₄ (1.6 mmol), 14.3 g (134.8 mmol) of K ₂ CO ₃ , 135 mL of toluene, 35 mL of ethanol, and 35 mL of distilled water were mixed and stirred at 90°C for one day. When the reaction was completed, it was cooled to room temperature, distilled water was added to the reactant, stirred, filtered, and washed with distilled water, methanol, and chloroform. The obtained solid compound was dried to obtain 8.9 g (yield: 82.0%) of a yellow solid compound (Intermediate (23)).

intermediate Synthesis example 15: Synthesis of intermediate (25)

(Synthesis of intermediate (24))

5.0 g (23.5 mmol) of 5-bromobenzo[b]thiophene, 2.5 g (28.2 mmol) of CuCN, and 15 mL of DMF were mixed and stirred under reflux at 160°C for 3 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature, 2N NaOH aqueous solution was added, and stirred for 30 minutes. The mixed solution was extracted with ethyl acetate, dried with anhydrous magnesium sulfate, filtered, and concentrated. The concentrate was purified through column chromatography (EA:HEX) to obtain 2.3 g (yield: 62.1%) of the compound (Intermediate (24)) as a yellow solid.

(Synthesis of intermediate (25))

To a solution of 2.3 g (14.5 mmol) of intermediate (24) dissolved in 83 mL of anhydrous THF, 10.2 mL (17.3 mmol, 1.7 M in pentane) of n-BuLi was slowly added dropwise at -78°C and stirred for 15 minutes. 43.0 mL (385.7 mmol) of trimethylborate was slowly added dropwise, stirred at -78°C for 15 minutes, and then stirred at room temperature for 2 hours. After confirming the completion of the reaction, 1M HCl aqueous solution was slowly added dropwise and concentrated. Distilled water was added to the concentrate and extracted with ethyl acetate. The separated organic layer was dried over anhydrous sodium sulfate, filtered, and concentrated. The concentrate was purified by column chromatography (MeOH/CHCl ₃ ) to obtain 1.2 g (yield: 40.9%) of the off-white solid compound (Intermediate (25)).

intermediate Synthesis example 16: Synthesis of intermediate (26)

3,6-dibromocarbazole 1.0 g (3.1 mmol), intermediate (25) 1.2 g (6.2 mmol), Tetrakis (triphenylphosphine) palladium) 153.8 mg (177.8 mmol), 2M potassium carbonate 6 mL (12.3 mmol), 12 mL of toluene, and 6 mL of ethanol were mixed. The mixed solution was heated to 90°C and reacted under reflux for 17 hours. After cooling to room temperature, the precipitated solid compound was filtered. After adding monochlorobenzene to the solid compound, it was filtered through a Celite pad and concentrated. The concentrated organic material was recrystallized with acetone to obtain 1.2 g (yield: 81.0%) of a white solid compound (Intermediate (26)).

intermediate Synthesis example 17: Synthesis of intermediate (28)

(Synthesis of intermediate (27))

4-Amino-3-bromobenzonitrile 50.0 g (253.8 mmol), 4-Bromobenzoyl chloride 55.7 g (253.8 mmol) and Pyridine 500 mL was added and refluxed and stirred for more than 12 hours. After confirming the completion of the reaction, the solvent was distilled under reduced pressure. It was solidified with diisopropyl ether (IPE) to obtain 75.6 g (yield: 78.3%) of a light yellow solid compound (Intermediate (27)).

(Synthesis of intermediate (28))

In a 1 L flask, 75.6 g (251.1 mmol) of intermediate (27), 2.39 g (12.6 mmol) of CuI, 4.5 g (25.1 mmol) of 1,10-Phenanthroline, 148.7 g (456.6 mmol) of Cs ₂ CO ₃ and nitrobenzene (Nitrobenzene) 800 mL was refluxed and stirred all day. After the reaction was completed, DCM was passed through a Celite pad. After removing the solvent, the solid was dissolved in chloroform and purified using column chromatography (CHCl ₃ ). It was solidified with methanol to obtain 42.3 g (yield: 56.3%) of a light yellow solid compound (Intermediate (28)).

Using the synthesized intermediate compounds, various carbazole derivatives were synthesized as follows.

Synthesis example 1: Synthesis of compound 6-4 (LT22-35-022)

In a two-neck 100 mL flask, 2.2 g (6.0 mmol) of intermediate (7), 4'-bromo-(1,1'-biphenyl)-4-carbonitrile (4'-bromo-[1,1'-biphenyl) ]-4-carbonitrile) 1.8 g (7.1 mmol), Pd ₂ (dba) ₃ 545.3 mg (595.5 μmol), S-Phos 977.9 mg (2.4 mmol), K ₃ PO ₄ 3.8 g (17.9 mmol) and xylene 30 After mixing mL, it was stirred at 130°C for two days. After the reaction was completed, it was cooled to room temperature, distilled water was added to the reactant, filtered, and washed with distilled water, methanol, and chloroform. The obtained solid compound was dissolved in monochlorobenzene, filtered through Celite, and solidified with monochlorobenzene to obtain 2.4 g (yield: 59.9%) of compound 6-4 (LT22-35-022) as a yellow solid.

Synthesis example 2: Synthesis of compound 6-9 (LT22-30-027)

In a two-neck 100 mL flask, 3.0 g (8.1 mmol) of intermediate (7), 3.0 g (9.7 mmol) of intermediate (6), 223.1 mg (243.6 μmol) of Pd ₂ (dba) ₃ , and 200.0 mg (487.2 μmol) of S-Phos. , 3.5 g (16.2 mmol) of K ₃ PO ₄ and 30 mL of xylene were mixed and stirred at 130°C for two days. After the reaction was completed, it was cooled to room temperature, distilled water was added to the reactant, filtered, and washed with distilled water, methanol, and chloroform. The obtained solid compound was dissolved in monochlorobenzene, filtered through Celite, and solidified with monochlorobenzene to obtain 2.0 g (yield: 41.3%) of compound 6-9 (LT22-30-027) as a yellow solid.

Synthesis example 3: Synthesis of compound 6-15 (LT22-30-022)

In one 250 mL flask, 3.4 g (9.2 mmol) of intermediate (7), 3.0 g (11.0 g) of 2-(4-bromophenyl)benzo[d]oxazole mmol), 0.4 g (0.5 mmol) of Pd ₂ (dba) ₃ , 0.9 g (1.8 mmol) of X-Phos, 5.9 g (27.6 mmol) of K ₃ PO ₄ and 92 mL of Refluxed and stirred. After confirming the completion of the reaction, the mixture was cooled to room temperature, then distilled water was added and stirred for 1 hour. The resulting solid was filtered and dried. The obtained solid was refluxed in monochlorobenzene and then filtered through Celite and silica gel. After cooling to room temperature, the resulting solid was filtered and dried to obtain 2.1 g (yield: 40.3%) of compound 6-15 (LT22-30-022) as a yellow solid.

Synthesis example 4: Synthesis of compound 6-20 (LT22-30-024)

In a 1-neck 250 mL flask, 3.4 g (9.2 mmol) of intermediate (7), 2.5 g (11.0 mmol) of intermediate (3), 0.4 g (0.5 mmol) of Pd ₂ (dba) ₃ , and 0.9 g (1.8 mmol) of X-Phos. , 5.9 g (27.6 mmol) of K ₃ PO ₄ and 92 mL of xylene were mixed, then refluxed and stirred for 18 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature, then distilled water was added and stirred for 1 hour. The resulting solid was filtered and dried. The obtained solid was refluxed in dichlorobenzene and then filtered through Celite and silica gel. After cooling to room temperature, the resulting solid was filtered and dried to obtain 1.8 g (yield: 34.6%) of compound 6-20 (LT22-30-024) as a yellow solid.

Synthesis example 5: Synthesis of compound 6-56 (LT22-30-026)

In a 1-neck 250 mL flask, intermediate (8) 3.0 g (8.1 mmol), intermediate (3) 1.9 g (8.1 mmol), Pd ₂ (dba) ₃ 223.1 mg (0.5 mmol), X-Phos 232.3 g (487.2 mmol) , 3.5 g (16.2 mmol) of K ₃ PO ₄ and 100 mL of xylene were mixed, then refluxed and stirred for 18 hours. After confirming the completion of the reaction, the mixture was cooled to room temperature, then distilled water was added and stirred for 1 hour. The resulting solid was filtered and dried. The obtained solid was refluxed in dichlorobenzene and then filtered through Celite and silica gel. After cooling to room temperature, the resulting solid was filtered and dried to obtain 2.0 g (yield: 43.9%) of compound 6-24 (LT22-30-024) as an ivory solid.

Synthesis example 6: Synthesis of compound 6-164 (LT22-30-025)

In a 1-neck 250 mL flask, 3.1 g (6.3 mmol) of intermediate (9), 1.9 g (8.2 mmol) of intermediate (3), 0.3 g (0.3 mmol) of Pd ₂ (dba) ₃ , and 0.6 g (1.3 mmol) of X-Phos. , 4.0 g (19.8 mmol) of K ₃ PO ₄ and 63 mL of xylene were mixed, then refluxed and stirred for 18 hours. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added, and the mixture was stirred for 1 hour. The resulting solid was filtered and dried. The obtained solid was refluxed in dichlorobenzene and then filtered through Celite and silica gel. After cooling to room temperature, the resulting solid was filtered and dried to obtain 1.9 g (yield: 48.7%) of compound 6-164 (LT22-30-025) as a yellow solid.

Synthesis example 7: Synthesis of compound 6-195 (LT21-30-447)

In a two-necked 100 mL flask, 4.0 g (8.5 mmol) of intermediate (12), 3.5 g (12.8 mmol) of 2-(4-bromophenyl)benzo[ d ]oxazole) mmol), 390.0 mg (425.9 μmol) of Pd ₂ (dba) _3, 349.7 mg (851.9 μmol) of S-Phos, 5.4 g (25.6 mmol) of K ₃ PO ₄ and 45 mL of xylene were mixed and incubated at 140°C for one day. Stirred. After the reaction was completed, it was cooled to room temperature, distilled water was added to the reaction product, filtered, and washed with ethyl acetate. The obtained solid compound was dissolved in hot monochlorobenzene, filtered through a silica gel pad, and solidified three times with monochlorobenzene. 2.4 g (yield: 42.2%) of compound 6-195 (LT21-30-447) as a light yellow solid was obtained.

Synthesis example 8: Synthesis of compound 6-200 (LT21-35-501)

In a two-neck 100 mL flask, 4.0 g (8.5 mmol) of intermediate (12), 1.9 g (8.5 mmol) of intermediate (3), 234.0 mg (255.6 μmol) of Pd ₂ (dba) ₃ , and 209.8 mg (511.1 μmol) of S-Phos. , 3.6 g (17.0 mmol) of K ₃ PO ₄ and 45 mL of xylene were mixed and stirred at 140°C for one day. After the reaction was completed, it was cooled to room temperature, distilled water was added to the reaction product, filtered, and washed with ethyl acetate. The obtained solid compound was dissolved in hot monochlorobenzene, filtered through a silica gel pad, and solidified three times with monochlorobenzene. 2.1 g (yield: 37.3%) of compound 6-200 (LT21-35-501) as a light yellow solid was obtained.

Synthesis example 9: Synthesis of compound 6-214 (LT21-35-502)

In a two-neck 100 mL flask, 4.0 g (8.5 mmol) of intermediate (12), 2.6 g (8.5 mmol) of intermediate (14), 234.0 mg (255.6 μmol) of Pd ₂ (dba) ₃ , and 209.8 mg (511.1 μmol) of S-Phos. , 3.6 g (17.0 mmol) of K ₃ PO ₄ and 45 mL of xylene were mixed and stirred at 140°C for one day. After the reaction was completed, it was cooled to room temperature, distilled water was added to the reaction product, filtered, and washed with ethyl acetate. The obtained solid compound was dissolved in hot monochlorobenzene, filtered through a silica gel pad, and solidified three times with monochlorobenzene. 2.2 g (yield: 35.1%) of compound 6-214 (LT21-35-502) as a yellow solid was obtained.

Synthesis example 10: Synthesis of compound 6-257 (LT21-30-452)

Intermediate (16) 5.0 g (11.6 mmol), Intermediate (15) 3.7 g (17.4 mmol), Pd ₂ (dba) ₃ 1.1 g (12.7 mmol), S-Phos 951.3 mg (2.3 mmol), K ₃ PO ₄ 7.4 g (34.8 mmol) and 60 mL of xylene were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the solid was filtered, washed with distilled water, methanol, and ethyl acetate, and dried. The dried solid was boiled and dissolved in monochlorobenzene, passed through a silica gel pad, and then concentrated under reduced pressure. After boiling and dissolving in monochlorobenzene again, the mixture was stirred at 80°C for 12 hours. The solid was filtered to obtain compound 6-257 (LT21-30-452) as a yellow solid. 1.5 g (yield: 20.8%) was obtained.

Synthesis example 11: Synthesis of compound 6-258 (LT21-35-505)

In a two-neck 100 mL flask, 3.0 g (7.0 mmol) of intermediate (16), 2.4 g (8.3 mmol) of intermediate (18), 191.0 mg (208.5 μmol) of Pd ₂ (dba) ₃ , and 171.2 mg (417.1 μmol) of S-Phos. , 3.0 g (13.9 mmol) of K ₃ PO ₄ and 30 mL of xylene were mixed and stirred at 140°C for one day. After the reaction was completed, it was cooled to room temperature, distilled water was added to the reaction product, filtered, and washed with ethyl acetate. The obtained solid compound was dissolved in hot monochlorobenzene, filtered through a silica gel pad, and solidified three times with monochlorobenzene. 1.9 g (yield: 43.1%) of compound 6-258 (LT21-35-505) as a light yellow solid was obtained.

Synthesis example 12: Synthesis of compound 6-260 (LT22-30-033)

In a two-neck 100 mL flask, 3.0 g (7.0 mmol) of intermediate (16), 2-(4-bromophenyl)naphthalene (2-(4-bromophenyl)naphthalene) 2.4 g (8.3 mmol), Pd ₂ (dba) ₃ 191.0 mg (208.5 μmol), 171.2 mg (417.1 μmol) of S-Phos, 3.0 g (13.9 mmol) of K ₃ PO ₄ and 30 mL of xylene were mixed and stirred at 130°C for two days. After the reaction was completed, it was cooled to room temperature, distilled water was added to the reactant, filtered, and washed with distilled water, methanol, and chloroform. The obtained solid compound was dissolved in monochlorobenzene, filtered through Celite, and solidified with monochlorobenzene to obtain 2.1 g (yield: 47.7%) of compound 6-260 (LT22-30-033) as a yellow solid.

Synthesis example 13: Synthesis of compound 6-261 (LT22-35-020)

In a two-neck 100 mL flask, 3.0 g (7.0 mmol) of intermediate (16), 2.1 g (7.0 mmol) of intermediate (6), 191.0 mg (208.5 μmol) of Pd ₂ (dba) ₃ , and 171.2 mg (417.1 μmol) of S-Phos. , 3.0 g (13.9 mmol) of K ₃ PO ₄ and 30 mL of xylene were mixed and stirred at 130°C for two days. After the reaction was completed, it was cooled to room temperature, distilled water was added to the reactant, filtered, and washed with distilled water, methanol, and chloroform. The obtained solid compound was dissolved in monochlorobenzene, filtered through Celite, and solidified with monochlorobenzene to obtain 1.9 g (yield: 41.5%) of compound 6-261 (LT22-35-020) as a yellow solid.

Synthesis example 14: Synthesis of compound 6-266 (LT22-30-036)

In a two-neck 100 mL flask, 3.0 g (7.0 mmol) of intermediate (16), 2.0 g (7.0 mmol) of intermediate (10), 191.0 mg (208.5 μmol) of Pd ₂ (dba) ₃ , and 171.2 mg (417.1 μmol) of S-Phos. , 3.0 g (13.9 mmol) of K ₃ PO ₄ and 30 mL of xylene were mixed and stirred at 130°C for two days. After the reaction was completed, it was cooled to room temperature, distilled water was added to the reactant, filtered, and washed with distilled water, methanol, and chloroform. The obtained solid compound was dissolved in monochlorobenzene, filtered through Celite, and solidified with monochlorobenzene to obtain 2.1 g (yield: 47.2%) of compound 6-266 (LT22-30-036) as a yellow solid.

Synthesis example 15: Synthesis of compound 6-267 (LT22-30-028)

In a 1-neck 250 mL flask, 3.8 g (8.8 mmol) of intermediate (16), 2-(4-bromophenyl)benzo[d]oxazole (2-(4-bromophenyl)benzo[d]oxazole) 2.9 g (10.6 mmol), 0.4 g (0.4 mmol) of Pd ₂ (dba) ₃ , 0.8 g (1.8 mmol) of X-Phos, 5.6 g (26.4 mmol) of K ₃ PO ₄ and 88 mL of Refluxed and stirred. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added, and the mixture was stirred for 1 hour. The resulting solid was filtered and dried. The obtained solid was refluxed in monochlorobenzene and then filtered through Celite and silica gel. After cooling to room temperature, the resulting solid was filtered and dried to obtain 3.1 g (yield: 56.4%) of compound 6-267 (LT22-30-028) as a yellow solid.

Synthesis example 16: Synthesis of compound 6-268 (LT22-30-032)

In one 250 mL flask, 3.8 g (8.8 mmol) of intermediate (16), 3.1 g (10.6 g) of 2-(4-bromophenyl)benzo[d]thiazole (2-(4-bromophenyl)benzo[d]thiazole) mmol), 0.4 g (0.4 mmol) of Pd ₂ (dba) ₃ , 0.8 g (1.8 mmol) of X-Phos, 5.6 g (26.4 mmol) of K ₃ PO ₄ and 88 mL of Refluxed and stirred. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added, and the mixture was stirred for 1 hour. The resulting solid was filtered and dried. The obtained solid was refluxed in monochlorobenzene and then filtered through Celite and silica gel. After cooling to room temperature, the resulting solid was filtered and dried to obtain 2.5 g (yield: 45.0%) of compound 6-268 (LT22-30-032) as a yellow solid.

Synthesis example 17: Synthesis of compound 6-270 (LT22-30-038)

In one 250 mL flask, 3.8 g (8.8 mmol) of intermediate (16), 2.8 g (10.6 mmol) of 3-bromodibenzo[b,d]thiophene, 0.4 g of Pd ₂ (dba) ₃ (0.4 _mmol ), _0.8 g (1.8 mmol) of After the reaction was completed, the mixture was cooled to room temperature, distilled water was added, and the mixture was stirred for 1 hour. The resulting solid was filtered and dried. The obtained solid was refluxed in monochlorobenzene and then filtered through Celite and silica gel. After cooling to room temperature, the resulting solid was filtered and dried to obtain 2.7 g (yield: 50.0%) of compound 6-270 (LT22-30-038) as a yellow solid.

Synthesis example 18: Synthesis of compound 6-272 (LT21-30-431)

Intermediate (16) 5.0 g (11.6 mmol), Intermediate (3) 2.9 g (12.7 mmol), Pd ₂ (dba) ₃ 1.1 g (1.2 mmol), S-Phos 951.3 mg (2.3 mmol), K ₃ PO ₄ 7.4 g (34.8 mmol) and 60 mL of xylene were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the solid was filtered, washed with water, methanol, and ethyl acetate, and dried. The dried solid was boiled and dissolved in monochlorobenzene, passed through a silica gel pad, and then concentrated under reduced pressure. After boiling and dissolving in monochlorobenzene again, it was stirred at 100°C for 12 hours. The solid was filtered to obtain 3.1 g (yield: 42.8%) of compound 6-272 (LT21-30-431) as a yellow solid.

Synthesis example 19: Synthesis of compound 6-282 (LT22-30-039)

In a 1-neck 250 mL flask, 5.0 g (11.6 mmol) of intermediate (16), 2-(4'-bromo-[1,1'-biphenyl]-4-yl)benzoxazole (2-(4'- bromo-[1,1'-biphenyl]-4-yl)benzo[d]oxazole)) 4.9 g (13.9 mmol), Pd ₂ (dba) ₃ 530.5,g (0.6 mmol), X-Phos 552.3 mg (1.2 mmol), 4.9 g (23.2 mmol) of K ₃ PO ₄ and 100 mL of xylene were mixed, then refluxed and stirred for 18 hours. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added, and the mixture was stirred for 1 hour. The resulting solid was filtered and dried. The obtained solid was refluxed in monochlorobenzene and then filtered through Celite and silica gel. After cooling to room temperature, the resulting solid was filtered and dried to obtain 3.6 g (yield: 44.3%) of compound 6-282 (LT22-30-039) as a yellow solid.

Synthesis example 20: Synthesis of compound 6-286 (LT22-35-051)

Intermediate (16) 4.0 g (9.3 mmol), Intermediate (14) 3.4 g (11.1 mmol), Pd ₂ (dba) ₃ 424.4 mg (0.5 mmol), S-Phos 380.5 mg (0.9 mmol), K ₃ PO ₄ 3.9 g (18.5 mmol) and 80 mL of xylene were mixed, and then stirred under reflux for 12 hours. After the reaction was completed, the solid was filtered, washed with water, methanol, and ethyl acetate, and dried. The dried solid was boiled and dissolved in monochlorobenzene, passed through a silica gel pad, and then concentrated under reduced pressure. After boiling and dissolving in monochlorobenzene again, it was stirred at 100°C for 12 hours. The solid was filtered to obtain 2.2 g (yield: 34.0%) of compound 6-286 (LT22-35-051) as a yellow solid.

Synthesis example 21: Synthesis of compound 6-303 (LT22-35-062)

In one 250 mL flask, 4.0 g (10.0 mmol) of intermediate (23), 3.3 g (12.0 mmol) of 2-(4-bromophenyl)benzo[d]oxazole) mmol), Pd ₂ (dba) ₃ 456.2 mg (0.5 mmol), X-Phos 475.0 mg (1.0 mmol), K ₃ PO ₄ 4.2 g (20.0 mmol) and 100 mL of Refluxed and stirred. After the reaction was completed, the mixture was cooled to room temperature, distilled water was added, and the mixture was stirred for 1 hour. The resulting solid was filtered and dried. The obtained solid was refluxed in monochlorobenzene and then filtered through Celite and silica gel. After cooling to room temperature, the resulting solid was filtered and dried to obtain 2.1 g (yield: 35.4%) of compound 6-303 (LT22-35-062) as a yellow solid.

Synthesis example 22: Synthesis of compound 6-329 (LT22-30-007)

In a two-neck 100 mL flask, 4.0 g (9.2 mmol) of intermediate (20), 2.4 g (11.1 mmol) of intermediate (15), 422.4 mg (461.3 μmol) of Pd ₂ (dba) ₃ , and 377.8 mg (922.6 μmol) of S-Phos. , 5.9 g (27.7 mmol) of K ₃ PO ₄ and 46 mL of xylene were mixed and stirred at 140°C for one day. After the reaction was completed, it was cooled to room temperature, distilled water was added to the reaction product, filtered, and washed with ethyl acetate. The obtained solid compound was dissolved in hot monochlorobenzene, filtered through a silica gel pad, and solidified three times with monochlorobenzene. 2.0 g (yield: 35.5%) of compound 6-329 (LT22-30-007) was obtained as a light yellow solid.

Synthesis example 23: Synthesis of compound 6-344 (LT21-30-464)

In a two-neck 100 mL flask, 4.0 g (9.2 mmol) of intermediate (20), 3.2 g (13.8 mmol) of intermediate (3), 422.4 mg (461.3 μmol) of Pd ₂ (dba) ₃ , and 377.8 mg (922.6 μmol) of S-Phos. , 5.9 g (27.7 mmol) of K ₃ PO ₄ and 46 mL of xylene were mixed and stirred at 140°C for one day. After the reaction was completed, it was cooled to room temperature, distilled water was added to the reaction product, filtered, and washed with ethyl acetate. The obtained solid compound was dissolved in hot monochlorobenzene, filtered through a silica gel pad, and solidified three times with monochlorobenzene. 1.6 g (yield: 28.3%) of compound 6-344 (LT21-30-464) as a light yellow solid was obtained.

Synthesis example 24: Synthesis of compound 6-373 (LT21-35-506)

In a 1-neck 2 L flask, 4.0 g (10.0 mmol) of 2,7-dibromo-9-phenyl-9H-carbazole, 7.0 g of intermediate (13) (21.9 mmol), 1.2 g (1.0 mmol) of Pd(PPh ₃ ) ₄ , 5.5 g (39.9 mmol) of K ₂ CO ₃ , 40 mL of toluene, 20 mL of ethanol, and 20 mL of distilled water were mixed and stirred under reflux for 12 hours. . After confirming the completion of the reaction, the formed solid was filtered and washed with distilled water and methanol. The obtained solid compound was dissolved in hot monochlorobenzene, filtered through a silica gel pad, and solidified three times with monochlorobenzene. 1.6 g (yield: 25.6%) of compound 6-373 (LT21-35-506) as a light yellow solid was obtained.

Synthesis example 25: Synthesis of compound 6-433 (LT21-35-333)

Intermediate (26) 3.0 g (7.0 mmol), Intermediate (28) 2.1 g (7.0 mmol), Pd(dba) ₂ 40.0 mg (69.5 umol), Xant-Phos 80.0 mg (139.0 umol), Cs ₂ CO ₃ 4.5 g (13.9 mmol) and 30 mL of xylene were mixed, then refluxed and stirred for 12 hours. After confirming the completion of the reaction, it was cooled to room temperature, distilled water was added, extraction was performed with chloroform, and the solvent was removed under reduced pressure. It was purified by silica gel column chromatography (DCM) and solidified with a mixed solvent (MCB/Acetone) to obtain 3.2 g (yield: 71.2%) of compound 6-433 (LT21-35-333) as a yellow solid.

Synthesis example 26: Synthesis of compound 6-437 (LT21-35-256)

Intermediate (16) 3.0 g (7.0 mmol), Intermediate (28) 2.1 g (7.0 mmol), Pd(dba) ₂ 40.0 mg (69.5 umol), Xant-Phos 80.0 mg (139.0 umol), Cs ₂ CO ₃ 4.5 g (13.9 mmol) and 30 mL of xylene were mixed, then refluxed and stirred for 12 hours. After confirming the completion of the reaction, it was cooled to room temperature, distilled water was added, extraction was performed with chloroform, and the solvent was removed under reduced pressure. It was purified by silica gel column chromatography (DCM) and solidified with a mixed solvent (MCB/Acetone) to obtain 3.2 g (yield: 71.2%) of compound 6-437 (LT21-35-256) as a yellow solid.

Synthesis example 27: Synthesis of compound 6-441 (LT21-35-145)

In a two-neck 100 mL flask, 6.0 g (12.2 mmol) of intermediate (26), 4'-bromo-[1,1'-biphenyl-4-carbonitrile (4'-bromo-[1,1'-biphenyl) -4-carbonitrile) 3.8 g (14.7 mmol), Pd ₂ (dba) ₃ 1.1 g (1.2 mmol), S-Phos 1.0 g (2.4 mmol), NaO tBu 3.5 g (36.7 mmol) and toluene 60 mL were mixed. Afterwards, the mixture was refluxed and stirred for one day. After confirming the completion of the reaction, it was cooled to room temperature, distilled water was added, filtered, and washed with distilled water, methanol, and hexane. The obtained solid mixture was dissolved in toluene and filtered through a silica pad. The obtained mixture was purified by silica gel column chromatography (Hex:Tol) and solidified with toluene to obtain 3.0 g (yield: 73.5%) of compound 6-441 (LT21-35-145) as a white solid.

Synthesis example 28: Synthesis of compound 6-477 (LT21-35-510)

In a two-neck 100 mL flask, 4.0 g (7.2 mmol) of intermediate (22), 2.0 g (8.7 mmol) of intermediate (3), 330.8 mg (361.3 μmol) of Pd ₂ (dba) ₃ , and 296.6 mg (722.5 μmol) of S-Phos. , 3.1 g (14.5 mmol) of K ₃ PO ₄ and 40 mL of xylene were mixed and stirred at 140°C for one day. After the reaction was completed, it was cooled to room temperature, distilled water was added to the reaction product, filtered, and washed with ethyl acetate. The obtained solid compound was dissolved in hot monochlorobenzene, filtered through a silica gel pad, and solidified three times with monochlorobenzene. 1.9 g (yield: 35.3%) of compound 6-477 (LT21-35-510) as a light yellow solid was obtained.

<Test example>

Regarding the compounds of the present invention, J.A. Measure n (refractive index) and k (extinction coefficient) using WOOLLAM's Ellipsometer device.

Fabrication of a single film for a test example:

To measure the optical properties of the compound, a glass substrate (0.7T) was washed with Ethanol, DI Water, and Acetone for 10 minutes each, and then a single film was produced by depositing 800Å of the compound on the glass substrate.

Single film production for comparative test example (Glass/REF01 (80 nm)):

The optical characteristic device was manufactured by depositing REF01 (80nm) on glass. Before depositing the compound, the glass was treated with oxygen plasma at 2×10 ^{- 2} Torr at 125 W for 2 minutes. A single film is produced by depositing the compound at a speed of 1Å/sec in a vacuum of 9×10 ^{- 7} Torr.

Comparative test example 1 (REF01) Comparative test example 2 (REF02) 6-20 (LT22-30-024)

6-195(LT21-30-447) 6-303(LT22-35-062) 6-344(LT21-30-464)

<Test Examples 1 to 4>

In the comparative test example, a single membrane was produced in the same manner as the comparative test example, except that each compound shown in Table 1 below was used instead of REF01.

The optical properties of the compounds for the comparative test examples and test examples 1 to 4 are shown in Table 1.

The optical properties are the refractive index (n) constant at wavelengths of 450 nm and 620 nm.

division compound n(450nm) n(620nm) Comparative test example 1 REF01 2.316 2.097 Comparative test example 2 REF02 2.215 2.031 Test example 1 6-20
(LT22-30-024) 2.409 2.147 Test example 2 6-195
(LT21-30-447) 2.520 2.220 Test example 3 6-303
(LT22-35-062) 2.421 2.146 Test example 4 6-344
(LT21-30-464) 2.446 2.149

Comparing Comparative Test Example 1 (REF01) and Test Example 1 (Compound (6-20)) in Table 1 above, the chemical structures are similar, but the refractive index of Test Example (2.409 compared to 2.316) increases depending on the substitution position of carbazole. was able to confirm.

It can be judged that as the refractive index increases, the effect of extracting light emitted from inside the electrode to the outside will increase.

The n value at 450 nm in Comparative Test Example 1 (REF01) was 2.316, whereas most of the example compounds were confirmed to have a refractive index generally higher than 2.400. This satisfies the high refractive index value required to secure a high viewing angle in the blue region.

<Example>

Device fabrication

To fabricate the device, ITO, a transparent electrode, was used as the anode layer, HT01 was the hole injection layer, NPB was the hole transport layer, αβ-ADN was the host of the emitting layer, Pyene-CN was the blue fluorescent dopant, ET201 was the electron transport layer, and Liq was the host. The electron injection layer, Mg:Ag, was used as a cathode. The structures of these compounds are shown in the following chemical formulas.

Comparative Example: ITO / HT01 (90 nm) / NPB (25 nm) / αβ-ADN: 5% Pyrene-CN (200 nm) / ET201: Liq (=1:1, 40 nm) / Liq (2 nm) / Mg:Ag (1:9, 10 nm) / REF01 (60 nm)

Blue fluorescent organic light emitting device is ITO / HT01 (90 nm) / NPB (25 nm) / αβ-ADN:5% Pyrene-CN (200 nm) / ET201: Liq (=1:1, 40 nm) / Liq (2 nm) ) / Mg:Ag (1:9, 10 nm)/REF01 (60 nm) was deposited in the following order to manufacture the device. Before depositing organic materials, the ITO electrode was treated with oxygen plasma at 2 × 10 ^{- 2} Torr at 125 W for 2 minutes. Organic materials were deposited at a vacuum ^{of 9} It was 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 sealed in a glove box filled with nitrogen gas to prevent contact with air and moisture. After forming a partition using 3M adhesive tape, barium oxide, a moisture absorbent that can remove moisture, was added and a glass plate was attached.

Comparative Test Example 1 (REF01) Comparative Test Example 2 (REF02)

<Examples 1 to 28>

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

Electrical luminescence characteristics of the organic light-emitting devices manufactured in Comparative Examples and Examples 1 to 28 are shown in Table 2.

division compound Driving voltage [V] Efficiency [cd/A] Lifespan (T _97% )[hr] Comparative Example 1 REF01 3.93 6.11 42 Comparative Example 2 REF02 3.92 6.09 39 Example 1 6-4
(LT22-35-022) 3.91 6.72 66 Example 2 6-9
(LT22-30-027) 3.91 6.80 71 Example 3 6-15
(LT22-30-022) 3.92 6.70 60 Example 4 6-20
(LT22-30-024) 3.91 6.65 61 Example 5 6-56
(LT22-30-026) 3.93 6.51 56 Example 6 6-164
(LT22-30-025) 3.92 6.48 53 Example 7 6-195
(LT21-30-447) 3.91 6.79 68 Example 8 6-200
(LT21-35-501) 3.92 6.82 77 Example 9 6-214
(LT21-35-502) 3.91 6.88 73 Example 10 6-257
(LT21-30-452) 3.92 6.69 66 Example 11 6-258
(LT21-35-505) 3.90 6.70 78 Example 12 6-260
(LT22-30-033) 3.92 6.44 60 Example 13 6-261
(LT22-35-020) 3.91 6.50 62 Example 14 6-266
(LT22-30-036) 3.92 6.50 60 Example 15 6-267
(LT22-30-028) 3.91 6.42 55 Example 16 6-268
(LT22-30-032) 3.92 6.50 60 Example 17 6-270
(LT22-30-038) 3.92 6.44 57 Example 18 6-272
(LT21-30-431) 3.90 6.88 81 Example 19 6-282
(LT22-30-039) 3.92 6.63 68 Example 20 6-286
(LT22-35-051) 3.91 6.80 70 Example 21 6-303
(LT22-35-062) 3.92 6.40 57 Example 22 6-329
(LT22-30-007) 3.91 6.69 65 Example 23 6-344
(LT21-30-464) 3.90 6.88 75 Example 24 6-373
(LT21-35-506) 3.91 6.60 65 Example 25 6-433
(LT21-35-333) 3.90 6.72 80 Example 26 6-437
(LT21-35-256) 3.92 6.77 78 Example 27 6-441
(LT21-35-145) 3.92 6.75 75 Example 28 6-477
(LT21-35-510) 3.91 6.85 77

From the results in Table 2, the carbazole derivative compound according to the present invention can be used as a material for the capping layer of organic electronic devices, including organic light-emitting devices, and organic electronic devices including organic light-emitting devices using the same have improved efficiency, driving voltage, It can be seen that it exhibits excellent characteristics in terms of stability, etc. In particular, the compound according to the present invention has excellent micro-cavity phenomenon ability and exhibits high efficiency characteristics.

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

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

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

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 (4)

Carbazole derivative for organic electroluminescent devices, represented by the following formula (1).
[Formula 1]

In Formula 1,
a, b and c are each independently integers from 0 to 2,
L ₁ , L ₂ and L ₃ are each independently a phenylene group with a substituted or unsubstituted cyano group; A naphthylene group with a substituted or unsubstituted cyano group; And a cyano group substituted or unsubstituted pyridylene group; is selected from,
x, y and z are each independently integers from 0 to 3,
Ar _{1 ,} Ar ₂ and Ar ₃ are each independently a phenyl group; naphthyl group; phenanthrene group; triphenylene group; triazine group; benzofuran group; benzothiophene group; carbazole group; Dibenzofuran group; Dibenzothiophene group; fluorene group; benzoxazole group and benzothiazole group; is selected from among According to clause 1,
The compound of Formula 1 is a carbazole derivative for an organic electroluminescent device selected from compounds represented by Formulas 2 to 5 below.
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 2 to 5,
Z _1, Z ₂ , Z ₃ and Z ₄ are each independently selected from O, S and NR ₁ (where R ₁ is a phenyl group),
Q ₁ and Q ₂ are each independently CH or N,
L ₁ , L ₂ , L ₃ , Ar ₁ , a, b, c, x, y and z are as defined in Formula 1 above. According to clause 1,
Formula 1 is a carbazole derivative for organic electroluminescent devices selected from the compounds of Formula 6 below.
[Formula 6]























































































first electrode;
An organic material layer composed of a plurality of organic material layers disposed on the first electrode;
a second electrode disposed on the organic layer; and
It includes a capping layer disposed on the second electrode,
The organic material layer or the capping layer is an organic electroluminescent device comprising the carbazole derivative according to any one of claims 1 to 3.