KR102263822B1 - Organic compounds and organic electro luminescence device comprising the same - Google Patents

Abstract

The present invention relates to a novel compound and an organic electroluminescent device comprising the same, wherein the compound according to the present invention is an organic material layer of an organic electroluminescent device, preferably a hole injection layer, a hole transport layer, a hole transport auxiliary layer, a light emitting layer, an electron transport layer or As the electron injection layer is used, the luminous efficiency, driving voltage, lifespan, etc. of the organic electroluminescent device can be improved.

Description

Organic compound and organic electroluminescent device including same {ORGANIC COMPOUNDS AND ORGANIC ELECTRO LUMINESCENCE DEVICE COMPRISING THE SAME}

The present invention relates to a novel organic compound that can be used as a material for an organic electroluminescent device and an organic electroluminescent device comprising the same.

Starting with the observation of organic thin film emission by Bernanose in the 1950s, research on organic electroluminescent (EL) devices that led to blue electroluminescence using anthracene single crystals continued in 1965. ) presented an organic electroluminescent device having a stacked structure divided into a functional layer of a hole layer and a light emitting layer. Since then, in order to make a high-efficiency, long-life organic electroluminescent device, it has been developed in the form of introducing each characteristic organic material layer in the device, leading to the development of a specialized material used for this.

In an organic electroluminescent device, when a voltage is applied between two electrodes, holes are injected into the organic material layer at the anode, and electrons are injected into the organic material layer at the cathode. When injected holes and electrons meet, excitons are formed, and when these excitons fall to the ground state, light is emitted. In this case, the material used as the organic material layer may be classified into a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. according to their function.

The light emitting material may be divided into blue, green, and red light emitting materials and yellow and orange light emitting materials necessary to realize a better natural color according to the emission color. In addition, in order to increase color purity and increase luminous efficiency through energy transfer, a host/dopant system may be used as a light emitting material.

The dopant material may be divided into a fluorescent dopant using an organic material and a phosphorescent dopant using a metal complex compound containing heavy atoms such as Ir and Pt. At this time, since the phosphorescent material can theoretically improve the luminous efficiency by 4 times compared to the fluorescent material, studies on phosphorescent host materials as well as phosphorescent dopants are in progress.

_{Until now, NPB, BCP, Alq 3} and the like have been widely known as materials for the hole injection layer, hole transport layer, hole blocking layer, and electron transport layer, and anthracene derivatives have been reported as materials for the light emitting layer. In particular, phosphorescent materials, which have advantages in terms of efficiency improvement among light emitting materials, are blue, green, and red dopant materials, such as Firpic, Ir(ppy) ₃ , (acac)Ir(btp) ₂ Metal complex compounds containing Ir such as these are used. So far, 4,4-dicarbazolybiphenyl (CBP) has shown excellent properties as a phosphorescent host material.

However, the existing materials are advantageous in terms of light emitting properties, but since the glass transition temperature is low and thermal stability is deteriorated, the situation is not satisfactory in terms of the lifespan of the organic electroluminescent device. Accordingly, there is a demand for the development of materials with better performance.

Republic of Korea Patent Publication No. 10-2016-0041745 Republic of Korea Patent Publication No. 10-1579490

An object of the present invention is to provide a novel organic compound capable of improving the bonding force between holes and electrons while having excellent thermal stability due to a high glass transition temperature.

In addition, an object of the present invention is to provide an organic electroluminescent device having a low driving voltage and high luminous efficiency, including the novel organic compound, and having an improved lifespan.

In order to achieve the above object, an example of the present invention provides a compound represented by the following formula (1).

In Formula 1,

X is O or S;

L is a single bond, C ₆ ~ C ₁₈ is selected from the group consisting of an arylene group and a heteroarylene group having 5 to 18 nuclear atoms,

Ar _{1 To} Ar _{2 Are} the same as or different from each other, and each independently hydrogen, deuterium (D), halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C ₆ ~ C ₆₀ aryl group, heteroaryl group of 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ Aryloxy group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C ₆₀ Arylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C the group of boron ₆₀ aryl, C ₆ ~ C ₆₀ aryl phosphine group, is selected from the group consisting of C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ C ₆₀ aryl group of an amine of,

R _{1 To} R _{5 Are} the same as or different from each other, and each independently hydrogen, deuterium (D), a halogen group, a cyano group, a nitro group, an amino group, a C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group , C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C ₆ ~ C ₆₀ aryl group, heteroaryl group of 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ Aryloxy group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C ₆₀ Arylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, arylboronic group of C ₆ ~ C _60, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~, or selected from the group consisting of an aryl amine of the C ₆₀ in, or which adjacent may combine with a group to form a condensed ring,

a, b, c and d are integers from 0 to 5, e is an integer from 0 to 3;

The arylene group, heteroarylene group and Ar ₁ , Ar ₂ and R ₁ to R ₅ of the above L are alkyl groups, alkenyl groups, alkynyl groups, cycloalkyl groups, heterocycloalkyl groups, aryl groups, heteroaryl groups, alkyloxy groups, arylox Group, alkylsilyl group, arylsilyl group, alkylboron group, arylboron group, arylphosphine group, arylphosphine oxide group and arylamine group are each independently deuterium, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ Alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, nucleus A heteroaryl group having 5 to 60 atoms, C ₁ to C ₄₀ Alkyloxy group, C ₆ to C ₆₀ Aryloxy group, C ₁ to C ₄₀ Alkylsilyl group, C ₆ to C ₆₀ Arylsilyl group, C group of ₁ to alkylboronic of C _40, C ₆ ~ C ₆₀ aryl boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ C ₆₀ aryl amine When unsubstituted or substituted with one or more substituents selected from the group consisting of a group, and a plurality of the substituents are the same or different from each other.

In addition, the present invention includes an anode, a cathode, and at least one organic material layer interposed between the anode and the cathode, wherein at least one of the at least one organic material layer comprises a compound represented by Formula 1 above. A light emitting device is provided.

Here, at least one of the one or more organic material layers including the compound represented by Formula 1 may be selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, and a hole transport layer and/or a light emitting layer It is preferable to be In this case, the compound represented by Formula 1 is a hole transport layer material.

Since the compound represented by Formula 1 according to an example of the present invention has excellent thermal stability, carrier transport ability, light emitting ability, and the like, it may be used as an organic material layer material of an organic electroluminescent device.

In addition, when the compound represented by Formula 1 according to an example of the present invention is used as an organic material layer material, an organic electroluminescent device with greatly improved aspects such as excellent light emitting performance, driving voltage, lifespan, and efficiency can be manufactured, and further, such organic The electroluminescent device can be effectively applied to a full-color display panel or the like.

Hereinafter, the present invention will be described in detail.

<New organic compound>

The organic compound according to the present invention has a structure in which a substituted or unsubstituted phenyl group is introduced at the 1st to 4th carbon positions of dibenzofuran or dibenzothiophene as a basic skeleton, and the dibenzofuran or dibenzothiophene It is a structure in which a diaryl amine is introduced at one of positions 6 to 9 of benzothiophene, and is characterized in that it is represented by Formula 1 above. When the organic electroluminescent device includes the compound represented by Formula 1, the device has a low driving voltage, high luminescence and current efficiency, and a long lifespan. Here, the carbon position number of dibenzofuran or dibenzothiophene is as follows.

(X = O, S)

(X = O, S)

As a host of a conventional organic electroluminescent device, a dibenzofuran compound in which one phenyl group is introduced at the 4th carbon position is known. In this case, since the glass transition temperature (Tg) of the compound is higher than that of the conventional organic material layer material, thermal stability is improved, and thus durability and lifespan characteristics of the device are improved. However, the dibenzofuran compound in which one phenyl group is introduced has a higher driving voltage of the organic electroluminescent device than the conventional organic material layer material (Alq3 or CBP) or similar to the conventional one.

According to the present invention, 4 phenyl groups are introduced at the 1st to 4th carbon positions of dibenzofuran or dibenzothiophene to have a spherical shape, so that more steric effects are obtained than when one phenyl group is introduced. This not only can lower the deposition temperature, but also increase the glass transition temperature (Tg) so that thermal stability can be improved. In addition, the hole transport characteristics in the blue organic light emitting diode may be improved due to the high glass transition temperature (Tg) and the stereoscopic effect. Therefore, the compound of the present invention can further improve thermal stability and hole transport properties compared to the conventional dibenzofuran compound in which one phenyl group is introduced.

In addition, since the diaryl amine is introduced into one of the 6th to 9th carbon positions of dibenzofuran or dibenzothiophene to improve hole transport ability, it can serve as a light emitting auxiliary layer. In addition, since it has a homo level between the hole transport layer and the light emitting layer, the movement of holes is facilitated, thereby improving driving voltage and efficiency. In addition, since the stability of the hole is also better, the effect of improving the lifespan may appear.

Therefore, when the compound of Formula 1 according to the present invention is used as a blue hole transport material or a blue host material of an organic electroluminescent device, organic electroluminescence compared _{to conventional organic material layer materials (eg, CBP, BCP, Alq 3 )} It is possible to further improve the driving voltage, light emission and current efficiency, durability, and lifespan characteristics of the device.

In Formula 1, X is O or S.

In addition, R ₁ to R ₅ are the same as or different from each other, and each independently hydrogen, deuterium (D), a halogen group, a cyano group, a nitro group, an amino group, a C ₁ to C ₄₀ alkyl group, C ₂ to C ₄₀ Alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C ₆ ~ C ₆₀ aryl group, heteroaryl of 5 to 60 nuclear atoms Group, C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ Aryloxy group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C ₆₀ Arylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C group ₆₀ arylboronic of, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~, or selected from the group consisting of an aryl amine of the C ₆₀ in, or They may combine with adjacent groups to form condensed rings.

In addition, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkylboron group of _{R 1} to R ₅ , aryl boron group, aryl phosphine group, aryl phosphine oxide group and arylamine group are each independently deuterium, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, heteroaryl group of 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ Aryloxy group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C ₆₀ Arylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ aryl of C ₆₀ boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ substituted or non-substituted with substituents at least one selected from the group consisting of an aryl amine of the C ₆₀ and a plurality of the substituents are the same or different from each other.

Preferably, the R ₁ to R ₄ are hydrogen or a C ₆ -C ₆₀ aryl group, and R ₅ is selected from the group consisting of hydrogen, a C ₁ to C ₄₀ alkyl group and a C ₆ to C _{60 aryl group, or} It may combine with adjacent groups to form a condensed ring.

Moreover, a, b, c, and d are the integers of 0-5, and e is the integer of 0-3. In this case, when a to e are 0, it means that the phenyl group is not substituted.

In addition, L is selected from the group consisting of a single bond, a C ₆ ~ C ₁₈ arylene group, and a heteroarylene group having 5 to 18 nuclear atoms.

In addition, the arylene group and heteroarylene group of L are each independently deuterium, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cyclo Alkyl group, heterocycloalkyl group having 3 to 40 nuclear atoms, C ₁ to C ₄₀ alkyl group, C ₆ to C ₆₀ aryl group, heteroaryl group having 5 to 60 nuclear atoms, C ₁ to C ₄₀ alkyloxy group , C ₆ ~ C ₆₀ Aryloxy group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C ₆₀ Arylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ C ₆₀ Aryl boron group , C ₆ ~ C ₆₀ Aryl phosphine group, C ₆ ~ C ₆₀ Aryl phosphine oxide group and C ₆ ~ C ₆₀ Unsubstituted or substituted with one or more substituents selected from the group consisting of an arylamine group, the substituent is In the case of a plurality, they are the same or different from each other.

According to one example, L is a single bond or is selected from the group consisting of structures represented by the following L-1 to L-11, but is not limited thereto.

In addition, Ar _{1 To} Ar _{2 Are} the same or different from each other, and each independently hydrogen, deuterium (D), halogen, cyano group, nitro group, C ₁ ~ C ₄₀ alkyl group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C ₆ ~ C ₆₀ aryl group, heteroaryl group of 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ Aryloxy group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C ₆₀ Arylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ arylboronic group of C _60, C ₆ ~ C ₆₀ aryl phosphine group, is selected from C ₆ ~ C ₆₀ aryl phosphine oxide group, and the group consisting of C ₆ - C ₆₀ aryl amine of the.

In addition, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a heterocycloalkyl group, an aryl group, a heteroaryl group, an alkyloxy group, an aryloxy group, an alkylsilyl group, an arylsilyl group, an alkylboron group of _{Ar 1} and Ar ₂ , aryl boron group, aryl phosphine group, aryl phosphine oxide group and arylamine group are each independently deuterium, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, heteroaryl group of 5 to 60 nuclear atoms, C ₁ ~ C ₄₀ Alkyloxy group, C ₆ ~ C ₆₀ Aryloxy group, C ₁ ~ C ₄₀ Alkylsilyl group, C ₆ ~ C ₆₀ Arylsilyl group, C ₁ ~ C ₄₀ Alkyl boron group, C ₆ ~ aryl of C ₆₀ boron group, C ₆ ~ C ₆₀ aryl phosphine group, C ₆ ~ C ₆₀ aryl phosphine oxide group, and a C ₆ ~ substituted or non-substituted with substituents at least one selected from the group consisting of an aryl amine of the C ₆₀ ring, and when the substituents are plural, they are the same or different from each other.

In one example, Ar ₁ and Ar ₂ may each independently be a substituent selected from the group consisting of structures represented by the following Ar-1 to Ar-7, but is not limited thereto.

Examples of the compound represented by Formula 1 according to the present invention include a compound represented by any one of the following Formulas 2 to 9, but is not limited thereto.

In Formulas 2 to 9,

R ₁ to R ₅ , a to e, L, Ar ₁ and Ar ₂ are each the same as defined in Formula 1 above.

The compound represented by Chemical Formula 1 according to an example of the present invention described above may be further embodied in the following compound structures consisting of A1 to A91 and B1 to B91. However, the compound represented by Formula 1 of the present invention is not limited by those exemplified below.

In the present invention, "alkyl" refers to a monovalent substituent derived from a linear or branched saturated hydrocarbon having 1 to 40 carbon atoms. Examples thereof include, but are not limited to, methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, and the like.

In the present invention, "alkenyl (alkenyl)" refers to a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon double bonds. Examples thereof include, but are not limited to, vinyl (vinyl), allyl (allyl), isopropenyl (isopropenyl), 2-butenyl (2-butenyl) and the like.

In the present invention, "alkynyl (alkynyl)" refers to a monovalent substituent derived from a straight or branched unsaturated hydrocarbon having 2 to 40 carbon atoms and having one or more carbon-carbon triple bonds. Examples thereof include, but are not limited to, ethynyl, 2-propynyl, and the like.

In the present invention, "aryl" refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 40 carbon atoms in which a single ring or two or more rings are combined. In addition, two or more rings may be simply attached to each other (pendant) or condensed form may be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, and the like.

In the present invention, "heteroaryl" refers to a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 5 to 40 nuclear atoms. In this case, one or more carbons, preferably 1 to 3 carbons in the ring are substituted with a heteroatom such as N, O, S or Se. In addition, a form in which two or more rings are simply attached to each other or condensed may be included, and further, a form condensed with an aryl group may be included. Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, indolyl ( polycyclic rings such as indolyl), purinyl, quinolyl, benzothiazole, and carbazolyl, and 2-furanyl, N-imidazolyl, and 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like, but is not limited thereto.

In the present invention, "aryloxy" is a monovalent substituent represented by RO-, wherein R means aryl having 5 to 40 carbon atoms. Examples of such aryloxy include, but are not limited to, phenyloxy, naphthyloxy, diphenyloxy, and the like.

In the present invention, "alkyloxy" is a monovalent substituent represented by R'O-, wherein R' means alkyl having 1 to 40 carbon atoms, and has a linear, branched or cyclic structure. may include. Examples of alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, pentoxy, and the like.

In the present invention, "arylamine" means an amine substituted with an aryl having 6 to 40 carbon atoms.

In the present invention, "cycloalkyl" means a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclopentyl, cyclohexyl, norbornyl, adamantine, and the like.

In the present invention, "heterocycloalkyl" means a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 nuclear atoms, and at least one carbon in the ring, preferably 1 to 3 carbons, is N, O, S or a hetero atom such as Se. Examples of such heterocycloalkyl include, but are not limited to, morpholine, piperazine, and the like.

In the present invention, "alkylsilyl" refers to silyl substituted with alkyl having 1 to 40 carbon atoms, and "arylsilyl" refers to silyl substituted with aryl having 5 to 40 carbon atoms.

In the present invention, "condensed ring" means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.

The compound of Formula 1 according to an example of the present invention can be synthesized in various ways with reference to Synthesis Examples. The detailed synthesis process for the compound of the present invention will be described in detail in the following Synthesis Examples.

<Organic electroluminescent device>

On the other hand, another aspect of the present invention relates to an organic electroluminescent device including the compound represented by the above-described formula (1).

Specifically, the organic electroluminescent device according to the present invention includes an anode, a cathode, and one or more organic material layers interposed between the anode and the cathode, wherein at least one of the one or more organic material layers is and a compound represented by Formula 1 above. In this case, the compound may be used alone, or two or more may be used in combination.

According to an example, the one or more organic material layers may be any one or more of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer, and at least one organic material layer may include a compound represented by Formula 1 above. have. Preferably, the organic layer including the compound of Formula 1 may be a light emitting layer and/or a hole transport layer, and more preferably a hole transport layer material. In addition, between the hole transport layer and the light emitting layer, it is also preferable to include a light emitting auxiliary layer composed of the compound represented by the above formula (1). In this case, the compound may be a phosphorescence auxiliary layer material.

The structure of the organic electroluminescent device according to the present invention is not particularly limited, and for example, it may be a structure in which one or two or more organic material layers are stacked between electrodes. Non-limiting examples thereof include (i) an anode, a light emitting layer, a cathode; (ii) an anode, a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, a cathode; or (iii) structures such as an anode, a hole injection layer, a hole transport layer, a light emitting layer, and a cathode.

In addition, the organic electroluminescent device according to the present invention has a structure in which an anode, one or more organic material layers and a cathode are sequentially stacked as described above, as well as an insulating layer or an adhesive layer may be inserted at the interface between the electrode and the organic material layer.

The organic electroluminescent device according to the present invention uses materials and methods known in the art, except that at least one layer of the organic material layer is formed to include the compound represented by Formula 1 of the present invention. It can be prepared by forming

The organic material layer including the compound represented by Formula 1 may be formed by a vacuum deposition method or a solution coating method. Examples of the solution coating method include, but are not limited to, spin coating, dip coating, doctor blading, inkjet printing, or thermal transfer method.

The substrate usable in the present invention is not particularly limited, and non-limiting examples include a silicon wafer, quartz, a glass plate, a metal plate, a plastic film, and a sheet.

In addition, examples of the anode material include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); combinations of metals and oxides such as ZnO:Al or SnO _{2 :Sb;} conductive polymers such as polythiophene, poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDT), polypyrrole or polyaniline; and carbon black, but is not limited thereto.

In addition, examples of the anode material include a metal such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, or lead, or an alloy thereof; and a multilayer structure material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

In addition, the hole injection layer, the hole transport layer, the light emitting layer, the electron injection layer and the electron transport layer are not particularly limited, and conventional materials known in the art may be used.

Hereinafter, the present invention will be described in detail through examples. However, the following examples are merely illustrative of the present invention, and the present invention is not limited by the following examples.

[Preparation Example 1] Synthesis of Core-1

<Step 1> 6'- chloro -3',4',5'- triphenyl -[1,1':2',1''- terphenyl ]-2- ol's synthesis

3',4'-Dichloro-5',6'-diphenyl-1,1':2',1''-terphenyl (45 g, 100 mmol) and (2-hydroxyphenyl)boronic acid (14 g, 100 mmol) ), Pd(PPh ₃ ) ₄ (4.6 g, 4 mmol), and NaOH (12 g, 300 mmol) were added to 500 ml THF and 200 ml H ₂ O and stirred at 75° C. for 8 hours. After completion of the reaction, the organic layer was separated by extraction with ethyl acetate, and water was removed using _{MgSO 4 .} After removing the solvent from the water-removed organic layer, it was purified by column chromatography to 6'-chloro-3',4',5'-triphenyl-[1,1':2',1''-terphenyl]-2- ol (50 g, yield 98%) was obtained.

¹ H-NMR: δ 5.35 (s, 1H), 7.01 (d, 1H), 7.07 (d, 1H), 7.24 (m, 1H), 7.41 (m, 4H), 7.51 (m, 8H), 7.52 ( m, 8H), 7.62 (d, 1H)

<Step 2> 1,2,3,4- of tetraphenyldibenzo[b,d]furan synthesis

6'-chloro-3',4',5'-triphenyl-[1,1':2',1''-terphenyl]-2-ol (50 g, 98 mmol) and sodium hydrosulfite (26 g, 147 mmol), KOH (8 g, 147 mmol) and tetrabutylammonium bromide (32 g, 98 mmol) in 500 ml DMF and stirred at 140° C. for 8 hours. After completion of the reaction, extraction was performed with methylene chloride, and MgSO ₄ was added thereto and filtered. After removing the solvent of the filtered organic layer, the target compound 1,2,3,4-tetraphenyldibenzo[b,d]furan (40 g, yield 87%) was obtained by column chromatography.

¹ H-NMR: δ 7.32 (t, 1H), 7.38 (t, 1H), 7.41 (m, 4H), 7.51 (m, 8H), 7.52 (m, 8H), 7.66 (d, 1H), 7.89 ( d, 1H)

<Step 3> (6,7,8,9- tetraphenyldibenzo[b,d]furan -4- yl ) Synthesis of boronic acid

1,2,3,4-tetraphenyldibenzo[b,d]furan (40 g, 85 mmol) was added to 300 ml THF and stirred at -75°C. After reaching -75°C, 2.5M n-BuLi (34 ml, 85 mmol) was added slowly. Then, after stirring for about 1 hour, triisopropyl borate (39 ml, 170 mmol) was slowly added. After stirring for about 2 hours, 500 ml 1N HCl was added to terminate the reaction. Then, the organic layer was separated by extraction with ethyl acetate, and water was removed using _{MgSO 4 .} After removing the solvent from the organic layer from which water was removed, MC was added and stirred. Then, the solid was filtered to obtain the target compound (6,7,8,9-tetraphenyldibenzo[b,d]furan-4-yl)boronic acid (35 g, yield 78%).

¹ H-NMR: δ 2.00 (s, 2H), 7.38 (t, 1H), 7.41 (m, 4H), 7.50 (d, 1H), 7.51 (m, 8H), 7.52 (m, 8H), 7.89 ( d, 1H)

<Step 4> Synthesis of Core-1

6,7,8,9-tetraphenyldibenzo[b,d]furan-4-yl)boronic acid (35 g, 68 mmol) and (2-1-bromo-3-chlorobenzene (13 g, 68 mmol) and Pd ( PPh ₃ ) ₄ (3.1 g, 3 mmol) and NaOH (8.1 g, 204 mmol) were added to 200 ml THF and 100 ml H ₂ O, and stirred for 8 hours at 75° C. After completion of the reaction, the organic layer was extracted with ethyl acetate. was separated and _{water was removed using MgSO 4.} After removing the solvent from the organic layer from which the water was removed, it was purified by column chromatography to obtain Core-1 (35 g, yield 88%).

¹ H-NMR: δ 7.38 (t, 1H), 7.40 (d, 1H), 7.41 (m, 4H), 7.45 (m, 2H), 7.50 (d, 1H), 7.51 (m, 8H), 7.52 ( m, 8H), 7.89 (d, 1H), 8.01 (s, 1H)

[Preparation Example 2] Synthesis of Core-2

<Step 1> 6'- chloro -2-( methylsulfinyl )-3',4',5'- triphenyl Synthesis of -1,1':2',1''-terphenyl

3',4'-Dichloro-5',6'-diphenyl-1,1':2',1''-terphenyl (45 g, 100 mmol) and (2-(methylsulfinyl)phenyl)boronic acid (18 g , 100 mmol) and Pd(PPh ₃ ) ₄ (4.6 g, 4 mmol), NaOH (12 g, 300 mmol) were put in 500 ml THF and 200 ml H ₂ O and stirred at 75° C. for 8 hours. After completion of the reaction, the organic layer was separated by extraction with ethyl acetate, and water was removed using _{MgSO 4 .} After removing the solvent from the organic layer from which water was removed, it was purified by column chromatography to 6'-chloro-2-(methylsulfinyl)-3',4',5'-triphenyl-1,1':2',1''- terphenyl (50 g, yield 91%) was obtained

¹ H-NMR: δ 2.64 (s, 3H), 7.01 (d, 1H), 7.07 (d, 1H), 7.24 (m, 1H), 7.41 (m, 4H), 7.51 (m, 8H), 7.52 ( m, 8H), 7.62 (d, 1H)

<Step 2> 1,2,3,4- of tetraphenyldibenzo[b,d]thiophene synthesis

Add 100 ml of sulfuric acid to 6'-chloro-2-(methylsulfinyl)-3',4',5'-triphenyl-1,1':2',1''-terphenyl (50 g, 90 mmol) for 6 hours stirred for a while. After completion of the reaction, 500 ml of 1N NaOH solution was added and stirred for 1 hour. The resulting solid was recrystallized using toluene after filtering to obtain the target compound, 1,2,3,4-tetraphenyldibenzo[b,d]thiophene (40 g, yield 91%).

¹ H-NMR: δ 7.32 (t, 1H), 7.38 (t, 1H), 7.41 (m, 4H), 7.51 (m, 8H), 7.52 (m, 8H), 7.66 (d, 1H), 7.98 ( d, 1H)

<Step 3> (6,7,8,9- tetraphenyldibenzo[b,d]thiophen -4- yl ) Synthesis of boronic acid

1,2,3,4-tetraphenyldibenzo[b,d]furan (40 g, 82 mmol) was added to 300 ml THF and stirred at -75°C. After reaching -75°C, 2.5M n-BuLi (33 ml, 82mmol) was slowly added. Then, after stirring for about 1 hour, triisopropyl borate (38 ml, 164 mmol) was slowly added. After stirring for about 2 hours, the reaction was terminated by adding 500 ml 1N HCl. Then, the organic layer was separated by extraction with ethyl acetate, and water was removed using _{MgSO 4 .} After removing the solvent from the organic layer from which water was removed, MC was added and stirred. And the solid was filtered to obtain the target compound (6,7,8,9-tetraphenyldibenzo[b,d]thiophen-4-yl)boronic acid (35 g, yield 80%).

¹ H-NMR: δ 2.00 (s, 2H), 7.38 (t, 1H), 7.41 (m, 4H), 7.50 (d, 1H), 7.51 (m, 8H), 7.52 (m, 8H), 7.98 ( d, 1H)

<Step 4> Synthesis of Core-2

6,7,8,9-tetraphenyldibenzo[b,d]thiophen-4-yl)boronic acid (35 g, 66 mmol) and (2-1-bromo-3-chlorobenzene (13 g, 66 mmol) and Pd ( PPh ₃ ) ₄ (2.6 g, 3 mmol) and NaOH (7.9 g, 198 mmol) were added to 200 ml THF and 100 ml H ₂ O, and stirred at 75° C. for 8 hours After completion of the reaction, the mixture was extracted with ethyl acetate and the organic layer After separation, _{water was removed using MgSO 4.} After removing the solvent from the organic layer from which water was removed, it was purified by column chromatography to obtain Core-2 (30 g, yield 76%).

¹ H-NMR: δ 7.38 (t, 1H), 7.40 (d, 1H), 7.41 (m, 4H), 7.45 (m, 2H), 7.50 (d, 1H), 7.51 (m, 8H), 7.52 ( m, 8H), 8.01 (s, 1H), 8.20 (d, 1H)

[ Synthesis example 1] Synthesis of compound A-43

Core-1 (5.0 g, 8.6 mmol), diphenylamine (1.5 g, 8.6 mmol) and Pd ₂ (dba) ₃ (0.3 g, 0.3 mmol), P(t-Bu) ₃ (0.1 g, 0.7 mmol), NaOt -Bu (2.5 g, 25.8 mmol) was added to 50 ml of Toluene and stirred at 110 for 4 hours. After completion of the reaction, the organic layer was separated by extraction with toluene, and then water was removed using _{MgSO 4 .} After removing the solvent from the organic layer from which water was removed, column chromatography was purified to obtain Compound A-43 (5 g, 82%).

[LCMS]: 715

[ Synthesis example 2] Synthesis of compound A-44

Core-1 (5.0 g, 8.6 mmol), N-phenyl-[1,1'-biphenyl]-4-amine (2.1 g, 8.6 mmol) and Pd ₂ (dba) ₃ (0.3 g, 0.3 mmol), P (t-Bu) ₃ (0.1 g, 0.7 mmol) and NaOt-Bu (2.5 g, 25.8 mmol) were added to 50 ml of Toluene and stirred at 110 for 4 hours. After completion of the reaction, the organic layer was separated by extraction with toluene, and then water was removed using _{MgSO 4 .} After removing the solvent from the organic layer from which water was removed, column chromatography was purified to obtain Compound A-44 (5 g, 73%).

[LCMS]: 791

[ Synthesis example 3] Synthesis of compound A-46

Core-1 (5.0 g, 8.6 mmol), N-phenylnaphthalen-2-amine (1.9 g, 8.6 mmol) and Pd ₂ (dba) ₃ (0.3 g, 0.3 mmol), P(t-Bu) ₃ (0.1 g) , 0.7 mmol) and NaOt-Bu (2.5 g, 25.8 mmol) were added to 50 ml of Toluene and stirred at 110 for 4 hours. After completion of the reaction, the organic layer was separated by extraction with toluene, and then water was removed using _{MgSO 4 .} After removing the solvent from the organic layer from which water was removed, column chromatography was purified to obtain Compound A-46 (5 g, 76%).

[LCMS]: 765

[ Synthesis example 4] Synthesis of compound A-48

Core-1 (5.0 g, 8.6 mmol), bis-([1,1'-biphenyl]-4-yl)amine (2.8 g, 8.6 mmol) and Pd ₂ (dba) ₃ (0.3 g, 0.3 mmol), P(t-Bu) ₃ (0.1 g, 0.7 mmol) and NaOt-Bu (2.5 g, 25.8 mmol) were added to 50 ml of Toluene and stirred at 110 for 4 hours. After completion of the reaction, the organic layer was separated by extraction with toluene, and then water was removed using _{MgSO 4 .} After removing the solvent from the organic layer from which water was removed, column chromatography was purified to obtain Compound A-48 (6 g, 81%).

[LCMS]: 867

[ Synthesis example 5] Synthesis of compound A-50

Core-1 (5.0 g, 8.6 mmol), N-phenyldibenzo[b,d]furan-3-amine (2.2 g, 8.6 mmol) and Pd ₂ (dba) ₃ (0.3 g, 0.3 mmol), P(t- Bu) ₃ (0.1 g, 0.7 mmol) and NaOt-Bu (2.5 g, 25.8 mmol) were added to 50 ml of Toluene and stirred at 110 for 4 hours. After completion of the reaction, the organic layer was separated by extraction with toluene, and then water was removed using _{MgSO 4 .} After removing the solvent from the organic layer from which water was removed, column chromatography was purified to obtain Compound A-50 (5 g, 72%).

[LCMS]: 805

[ Synthesis example 6] Synthesis of compound B-43

Core-2 (5.2 g, 8.6 mmol), diphenylamine (1.5 g, 8.6 mmol) and Pd ₂ (dba) ₃ (0.3 g, 0.3 mmol), P(t-Bu) ₃ (0.1 g, 0.7 mmol), NaOt -Bu (2.5 g, 25.8 mmol) was added to 50 ml of Toluene and stirred at 110 for 4 hours. After completion of the reaction, the organic layer was separated by extraction with toluene, and then water was removed using _{MgSO 4 .} After removing the solvent from the organic layer from which water was removed, column chromatography was purified to obtain Compound B-43 (5 g, 79%).

[LCMS]: 731

[ Synthesis example 7] Synthesis of compound B-44

Core-2 (5.2 g, 8.6 mmol), N-phenyl-[1,1'-biphenyl]-4-amine (2.1 g, 8.6 mmol) and Pd ₂ (dba) ₃ (0.3 g, 0.3 mmol), P (t-Bu) ₃ (0.1 g, 0.7 mmol) and NaOt-Bu (2.5 g, 25.8 mmol) were added to 50 ml of Toluene and stirred at 110 for 4 hours. After completion of the reaction, the organic layer was separated by extraction with toluene, and then water was removed using _{MgSO 4 .} After removing the solvent from the organic layer from which water was removed, column chromatography was purified to obtain Compound B-44 (5 g, 72%).

[LCMS]: 807

[ Synthesis example 8] Synthesis of compound B-46

Core-2 (5.2 g, 8.6 mmol), N-phenylnaphthalen-2-amine (1.9 g, 8.6 mmol) and Pd ₂ (dba) ₃ (0.3 g, 0.3 mmol), P(t-Bu) ₃ (0.1 g) , 0.7 mmol) and NaOt-Bu (2.5 g, 25.8 mmol) were added to 50 ml of Toluene and stirred at 110 for 4 hours. After completion of the reaction, the organic layer was separated by extraction with toluene, and then water was removed using _{MgSO 4 .} After removing the solvent from the organic layer from which water was removed, column chromatography was purified to obtain Compound B-46 (5 g, 75%).

[LCMS]: 781

[ Synthesis example 9] Synthesis of compound B-48

Core-2 (5.2 g, 8.6 mmol), bis-([1,1'-biphenyl]-4-yl)amine (2.8 g, 8.6 mmol) and Pd ₂ (dba) ₃ (0.3 g, 0.3 mmol), P(t-Bu) ₃ (0.1 g, 0.7 mmol) and NaOt-Bu (2.5 g, 25.8 mmol) were added to 50 ml of Toluene and stirred at 110 for 4 hours. After completion of the reaction, the organic layer was separated by extraction with toluene, and then water was removed using _{MgSO 4 .} After removing the solvent from the organic layer from which water was removed, column chromatography was purified to obtain Compound B-48 (5 g, 66%).

[LCMS]: 883

[ Synthesis example 10] Synthesis of compound B-50

Core-2 (5.2 g, 8.6 mmol), N-phenyldibenzo[b,d]furan-3-amine (2.2 g, 8.6 mmol) and Pd ₂ (dba) ₃ (0.3 g, 0.3 mmol), P(t- Bu) ₃ (0.1 g, 0.7 mmol) and NaOt-Bu (2.5 g, 25.8 mmol) were added to 50 ml of Toluene and stirred at 110 for 4 hours. After completion of the reaction, the organic layer was separated by extraction with toluene, and then water was removed using _{MgSO 4 .} After removing the solvent from the organic layer from which water was removed, column chromatography was purified to obtain Compound B-50 (5 g, 71%).

[LCMS]: 805

[Example 1] Fabrication of blue organic EL device

After high-purity sublimation purification of Compound A-43 synthesized in Synthesis Example 1 by a commonly known method, a blue organic EL device was manufactured according to the following procedure.

First, a glass substrate coated with indium tin oxide (ITO) to a thickness of 1500 Å was washed with distilled water ultrasonically. After washing with distilled water, it is ultrasonically cleaned with a solvent such as isopropyl alcohol, acetone, methanol, etc., dried, transferred to a UV OZONE cleaner (Power sonic 405, Hwashin Tech), and then the substrate is cleaned using UV for 5 minutes and vacuum evaporator The substrate was transferred to

On the prepared ITO transparent electrode, DS-205 (Doosan) (80 nm) / NPB (15 nm) / Compound A-43 (15 nm) / ADN+5%DS-405 (Doosan) (300 nm) / BCP (10 nm) / Alq ₃ (30 nm) / LiF (1 nm) / Al (200 nm) was laminated in the order to prepare an organic electroluminescent device.

[Examples 2 to 10] Fabrication of blue organic EL device

Compounds A-44, A-46, A-48, A-50, B-43, B-44, B-46, B- synthesized in Synthesis Examples 2 to 10 instead of Compound A-43 used in Example 1 A blue organic electroluminescent device was prepared in the same manner as in Example 1, except that 48 and B-50 were used, respectively.

[Comparative Example 1] Fabrication of blue organic EL device

A blue organic electroluminescent device was prepared in the same manner as in Example 1, except that Compound Cpd 1 was used instead of Compound A-43 used in Example 1.

[Comparative Example 2] Fabrication of blue organic EL device

A blue organic electroluminescent device was prepared in the same manner as in Example 1, except that Compound Cpd 2 was used instead of Compound A-43 used in Example 1.

[Comparative Example 3] Fabrication of blue organic EL device

A blue organic electroluminescent device was prepared in the same manner as in Example 1, except that it was prepared without a light-emitting auxiliary layer.

The structures of NPB, AND, BCP, compound Cpd 1 and compound Cpd 2 used in Examples 1 to 10 and Comparative Examples 1 to 3 are as follows.

[ evaluation example ]

For each of the blue organic electroluminescent devices manufactured in Examples 1 to 10 and Comparative Examples 1 to 3, the driving voltage and current efficiency at a current density of 10 mA/cm 2 were measured, and the results are shown in Table 1 below. .

Sample light emitting layer drive voltage
(V) EL peak
(nm) current efficiency
(cd/A) Example 1 A-43 5.50 455 6.9 Example 2 A-44 5.50 455 7.0 Example 3 A-46 5.32 455 7.2 Example 4 A-48 5.43 455 7.1 Example 5 A-50 5.41 455 7.0 Example 6 B-43 5.55 455 6.9 Example 7 B-44 5.23 455 6.4 Example 8 B-46 5.24 455 6.3 Example 9 B-48 5.45 455 6.5 Example 10 B-50 5.55 455 6.9 Comparative Example 1 One 5.67 455 6.2 Comparative Example 2 2 5.75 456 6.4 Comparative Example 3 - 6.05 455 5.5

As shown in Table 1, the blue color of Examples 1 to 10 using the compound (Compounds A-1 to A-91, B-1 to B-91) of Formula 1 according to the present invention as a light emitting auxiliary layer material The organic electroluminescent device, the blue organic electroluminescent device of Comparative Examples 1 and 2 using the compound Cpd1 and the compound Cpd2 as the light emitting auxiliary layer material, and the blue organic electroluminescent of Comparative Example 3 using ADN as the light emitting layer material without the light emission auxiliary layer It was found that the driving voltage and current efficiency were better than those of the device.

Claims (9)

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

In Formula 1,
X is O or S;
L is a single bond, C ₆ ~ C ₁₈ is selected from the group consisting of an arylene group and a heteroarylene group having 5 to 18 nuclear atoms,
Ar _{1 To} Ar _{2 Are} the same or different from each other, and each independently selected from the group consisting of hydrogen, deuterium (D), a C ₆ ~ C ₆₀ aryl group and a heteroaryl group having 5 to 60 nuclear atoms,
The arylene group, heteroarylene group and Ar ₁ , Ar ₂ aryl group, heteroaryl group of L are each independently deuterium, halogen, cyano group, nitro group, C ₂ ~ C ₄₀ alkenyl group, C ₂ ~ C ₄₀ alkynyl group, C ₃ ~ C ₄₀ cycloalkyl group, heterocycloalkyl group of 3 to 40 nuclear atoms, C ₁ ~ C ₄₀ alkyl group, C ₆ ~ C ₆₀ aryl group, heteroaryl group of 5 to 60 nuclear atoms And C ₆ ~ C _{60 When} substituted or unsubstituted with one or more substituents selected from the group consisting of an arylamine group, and a plurality of the substituents, they are the same or different from each other. According to claim 1, wherein the compound represented by Formula 1 is a compound represented by any one of Formulas 2 to 9:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

In Formulas 2 to 9,
L, Ar ₁ and Ar ₂ are each the same as defined in claim 1. According to claim 1,
Ar ₁ and Ar ₂ are each independently selected from the group consisting of structures represented by the following Ar-1 to Ar-7.

According to claim 1,
Wherein L is a single bond, an organic compound selected from the group consisting of structures represented by the following L-1 to L-11.

According to claim 1,
The compound represented by Formula 1 is a compound selected from the group consisting of compounds represented by the following A1 to B91.

According to claim 1,
The compound represented by Formula 1 is represented by the following compounds A-43, A-44, A-46, A-48, A-50, B-43, B-44, B-46, B-48 or B-50. the compound shown.

An anode, a cathode, and one or more organic material layers interposed between the anode and the cathode,
At least one of the one or more organic material layers is an organic electroluminescent device comprising the compound according to any one of claims 1 to 6. 8. The method of claim 7,
The organic material layer comprising the compound is an organic electroluminescent device selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer and an electron injection layer. 8. The method of claim 7,
The organic electroluminescent device includes a light emitting auxiliary layer between the hole transport layer and the light emitting layer,
The light emitting auxiliary layer is an organic electroluminescent device comprising a compound represented by the formula (1).