KR102128702B1 - Novel organic electroluminescence compounds and organic electroluminescence device containing the same - Google Patents

Abstract

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device comprising the same. The organic electroluminescent compound according to the present invention has the advantage of reducing the driving voltage of the device and at the same time manufacturing an OLED device with improved power efficiency.

Description

Novel organic electroluminescence compounds and organic electroluminescence devices containing the same}

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device comprising the same.

Among the display elements, the organic electroluminescent element (OLED) is a self-emission type display element, and has a wide viewing angle, excellent contrast, and a fast response speed. In 1987, Eastman Kodak first developed an organic EL device using a low molecular weight aromatic diamine and an aluminum complex as a material for forming a light emitting layer [Appl. Phys. Lett. 51, 913, 1987].

The most important factor in determining the luminous efficiency in an organic electroluminescent device is a luminescent material. Fluorescent luminescent materials have been widely used as luminescent materials to date, but the research on the development of phosphorescent luminescent materials has been widely conducted in that phosphorescent luminescent materials can theoretically improve luminous efficiency up to 4 times compared to fluorescence luminescent materials due to the mechanism of electroluminescence. Is being performed. Until now, the iridium (III) complex family is widely known as a phosphorescent material, and bis(2-(2'-benzothienyl)-pyridine-N,C-3') iridium (acetylacetonate) for each RGB ) [(acac)Ir(btp) ₂ ], tris(2-phenylpyridine)iridium [Ir(ppy) ₃ ] and bis(4,6-difluorophenylpyridinato-N,C2)picolini Materials such as Toyridium (Firpic) are known.

In order to improve color purity, luminous efficiency and stability, a luminescent material is also used by mixing a luminescent material (dopant) with a host material. When using such a light emitting material (dopant)/host material system, the selection of the host material is important because the host material greatly affects the efficiency and performance of the light emitting device.

In the prior art, 4,4'-N,N'-dicarbazole-biphenyl (CBP) is the most widely known host material for phosphorescence. Recently, Bathocuproine (BCP) and aluminum (III) bis(2-methyl-8-quinolinate) (4-phenylphenolate), which were used as materials for the hole blocking layer by Japanese pioneers, etc. Balq) and the like have been developed as high performance organic electroluminescent devices.

However, these conventional phosphorescent host materials have advantages in terms of luminescence properties, but have the following disadvantages: (1) The glass transition temperature is low and the thermal stability is low, so the material changes when subjected to a high temperature deposition process under vacuum. . (2) In the organic electroluminescent device, power efficiency = [(π/voltage) × current efficiency], so power efficiency is inversely proportional to voltage. Organic electroluminescent devices using phosphorescent host materials are organic electroluminescent devices using fluorescent materials. The current efficiency (cd/A) is higher than that of the light emitting device, but the driving voltage is also quite high, so there is no great advantage in terms of power efficiency (lm/w). (3) In addition, when used in an organic electroluminescent device, it is not satisfactory in terms of operating life, and the luminous efficiency is still required to be improved.

On the other hand, copper phthalocyanine (CuPc), 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB), N,N' as a hole injection and transport material in an organic electroluminescent device -Diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4,4',4"-tris(3-methylphenylphenyl Amino) triphenylamine (MTDATA) has been used, but in the case of using such a material, the organic electroluminescent device has a problem in that quantum efficiency and lifespan are lowered. When the organic electroluminescent device is driven at a high current, This is because thermal stress occurs between the anode and the hole injection layer, and the life of the device is rapidly reduced due to the thermal stress.In addition, since the organic material used in the hole injection layer has a large hole mobility, , The hole-electron charge balance is broken, thereby lowering the quantum efficiency (cd/A).

International Publication No. WO 2011/040607 includes two carbazole skeletons having different carbazole linking positions (one is a structure connected to nitrogen of carbazole, and the other is a structure connected to carbon of carbazole). An amine compound is disclosed as a compound for an organic electroluminescent device.

In addition, Korean Patent Publication No. KR 2011/102055 A discloses an amine compound containing carbazole and triazine as a compound for an organic electroluminescent device.

However, organic EL devices including the compounds disclosed in the above documents are still not satisfactory in terms of power efficiency, luminous efficiency, quantum efficiency, and lifetime.

International Publication No. WO 2011/040607 (published April 7, 2011) Korean Patent Publication KR 2011/102055 A (published on September 16, 2011)

Accordingly, an object of the present invention is to provide an organic electroluminescent compound having a better luminous efficiency and lifetime efficiency than a conventional material, and second, to provide a high-efficiency and long-life organic electroluminescent device comprising the organic electroluminescent compound. .

As a result of earnest research to solve the above technical problem, the present inventors have completed the present invention by discovering that the compound represented by the following Chemical Formula 1 achieves the above object.

[Formula 1]

In Chemical Formula 1,

L ₁ is substituted or unsubstituted (C6-C30)arylene or substituted or unsubstituted (5-30 membered) heteroarylene;

L ₂ And L ₃ are each independently a single bond, substituted or unsubstituted (C6-C30)arylene or substituted or unsubstituted (5-30 membered) heteroarylene;

Ar ₁ is substituted or unsubstituted (C6-C30)aryl or substituted or unsubstituted (5-30 membered) heteroaryl;

R ₁ to R ₄ are each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxy, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C2-C30)alkenyl, substituted Or unsubstituted (C2-C30)alkynyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted (C3-C30) cycloalkenyl, substituted or unsubstituted Cyclic (3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (5-30 membered) heteroaryl, -NR ₁₁ R ₁₂ , -SiR ₁₃ R ₁₄ R ₁₅ ,- SR ₁₆ , -OR ₁₇ , -COR ₁₈ or -B(OR ₁₉ )(OR ₂₀ ); Connected to adjacent substituents (3-30 members) to form a monocyclic or polycyclic alicyclic or aromatic ring, and the formed carbon atom of the alicyclic or aromatic ring is replaced by one or more heteroatoms selected from nitrogen, oxygen and sulfur Can be;

R ₁₁ to R ₂₀ are each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxy, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C2-C30)alkenyl, substituted Or unsubstituted (C2-C30)alkynyl, substituted or unsubstituted (C1-C30)alkoxy, substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted (C3-C30)cycloalkenyl, substituted or unsubstituted Ring (3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30)aryl or substituted or unsubstituted (5-30 membered) heteroaryl, or linked to adjacent substituents (3-30 membered) monocyclic or May form a polycyclic alicyclic or aromatic ring, and the carbon atom of the alicyclic or aromatic ring formed may be replaced by one or more heteroatoms selected from nitrogen, oxygen and sulfur;

a, b and c are each independently an integer of 1 to 4, and in the case of an integer of 2 or more, each R ₁ , each R ₂ or each R ₃ may be the same or different;

d is an integer of 1 to 3, and in the case of an integer of 2 or more, each R ₄ may be the same or different.

The compound according to the present invention has the advantage of being capable of producing an organic electroluminescent device having excellent luminous efficiency and excellent lifespan characteristics, and excellent driving life of the device. In addition, the compound according to the present invention has the advantage of reducing the driving voltage of the device and at the same time it is possible to manufacture an organic electroluminescent device with improved power efficiency.

The present invention will be described in more detail below, but it is for illustrative purposes and should not be interpreted as a method of limiting the scope of the invention.

The compound represented by Chemical Formula 1 of the present invention has a structure of an amine compound including a carbazole skeleton and a dibenzothiophene skeleton, which will be described in more detail as follows.

In Chemical Formula 1, L ₁ is substituted or unsubstituted (C6-C30)arylene or substituted or unsubstituted (5-30 membered) heteroarylene, substituted or unsubstituted (C6-C20)arylene, or substituted or It is preferable that it is unsubstituted (5-21 membered) heteroarylene, and unsubstituted (C6-C20)arylene; (C6-C20)arylene substituted with (C1-C6)alkyl; Or more preferably unsubstituted (5-21 membered) heteroarylene, even more preferably phenylene, naphthylene, biphenylene, terphenylene, dimethylfluorenylene, pyridylene or isoquinoylene. Do.

In Formula 1, L ₂ and L ₃ are each independently a single bond, a substituted or unsubstituted (C6-C30) arylene, or a substituted or unsubstituted (5-30 membered) heteroarylene, each independently a single bond, It is preferably a substituted or unsubstituted (C6-C20)arylene, or a substituted or unsubstituted (5-21 membered) heteroarylene, single bond; Unsubstituted (C6-C20)arylene; (C6-C20)arylene substituted with (C1-C6)alkyl; Or more preferably unsubstituted (5-21 membered) heteroarylene, even more preferably a single bond, phenylene, biphenylene, naphthylene, dimethylfluorenylene, pyridylene or pyrimidineylene.

In Formula 1, Ar ₁ is substituted or unsubstituted (C6-C30)aryl or substituted or unsubstituted (5-30 membered) heteroaryl, substituted or unsubstituted (C6-C20)aryl, or substituted or unsubstituted ( 5-21 membered) Heteroaryl is preferred, (C1-C6)alkyl, (C6-C20)aryl, (C1-C6)alkyl(C6-C20)aryl, di(C6-C20)arylamino, (C6) -C20) aryl(5-21 membered) heteroarylamino or (5-21 membered) heteroaryl substituted or unsubstituted (C6-C20)aryl; More preferred is (C6-C20)aryl, (C1-C6)alkyl(C6-C20)aryl or di(C6-C20)arylamino or unsubstituted (5-21 membered) heteroaryl, phenyl, naph. Til, biphenyl, terphenyl, naphthylphenyl, phenyl substituted with dimethylfluorenyl, phenyl substituted with pyridyl, phenyl substituted with diphenylamino, phenyl substituted with phenylpyridylamino, substituted with diphenylamino Even more preferably, it is a naphthyl, dimethylfluorenyl, pyridyl, pyridyl substituted with phenyl, pyridyl substituted with naphthyl, pyridyl substituted with dimethylfluorenyl or pyridyl substituted with diphenylamino Do.

In Formula 1, R ₁ to R ₄ are each independently hydrogen, deuterium, halogen, cyano, carboxyl, nitro, hydroxy, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C2-C30) Alkenyl, substituted or unsubstituted (C2-C30) alkynyl, substituted or unsubstituted (C1-C30) alkoxy, substituted or unsubstituted (C3-C30) cycloalkyl, substituted or unsubstituted (C3-C30) cycloal Kenyl, substituted or unsubstituted (3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (5-30 membered) heteroaryl, -NR ₁₁ R ₁₂ , -SiR ₁₃ R ₁₄ R ₁₅ , -SR ₁₆ , -OR ₁₇ , -COR ₁₈ or -B(OR ₁₉ )(OR ₂₀ ); Connected to adjacent substituents (3-30 members) to form a monocyclic or polycyclic alicyclic or aromatic ring, and the formed carbon atom of the alicyclic or aromatic ring is replaced by one or more heteroatoms selected from nitrogen, oxygen and sulfur Preferably, each independently hydrogen, halogen, substituted or unsubstituted (C1-C15)alkyl, substituted or unsubstituted (C6-C20)aryl, substituted or unsubstituted (5-21 membered) heteroaryl, Hydrogen; halogen; Unsubstituted (C1-C6)alkyl; (C1-C6)alkyl substituted or unsubstituted (C6-C20)aryl; Or more preferably unsubstituted (5-21 membered) heteroaryl, phenyl or di substituted with hydrogen, fluorine, n-propyl, isopropyl, tert-butyl, phenyl, naphthyl, biphenyl, tert-butyl Even more preferred is benzofuranyl.

According to an embodiment of the present invention, in Chemical Formula 1, L ₁ is substituted or unsubstituted (C6-C20)arylene, or substituted or unsubstituted (5-21 membered) heteroarylene, L ₂ and L ₃ Each independently represents a single bond, substituted or unsubstituted (C6-C20)arylene, or substituted or unsubstituted (5-21 membered) heteroarylene, Ar ₁ is substituted or unsubstituted (C6-C20)aryl, or Substituted or unsubstituted (5-21 membered) heteroaryl, R ₁ to R ₄ are each independently hydrogen, halogen, substituted or unsubstituted (C1-C15)alkyl, substituted or unsubstituted (C6-C20)aryl, substituted Or unsubstituted (5-21 membered) heteroaryl.

According to another embodiment of the present invention, in Chemical Formula 1, L ₁ is unsubstituted (C6-C20)arylene; (C6-C20)arylene substituted with (C1-C6)alkyl; Or unsubstituted (5-21 membered) heteroarylene, L ₂ and L ₃ are each independently a single bond; Unsubstituted (C6-C20)arylene; (C6-C20)arylene substituted with (C1-C6)alkyl; Or unsubstituted (5-21 membered) heteroarylene, Ar ₁ is (C1-C6)alkyl, (C6-C20)aryl, (C1-C6)alkyl(C6-C20)aryl, di(C6-C20) Arylamino, (C6-C20)aryl(5-21 membered) heteroarylamino or (5-21 membered) heteroaryl substituted or unsubstituted (C6-C20)aryl; (C6-C20)aryl, (C1-C6)alkyl(C6-C20)aryl or di(C6-C20)arylamino substituted or unsubstituted (5-21 membered) heteroaryl, R ₁ to R ₄ are each Hydrogen independently; halogen; Unsubstituted (C1-C6)alkyl; (C1-C6)alkyl substituted or unsubstituted (C6-C20)aryl; Or unsubstituted (5-21 membered) heteroaryl.

Specific examples of “alkyl” described in the present invention include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl, and the like. Specific examples of “alkenyl” herein include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, and the like. Examples of “alkynyl” herein include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, and the like. Examples of “cycloalkyl” herein include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like. As used herein, “(3-7 membered) heterocycloalkyl” has 3 to 7 ring skeleton atoms, and one or more heteroatoms selected from the group consisting of B, N, O, S, P(=O), Si and P, Preferably it means a cycloalkyl containing one or more heteroatoms selected from O, S and N, for example, tetrahydrofuran, pyrrolidine, thiolane, tetrahydropyran and the like. “Aryl (ren)” as used herein refers to a monocyclic or fused ring radical derived from an aromatic hydrocarbon, such as phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl , Triphenylenyl, pyrenyl, tetrasenyl, perillynyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like. As used herein, “(5-30 membered) heteroaryl (ren)” has 5 to 30 ring skeleton atoms, and one or more hetero selected from the group consisting of B, N, O, S, P(=O), Si and P. It means an aryl group containing an atom. The number of heteroatoms is preferably 1 to 4, and may be a single ring system or a fused ring system fused with one or more benzene rings, and may be partially saturated. In addition, the heteroaryl (ren) herein also includes a form in which one or more heteroaryl or aryl groups are connected to a heteroaryl group by a single bond. Examples of the heteroaryl include furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl Monocyclic heteroaryl such as triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, di Benzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzooxazolyl, isoindoleyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cin And fused ring heteroaryls such as nolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxanil, phenanthridinyl, and benzodioxolyl. “Halogen” as used herein includes F, Cl, Br and I atoms.

In addition, in the "substituted or unsubstituted" substrate described in the present invention, "substituted" means that a hydrogen atom is replaced with another atom or another functional group (ie, a substituent) in a certain functional group. In Formula 1, the substituents of substituted alkyl, substituted alkenyl, substituted alkynyl, substituted alkoxy, substituted cycloalkyl, substituted cycloalkenyl, substituted heterocycloalkyl, substituted aryl (ren), and substituted heteroaryl (ren) are independent of each other. Deuterium, halogen, cyano, carboxyl, nitro, hydroxy, (C1-C30)alkyl, halo(C1-C30)alkyl, (C2-C30)alkenyl, (C2-C30)alkynyl, (C1- C30)alkoxy, (C1-C30)alkylthio, (C3-C30)cycloalkyl, (C3-C30)cycloalkenyl, (3-7 membered) heterocycloalkyl, (C6-C30)aryloxy, (C6- C30) arylthio, (C6-C30) aryl substituted or unsubstituted (5-30 member) heteroaryl, (5-30 member) heteroaryl substituted or unsubstituted (C6-C30) aryl, tri(C1) -C30)alkylsilyl, tri(C6-C30)arylsilyl, di(C1-C30)alkyl(C6-C30)arylsilyl, (C1-C30)alkyldi(C6-C30)arylsilyl, amino, mono or di (C1-C30)alkylamino, mono or di(C6-C30)arylamino, (C1-C30)alkyl(C6-C30)arylamino, (C6-C30)aryl(5-30 membered) heteroarylamino, ( C1-C30)alkylcarbonyl, (C1-C30)alkoxycarbonyl, (C6-C30)arylcarbonyl, di(C6-C30)arylcarbonyl, di(C1-C30)alkylcarbonyl, (C1 -C30) Alkyl (C6-C30) arylboronil, (C6-C30) ar (C1-C30) alkyl and (C1-C30) alkyl (C6-C30) It is preferably at least one member selected from the group consisting of aryl. And (C1-C6)alkyl, (C6-C20)aryl, (C1-C6)alkyl(C6-C20)aryl, (5-21 membered) heteroaryl, di(C6-C20)arylamino and (C6- C20) Aryl (5-21 membered) Heteroarylamino is more preferably one or more selected from the group consisting of methyl, tert-butyl, phenyl, naphthyl, dimethylfluorenyl, pyridyl, diphenylamino and phenyl. It is even more preferable that it is one or more selected from the group consisting of pyridylamino.

Examples of the organic electroluminescent compound according to the present invention include the following compounds, but are not limited thereto.

The compounds according to the present invention can be prepared by synthetic methods known to those skilled in the art, for example, according to Scheme 1 below.

[Scheme 1]

In Reaction Scheme 1, L ₁ , L ₂ , L ₃ , Ar _{1 ,} R ₁ to R ₄ , a, b, c and d are the same as defined in Chemical Formula 1, and Hal is halogen.

The present invention provides an organic electroluminescent device comprising the compound of Formula 1 in a further aspect. The organic electroluminescent device according to the present invention includes a first electrode; A second electrode; And one or more organic material layers interposed between the first electrode and the second electrode, and the organic material layer may include one or more compounds of Formula 1.

One of the first electrode and the second electrode may be an anode and the other may be a cathode. The organic material layer may include a light emitting layer, and may further include at least one layer selected from a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, and an electron blocking layer.

The compound of Formula 1 of the present invention may be included in one or more of the light emitting layer and the hole transport layer. When used in a hole transport layer, the compound of Formula 1 of the present invention may be included as a hole transport material. When used in a light emitting layer, the compound of formula 1 of the present invention can be included as a host material; Preferably it may further comprise one or more dopants; If necessary, compounds other than the compound of Formula 1 of the present invention may further include a second host material.

The second host material may be any known phosphorescent host, but it is particularly preferable in terms of luminous efficiency that it is selected from the group consisting of compounds represented by the following Chemical Formulas 2 to 4.

[Formula 2]

[Formula 3]

[Formula 4]

In Chemical Formulas 2 to 4,

Cz is the following structure,

R ₂₁ to R ₂₄ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (5-30 membered) Heteroaryl or R ₂₅ R ₂₆ R ₂₇ Si-, R ₂₅ to R ₂₇ are each independently substituted or unsubstituted (C1-C30)alkyl, or substituted or unsubstituted (C6-C30)aryl; L ₄ is a single bond, substituted or unsubstituted (C6-C30)arylene, or substituted or unsubstituted (5-30 membered) heteroarylene; M is substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (5-30 membered) heteroaryl; Y ₁ and Y ₂ are -O-, -S-, -N(R ₃₁ )-, -C(R ₃₂ )(R ₃₃ )-, and Y ₁ and Y ₂ are not present at the same time; R ₃₁ to R ₃₃ are each independently substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (5-30 membered) heteroaryl, R ₃₂ And R ₃₃ may be the same or different; h and i are each independently an integer of 1 to 3, j, k, l and m are each independently an integer of 0 to 4, and h, i, j, k, l or m is an integer of 2 or more, respectively (Cz-L ₄ ), each (Cz), each R ₂₁ , each R ₂₂ , each R ₂₃ or each R ₂₄ can be the same or different.

Specifically, a preferred example of the second host material is as follows.

The dopant is preferably one or more phosphorescent dopants. The phosphorescent dopant material applied to the organic electroluminescent device of the present invention is not particularly limited, but a complex compound of a metal atom selected from iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt) is preferred. , Ortho metallized complex compounds of metal atoms selected from iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt) are more preferred, and ortho metallized iridium complex compounds are even more preferred.

The phosphorescent dopant is preferably selected from the group consisting of compounds represented by the following Chemical Formulas 5 to 7.

[Formula 5] [Formula 6] [Formula 7]

In Chemical Formulas 5 to 7, L is selected from the following structures;

R ₁₀₀ is hydrogen or substituted or unsubstituted (C1-C30)alkyl; R ₁₀₁ to R ₁₀₉ And R ₁₁₁ To R ₁₂₃ are each independently hydrogen, deuterium, halogen, halogen substituted or unsubstituted (C1-C30)alkyl, cyano, or substituted or unsubstituted (C1-C30)alkoxy; R ₁₂₀ to R ₁₂₃ may form a quinoline by forming a fused ring during an adjacent substitution period; R ₁₂₄ to R ₁₂₇ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, or substituted or unsubstituted (C1-C30)aryl; When R ₁₂₄ to R ₁₂₇ are aryl groups, fluorene may be formed by forming a fused ring with an adjacent group; R ₂₀₁ To R ₂₁₁ are each independently hydrogen, deuterium, halogen, or halogen substituted or unsubstituted (C1-C30)alkyl; f and g are each independently an integer of 1 to 3, and when f or g is an integer of 2 or more, each R ₁₀₀ may be the same or different from each other; n is an integer from 1 to 3.

Specific examples of the phosphorescent dopant material are as follows.

The present invention in a further aspect provides a composition for manufacturing an organic electroluminescent device. The composition includes a first host material and a second host material, and may include the compound of the present invention as the first host material.

At this time, the weight ratio of the first host material and the second host material may range from 1:99 to 99:1.

In addition, the organic electroluminescent device of the present invention comprises a first electrode; A second electrode; And one or more organic material layers interposed between the first electrode and the second electrode, the organic material layer including a light emitting layer, and the light emitting layer comprising the composition for an organic electroluminescent device of the present invention and a phosphorescent dopant material, The composition for an organic electroluminescent device can be used as a host material.

The organic electroluminescent device of the present invention includes the compound of Formula 1 in the organic layer, and at the same time may include one or more compounds selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.

In addition, in the organic electroluminescent device of the present invention, the organic material layer is selected from the group consisting of Group 1, Group 2, Period 4, Cycle 5 transition metals, lanthanide series metals and organic metals of d-transition elements in addition to the compound of Formula 1 above. It may further include at least one metal or complex compound, and further, the organic material layer may further include at least one light emitting layer and a charge generating layer.

In addition, the organic electroluminescent device of the present invention may emit white light by further including at least one light emitting layer containing a blue, red, or green light emitting compound known in the art in addition to the compound of the present invention. Further, if necessary, a yellow or orange light emitting layer may be further included.

In the organic electroluminescent device of the present invention, one layer selected from a chalcogenide layer, a metal halide layer, and a metal oxide layer on at least one inner surface of a pair of electrodes (hereinafter, referred to as "surface layer") The above can be arranged. Specifically, it is preferable to arrange a chalcogenide (including oxide) layer of a metal of silicon and aluminum on the anode surface on the side of the light emitting medium layer and a metal halide layer or a metal oxide layer on the cathode surface on the side of the light emitting medium layer. Do. Thus, stabilization of the drive can be obtained. Preferred examples of the chalcogenide include SiOX (1≤X≤2), AlOX (1≤X≤1.5), SiON or SiAlON, and preferred examples of halogenated metals are LiF, MgF ₂ , CaF ₂ , and fluorinated rare earth metals. Etc., and preferred examples of the metal oxide include Cs ₂ O, Li ₂ O, MgO, SrO, BaO, CaO, and the like.

Further, in the organic electroluminescent device of the present invention, a mixed region of an electron transport compound and a reductive dopant or a mixed region of a hole transport compound and an oxidative dopant may be disposed on at least one surface of a pair of electrodes thus produced. have. In this way, since the electron transport compound is reduced to an anion, electrons are easily injected and transported from the mixed region to the light emitting medium. In addition, since the hole transport compound is oxidized to become a cation, it is easy to inject and transport holes from the mixed region to the light emitting medium. Preferred oxidizing dopants include various Lewis acids and acceptor compounds, and preferred reducing dopants include alkali metals, alkali metal compounds, alkaline earth metals, rare earth metals, and mixtures thereof. In addition, a white organic electroluminescent device having two or more light emitting layers can be manufactured by using a reducing dopant layer as a charge generating layer.

Hereinafter, for a detailed understanding of the present invention, a representative compound of the present invention will be described to describe the compound according to the present invention, a method for manufacturing the same, and light emitting characteristics of the device.

[ Example 1] Preparation of compound C-3

Preparation of compound 1-1

2-bromodibenzothiophene 20 g (76 mmol), aniline 14 g (152 mmol), Pd(OAc) ₂ 0.5 g (2.3 mmol), P(t-Bu) ₃ 3 mL (50 wt% xylene solution , 7.6 mmol) and 400 mL of xylene to Cs ₂ CO ₃ 50 g (152 mmol). The mixture was stirred at 160° C. for 12 hours. The reaction mixture was extracted with ethyl acetate (EA)/H ₂ O, and dried over MgSO ₄ . After removing the solvent with a rotary evaporator, column purification gave compound 1-1, 12 g (56%).

Preparation of compound C-3

Compound 1-1, 8.5 g (31 mmol), 9-(4-bromophenyl)-9H-carbazole 10 g (31 mmol), Pd(OAc) ₂ 0.57 g (0.62 mmol), P(t-Bu ) ₃ 1 mL (3.1 mmol) and NaOtBu 4.5 g (47 mmol) were added with 150 mL of xylene. The mixture was stirred at 160° C. for 12 hours. After the reaction was completed, the mixture was washed with distilled water, extracted with EA, and then the organic layer was dried over MgSO ₄ and the solvent was removed with a rotary evaporator, followed by column purification to obtain compound C-3, 9.2 g (57%).

MS/EIMS found 517.5; Calculated 516.17

[ Example 2] Preparation of Compound C-104

Preparation of compound 2-1

4-bromo-iodobenzene 20 g (71 mmol), dibenzo[b,d]thiophen-4-yl boronic acid 17.7 g (77 mmol), Pd(PPh ₃ ) ₄ 3.3 g (2.8 mmol), Na ₂ CO ₃ 18.8 g (177 mmol), toluene 360 mL, ethanol 90 mL and water 90 mL were added and stirred at 120° C. for 2.5 hours. The reaction mixture was extracted with ethyl acetate (EA)/H ₂ O, dried over MgSO ₄ and distilled under reduced pressure. Column purification gave compound 2-1, 19 g (79%).

Preparation of compound 2-2

Compound 2-1, 18.5 g (54 mmol), aniline 5.9 mL (65 mmol), Pd(OAc) ₂ 0.69 g (2.7 mmol), P(t-Bu) ₃ 2.6 mL (5.4 mmol), NaOtBu 10.4 g ( 108 mmol) and 260 mL of toluene, and stirred at 120° C. for 5 hours. The reaction mixture was extracted with ethyl acetate (EA)/H ₂ O, dried over MgSO ₄ and distilled under reduced pressure. Column purification gave compound 2-2, 15 g (79%).

Preparation of compound 2-3

Compound 2-2, 15.3 g (44 mmol), 4,4'-dibromobiphenyl 27 g (87 mmol), Pd ₂ (dba) ₃ 1.2 g (1.3 mmol), P(o-tol) ₃ 1.06 g (3.5 mmmol), NaOtBu 8.4 g (87 mmol) and toluene 450 mL were added and stirred at 120°C for 1.5 hours. The reaction mixture was extracted with ethyl acetate (EA)/H ₂ O, water was removed with MgSO ₄ and distilled under reduced pressure. Column purification gave compound 2-3, 13.4 g (53%) as a yellow solid.

Preparation of compound C-104

Compound 2-3, 13.4 g (23 mmol), carbazole 3.5 g (21 mmol), CuI 2 g (10 mmol), K ₃ PO ₄ 13.4 g (63 mmol), 2.8 mL (42 mmol) of ethylenediamine and toluene 120 mL was added and stirred at 120° C. for 8 hours. The reaction mixture was extracted with ethyl acetate (EA)/H ₂ O, water was removed with MgSO ₄ and distilled under reduced pressure. Column purification gave C-104, 5.0 g (35%) of a white solid.

MS/EIMS found 668.8; Calculated 668.23

[ Example 3] Preparation of compound C-16

Preparation of compound 3-1

4-bromoaniline 30 g (0.174 mol), phenyl boronic acid 28 g (0.227 mol), Pd(PPh ₃ ) ₄ 6 g (0.005 mol), K ₂ CO ₃ 60 g (0.435 mol), toluene 350 mL, After adding 150 mL of ethanol and 150 mL of water, the mixture was stirred at 120°C for 12 hours. After completion of the reaction, the mixture was extracted with ethyl acetate (EA), and then the organic layer was dried over MgSO ₄ , filtered and the solvent was removed under reduced pressure, followed by column purification to obtain compound 3-1, 20 g (68%).

Preparation of compound 3-2

Compound 3-1, 12 g (59 mmol), 2-bromo-dibenzo[b,d]thiophene 17 g (65 mmol), Pd(OAc) ₂ 0.5 g (2.03 mmol), P(t-Bu ) ₃ 1.43 ml (7.09 mmol), NaOt-Bu 14 g (118 mmol) and xylene 350 mL were added, followed by stirring at 150° C. for 24 hours. After the reaction mixture was extracted with ethyl acetate (EA), the organic layer was dried over MgSO ₄ and distilled under reduced pressure. Column purification gave compound 3-2, 6 g (40%).

Preparation of compound 3-3

Carbazole 20 g (119 mmol), 4-bromo-4'-iodo-1,1'-biphenyl 70 g (239 mmol), CuI 11.4 g (60 mmol), K ₃ PO ₄ 76 g (358 mmol) and toluene were added to 600 mL, followed by stirring at 80°C for 10 minutes. Then, 16 ml (239 mmol) of ethylenediamine (EDA) was added, followed by stirring at 140° C. for 12 hours. After the reaction mixture was extracted with ethyl acetate (EA), the organic layer was dried over MgSO ₄ and distilled under reduced pressure. Column purification gave compound 3-3, 40 g (84%).

Preparation of compound C-16

Compound 3-2, 6 g (17 mmol), compound 3-3, 7.5 g (19 mmol), Pd(OAc) ₂ 0.11 g (0.51 mmol), P(t-Bu) ₃ 0.4 mL (1.7 mmol), 5 g (51 mmol) of NaOt-Bu and 120 mL of xylene were added, followed by stirring at 150°C for 4 hours. After the reaction mixture was extracted with ethyl acetate (EA), the organic layer was dried over MgSO ₄ and distilled under reduced pressure. Column purification gave compound C-16, 3 g (26%) as a white solid.

MS/EIMS found 669; Calculated 668.85

[ Example 4] Preparation of compound C-25

Preparation of compound 4-1

Compound 3-1, 6 g (36 mmol), 4-bromo-dibenzo[b,d]thiophene 10 g (38 mmol), Pd(OAc) ₂ 0.2 g (1.0 mmol), P(t-Bu ) ₃ 0.87 mL (3.7 mmol), NaOt-Bu 7 g (72 mmol) and xylene 180 mL were added, followed by stirring at 150° C. for 24 hours. After the reaction mixture was extracted with ethyl acetate (EA), the organic layer was dried over MgSO ₄ and distilled under reduced pressure. Column purification gave compound 4-1, 6 g (48%).

Preparation of compound C-25

Compound 4-1, 5.3 g (15 mmol), compound 3-3, 5.5 g (14 mmol), Pd(OAc) ₂ 0.11 g (0.45 mmol), P(t-Bu) ₃ 0.36 ml (1.5 mmol), After adding 4.3 g (45 mmol) of NaOt-Bu and 100 mL of xylene, the mixture was stirred at 150°C for 4 hours. After the reaction mixture was extracted with ethyl acetate (EA), the organic layer was dried over MgSO ₄ and distilled under reduced pressure. Column purification gave compound C-25, 4 g (40%) as a white solid.

MS/EIMS measurement 668; Calculated 668.85

[device Manufacturing example 1] Using the compound for organic electronic materials according to the present invention OLED Device fabrication

An OLED device having a structure using the light emitting material of the present invention was produced. First, the transparent electrode ITO thin film (15 Ω/□) obtained from the glass for OLED (manufactured by Samsung-Corning Co., Ltd.) is subjected to ultrasonic cleaning using sequentially chloroethylene, acetone, ethanol, distilled water, and then stored in isopropanol. Used. Next, after mounting the ITO substrate on the substrate holder of the vacuum deposition equipment, N ¹ ,N ^1' -([1,1'-biphenyl]-4,4'-diyl)bis(N) ¹ -(naphthalen- ¹ -yl)-N ⁴ ,N ⁴ -diphenylbenzene-1,4-diamine) was added and exhausted until the vacuum in the chamber reached 10 ^-6 torr, and then a current was applied to the cell. And evaporated to deposit a 60 nm thick hole injection layer on the ITO substrate. Subsequently, Compound C-3 was put into another cell in the vacuum deposition equipment, and a current was applied to the cell to evaporate to deposit a 20 nm thick hole transport layer on the hole injection layer. After forming a hole injection layer and a hole transport layer, a light emitting layer was deposited thereon as follows. 5-(4-([1,1':4',1"-terphenyl]-3-yl)pyrimidin-2-yl)-5H-benzo[4,5] as a host in one cell in the vacuum deposition equipment ] Thieno[3,2-c]carbazole is added, and compound D-1 is added as a dopant to another cell, and then evaporation of the two materials at different rates makes the dopant 15 for the entire dopant and the host. A light-emitting layer having a thickness of 30 nm was deposited on the hole transport layer by doping in an amount of weight percent, and then a 2-(4-(9,10-di(naphthalen-2-yl)anthracene-) in one cell as an electron transport layer on the light-emitting layer. 2-yl)phenyl)-1-phenyl-1H-benzo[d] imidazole was added, and lithium quinolate was added to another cell, and the two substances were evaporated at the same rate to obtain 50% by weight. An electron transport layer of 30 nm was deposited by doping with a positive amount, followed by depositing lithium quinolate to a thickness of 2 nm as an electron injection layer, and then depositing an Al cathode to a thickness of 150 nm using another vacuum deposition equipment to deposit the OLED device. Each compound was used by vacuum sublimation purification under 10 ^-6 torr.

As a result, a current of 14.9 mA/cm ² flowed, and green emission of 6520 cd/m ² was confirmed.

[device Manufacturing example 2] Using the compound for organic electronic materials according to the present invention OLED Device fabrication

An OLED device was manufactured in the same manner as in Device Manufacturing Example 1, except that C-104 was used as the hole transport layer.

As a result, a current of 8.6 mA/cm ² flowed, and green emission of 3855 cd/m ² was confirmed.

[ Comparative example 1] Using conventional light emitting materials OLED Device fabrication

As a hole transport layer, N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl was deposited to a thickness of 20 nm and as a light emitting material, Compound D-15 is used as 4,4'-N,N'-dicarbazole-biphenyl, dopant, and a 30 nm thick light emitting layer is deposited on the hole transport layer, and aluminum (III) bis(2) is used as the hole blocking layer. An OLED device was manufactured in the same manner as Device Manufacturing Example 1, except that -methyl-8-quinolinato)4-phenylphenolate was deposited to a thickness of 10 nm.

As a result, a current of 6.6 mA/cm ² flowed, and green emission of 2250 cd/m ² was confirmed.

The luminescence properties of the organic electroluminescent compounds developed in the present invention show superior properties compared to conventional materials, and it can be confirmed that the device using the organic electroluminescent compound according to the present invention has excellent luminescence properties.

Claims (6)

Compound represented by the formula (1).
[Formula 1]

In Chemical Formula 1,
L ₁ is phenylene unsubstituted or substituted with deuterium, biphenylene unsubstituted or substituted with deuterium, terphenylene unsubstituted or substituted with deuterium, or naphthylene unsubstituted or substituted with deuterium;
L ₂ is a single bond, phenylene unsubstituted or substituted with deuterium, biphenylene unsubstituted or substituted with deuterium, terphenylene unsubstituted or substituted with deuterium, or naphthylene unsubstituted or substituted with deuterium;
L ₃ is a single bond, phenylene unsubstituted or substituted with deuterium, biphenylene unsubstituted or substituted with deuterium, terphenylene unsubstituted or substituted with deuterium, or naphthylene unsubstituted or substituted with deuterium;
Ar ₁ is phenyl unsubstituted or substituted with deuterium, naphthyl unsubstituted or substituted with deuterium, biphenyl unsubstituted or substituted with deuterium, terphenyl unsubstituted or substituted with deuterium, or unsubstituted or substituted with deuterium. Naphthylphenyl;
R ₁ to R ₄ are each independently hydrogen or deuterium;
a, b and c are each independently an integer of 1 to 4, and in the case of an integer of 2 or more, each R ₁ , each R ₂ or each R ₃ may be the same or different;
d is an integer of 1 to 3, and in the case of an integer of 2 or more, each R ₄ may be the same or different. delete delete delete The compound according to claim 1, wherein the compound represented by Formula 1 is selected from the following compounds.

An organic electroluminescent device comprising the compound of claim 1.