KR102160902B1 - An Organic Electroluminescent Compound and an Organic Electroluminescent Device Comprising the Same - Google Patents

Abstract

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device including the same. The organic electroluminescent compound of the present invention has excellent thermal stability due to a high glass transition temperature, and when the organic electroluminescent compound of the present invention is used, an organic electroluminescent device having excellent current/power efficiency and lifetime can be manufactured.

Description

An organic electroluminescent compound and an organic electroluminescent device comprising the same

The present invention relates to an organic electroluminescent compound and an organic electroluminescent device including the same.

Among display devices, an electroluminescent device (EL device) is a self-luminous display device that has a wide viewing angle, excellent contrast, and high response speed. In 1987, Eastman Kodak Co., Ltd. first developed an organic EL device using a low-molecular aromatic diamine and aluminum complex as a material for forming a light emitting layer [Appl. Phys. Lett. 51, 913, 1987].

The most important factor determining luminous efficiency in an organic electroluminescent device is a light-emitting material. Fluorescent materials have been widely used as luminescent materials until now. However, due to the mechanism of electroluminescence, phosphorescent luminescent materials can theoretically improve luminous efficiency up to 4 times compared to fluorescent materials. Has become. Until now, iridium (III) complex series are widely known as phosphorescent materials, and for each RGB, bis(2-(2'-benzothienyl)-pyridinato-N,C-3') iridium (acetylacetonate ) [(acac)Ir(btp) ₂ ], tris(2-phenylpyridine)iridium [Ir(ppy) ₃ ] and bis(4,6-difluorophenylpyridinato-N,C2)picolinei Materials such as toiridium (Firpic) are known.

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

However, conventional materials have advantages in terms of light-emitting properties, but have the following disadvantages: (1) The glass transition temperature is low and thermal stability is low, so that it deteriorates during a high-temperature evaporation process under vacuum, and the life of the device is reduced. (2) In organic electroluminescent devices, power efficiency = [(π voltage)> current efficiency], so power efficiency is inversely proportional to voltage. Organic electroluminescent devices using phosphorescent host materials use fluorescent materials. Compared to the device, the current efficiency (cd/A) is high, but the driving voltage is also considerably high, so there is no significant advantage in terms of power efficiency (lm/w). (3) In addition, when used in an organic electroluminescent device, the operating life is not satisfactory, and the luminous efficiency is still required to be improved.

Meanwhile, the organic electroluminescent device has a multilayer structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer in order to increase the efficiency and stability thereof. In this case, selection of a compound included in the hole transport layer or the like is recognized as a means for improving device characteristics such as hole transport efficiency, light emission efficiency, and lifetime time to the light emitting layer.

In this regard, copper phthalocyanine (CuPc), 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB), N,N as hole injection and transfer materials in organic electroluminescent devices '-Diphenyl-N,N'-bis(3-methylphenyl)-(1,1'-biphenyl)-4,4'-diamine (TPD), 4,4',4"-tris(3-methylphenyl) Phenylamino) triphenylamine (MTDATA), etc. have been used, but when these materials are used, the quantum efficiency and lifetime of the organic electroluminescent device are deteriorated, because when the organic electroluminescent device is driven at a high current, , This is because a thermal stress occurs between the anode and the hole injection layer, and the life of the device is drastically reduced by this thermal stress, and the organic material used for the hole injection layer has very high hole mobility. Therefore, the hole-electron charge balance is broken, and the quantum efficiency (cd/A) is lowered.

Accordingly, there is still a need for development of a hole transport layer for improving durability of an organic electroluminescent device.

Japanese Patent Publication No. JP3065125B discloses a compound in which a diarylamine is substituted at the 2nd carbon position of fluorene as a compound for an organic electroluminescent device. However, the document does not specifically disclose an organic electroluminescent device using a compound substituted with a diarylamine or heteroarylamine at the 9th carbon position of fluorene and fluorene, dibenzothiophene or dibenzofuran. .

Japanese Patent Publication JP3065125B (issued on July 12, 2000)

An object of the present invention is to provide an organic electroluminescent compound having excellent current/power efficiency and lifetime.

As a result of intensive research in order to solve the above technical problem, the present inventors have completed the present invention by discovering that the organic electroluminescent compound represented by the following formula (1) achieves the above object.

[Formula 1]

In Formula 1,

Ar ₁ and Ar ₂ are each independently substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (3-30 membered) heteroaryl; It is connected with an adjacent substituent to form a (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring, and the carbon atom of the formed alicyclic or aromatic ring is replaced by one or more heteroatoms selected from nitrogen, oxygen and sulfur. Can be;

X is -O-, -S- or -C(R ₅ )(R ₆ )-;

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)cyclo Alkenyl, substituted or unsubstituted (3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (3-30 membered) heteroaryl, -NR ₇ R ₈ , -SiR ₉ R ₁₀ R ₁₁ , -SR ₁₂ , -OR ₁₃ , -COR ₁₄ or -B(OR ₁₅ )(OR ₁₆ ); It is connected with an adjacent substituent to form a (C3-C30) monocyclic or polycyclic substituted or unsubstituted alicyclic or aromatic ring, and the carbon atom of the formed alicyclic or aromatic ring is selected from nitrogen, oxygen and sulfur. May be replaced by one or more heteroatoms;

R ₅ to R ₁₆ are each independently a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3-30 membered) heteroaryl; May be connected to adjacent substituents to form a (C3-C30) monocyclic or polycyclic substituted or unsubstituted alicyclic or aromatic ring;

n is an integer from 0 to 2;

when n is 1 or 2, L ₁ is a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3-30 membered) heteroarylene;

when n is 0, L ₁ is substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (3-30 membered)heteroaryl;

a, b and d are each independently an integer of 1 to 4, and when a, b or d is an integer of 2 or more, each R ₁ , each R ₂ , and each R ₄ may be the same or different;

c is an integer of 1 to 3, and when c is an integer of 2 or more, each R ₃ may be the same or different;

The heterocycloalkyl and heteroaryl (ene) each independently include one or more heteroatoms selected from B, N, O, S, P(=O), Si and P.

The organic electroluminescent compound according to the present invention has an advantage of being able to manufacture an organic electroluminescent device having excellent current/power efficiency and lifetime.

Hereinafter, the present invention will be described in more detail, but this is for illustration and should not be construed as a method of limiting the scope of the present invention.

The present invention relates to an organic electroluminescent compound represented by Chemical Formula 1, an organic electroluminescent material including the organic electroluminescent compound, and an organic electroluminescent device including the material.

The present invention was invented to provide a hole transport material used in an organic electroluminescent device capable of solving the problems of the prior art. An ideal hole transport material requires a glass transition temperature of a certain level or higher, hole injectability and hole transfer, adequate triplet energy and LUMO energy. When the glass transition temperature is low, crystallization may occur due to a thin film formation process or a thermal stress applied after the thin film formation process, which directly causes a decrease in device life. Although arylamine derivatives exhibit excellent hole-transporting ability and low driving voltage, many arylamine derivatives can achieve an appropriate level of glass transition temperature by increasing the molecular weight by introducing a large amount of substituents. However, in such a case, the pi-conjugation becomes long and the triplet energy or LUMO energy is lowered, resulting in a problem of deteriorating device performance. The reason is that if the triplet energy is high, excitons formed in the host are blocked from passing to the hole transport layer, and if the LUMO energy is high, electrons coming to the host through the electron transport layer are blocked from passing to the hole transport layer. Because it contributes.

Another problem that occurs when the molecular weight of the hole transport material increases due to the introduction of many substituents is the decrease in easiness of deposition. When the molecular weight increases, the deposition temperature also increases, and the probability of the molecule being decomposed or damaged in various forms is very high. Therefore, it is important to properly introduce a substituent to secure an appropriate glass transition temperature, but maintain a low deposition temperature compared to a large molecular weight. Therefore, the present invention proposes as a solution to introduce an arylamine and a selected heteroaryl or fluorene at the 9th position of fluorene.

When the selected heteroaryl or fluorenes are introduced at the 9th position of fluorene, the deposition temperature can be lower than that of introducing the substituent at the 2nd position while improving the glass transition temperature. This is because the linearity of the molecule is relatively reduced. The closer the molecule is to the linear shape, the stronger the intermolecular force and the higher the deposition temperature.

On the other hand, the reason for introducing the arylamine at position 9 instead of 2 is to obtain a relatively high triplet energy through short conjugation. In order to obtain high triplet energy, it is most advantageous not to introduce a substituent, but by introducing arylamine even if the triplet energy is slightly lowered, excellent hole injection/transfer, excellent power efficiency, and lifespan can be obtained. In addition, by introducing heteroaryl or fluorene at the 9th position instead of the 2nd position, it is possible to obtain an appropriate level of glass transition temperature without significantly increasing the deposition temperature compared to the molecular weight by reducing the relative linearity of the molecule.

The organic electroluminescent compound represented by Formula 1 will be described in more detail as follows.

"(C1-C30)alkyl" as described in the present invention means a straight or branched chain alkyl having 1 to 30 carbon atoms, wherein the number of carbon atoms is preferably 1 to 10, more preferably 1 to 6 . Specific examples of the alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. As used herein, "(C2-C30)alkenyl" refers to a straight-chain or branched alkenyl having 2 to 30 carbon atoms, preferably having 2 to 20 carbon atoms, and more preferably having 2 to 10 carbon atoms. Specific examples of the alkenyl include vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, and 2-methylbut-2-enyl. As used herein, "(C2-C30)alkynyl" refers to a straight-chain or branched-chain alkynyl having 2 to 30 carbon atoms, where it is preferably 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms. Examples of the alkynyl include ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, and the like. As used herein, "(C3-C30)cycloalkyl" refers to a monocyclic or polycyclic hydrocarbon having 3 to 30 carbon atoms, and preferably 3 to 20 carbon atoms, and more preferably 3 to 7 carbon atoms. Examples of the cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl. As used herein, "(3-7 membered) heterocycloalkyl" has 3 to 7 ring skeleton atoms, and at least one heteroatom 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, and examples include tetrahydrofuran, pyrrolidine, thiolane, and tetrahydropyran. As used herein, "(C6-C30)aryl (ene)" refers to a monocyclic or fused cyclic radical derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, wherein the cyclic skeletal carbon number is preferably 6 to 20, and 6 It is more preferably 15 to 15. Examples of the aryl include phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenane Trenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like. As used herein, "(5-30 membered) heteroaryl (ene)" has 5 to 30 ring skeleton atoms, and at least one 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 condensed with one or more benzene rings, and may be partially saturated. In addition, the heteroaryl (ene) herein includes a form in which one or more heteroaryl or aryl groups are linked 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 , Triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl and other single ring heteroaryl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, di Benzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, sine Fused ring heteroaryl such as nolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazyl, phenanthridinyl, and benzodioxolyl. "Halogen" herein includes F, Cl, Br and I atoms.

In addition, in the description of "substituted or unsubstituted" 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 the above Ar ₁ and Ar ₂ , R ₁ to R ₄ and L ₁ of Formula 1, substituted (C1-C30) alkyl, substituted (C2-C30) alkenyl, substituted (C2-C30) alkynyl, substituted (C1- C30) alkoxy, substituted (C3-C30) cycloalkyl, substituted (C3-C30) cycloalkenyl, substituted (3-7 members) heterocycloalkyl, substituted (C6-C30) aryl (ene), substituted (3-30 One) heteroaryl (ene), substituted (C6-C30) ar (C1-C30) alkyl substituents are each independently 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, (3-30 membered) hetero substituted or unsubstituted with (C6-C30)aryl Aryl, (C6-C30) aryl unsubstituted or substituted with (3-30 membered) heteroaryl, 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, (C1-C30)alkylcarbonyl, (C1-C30)alkoxycarbonyl, (C6-C30)arylcarbonyl, di(C6-C30)arylboronyl , Di(C1-C30)alkylboronyl, (C1-C30)alkyl(C6-C30)arylboronyl, (C6-C30)ar(C1-C30)alkyl, (C1-C30)alkyl(C6- It means at least one selected from the group consisting of C30)aryl, and is preferably at least one selected from the group consisting of (C1-C6)alkyl and (C6-C15)aryl each independently.

In Formula 1, Ar ₁ and Ar ₂ are each independently substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (3-30 members) Is heteroaryl; It is connected with an adjacent substituent to form a (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring, and the carbon atom of the formed alicyclic or aromatic ring is replaced by one or more heteroatoms selected from nitrogen, oxygen and sulfur. May be, and preferably each independently a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5-20 membered) heteroaryl, more preferably each independently (C1-C6) (C6-C20)aryl unsubstituted or substituted with alkyl or (C6-C12)aryl; Or (C6-C12) aryl substituted or unsubstituted (5-20 membered) heteroaryl.

The 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)al Kenyl, 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 (3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (3-30 membered) heteroaryl, -NR ₇ R ₈ , -SiR ₉ R ₁₀ R ₁₁ , -SR ₁₂ , -OR ₁₃ , -COR ₁₄ or -B(OR ₁₅ )(OR ₁₆ ); It is connected with an adjacent substituent to form a (C3-C30) monocyclic or polycyclic substituted or unsubstituted alicyclic or aromatic ring, and the carbon atom of the formed alicyclic or aromatic ring is selected from nitrogen, oxygen and sulfur. May be replaced by one or more heteroatoms, preferably each independently hydrogen or -NR ₇ R ₈ ; May be connected to adjacent substituents to form a (C6-C20) monocyclic or polycyclic substituted or unsubstituted alicyclic or aromatic ring, more preferably each independently hydrogen or -NR ₇ R ₈ ; It may be connected with an adjacent substituent to form a (C6-C20) monocyclic unsubstituted aromatic ring.

Each of R ₅ to R ₁₆ is independently a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3-30 membered) heteroaryl; Can be connected to adjacent substituents to form a (C3-C30) monocyclic or polycyclic substituted or unsubstituted alicyclic or aromatic ring, and preferably each independently substituted or unsubstituted (C1-C6)alkyl, or Substituted or unsubstituted (C6-C20)aryl; It is connected with adjacent substituents to form a (C3-C30) monocyclic or polycyclic substituted or unsubstituted alicyclic or aromatic ring, more preferably each independently unsubstituted (C1-C6)alkyl, or Is a cyclic (C6-C20)aryl; It may be connected with an adjacent substituent to form a (C3-C30) monocyclic or polycyclic substituted or unsubstituted alicyclic or aromatic ring.

When n is 1 or 2, L ₁ is a single bond, a substituted or unsubstituted (C6-C30) arylene, or a substituted or unsubstituted (3-30 membered) heteroarylene, preferably a single It is bonded or substituted or unsubstituted (C6-C20)arylene, more preferably unsubstituted (C6-C20)arylene.

When n is 0, L ₁ is a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3-30 membered)heteroaryl. , Preferably substituted or unsubstituted (C6-C20)aryl, more preferably unsubstituted (C6-C20)aryl.

According to an embodiment of the present invention, in Formula 1, Ar ₁ and Ar ₂ are each independently a substituted or unsubstituted (C6-C20)aryl, or a substituted or unsubstituted (5-20 membered) heteroaryl; X is -O-, -S- or -C(R ₅ )(R ₆ )-; R ₁ to R ₄ are each independently hydrogen or -NR ₇ R _8, or may be connected to an adjacent substituent to form a (C6-C20) monocyclic or polycyclic substituted or unsubstituted alicyclic or aromatic ring; R ₅ to R ₈ are each independently a substituted or unsubstituted (C1-C6) alkyl, or a substituted or unsubstituted (C6-C20) aryl, or is connected to an adjacent substituent to (C3-C30) monocyclic or polycyclic A substituted or unsubstituted alicyclic or aromatic ring may be formed; when n is 1 or 2, L ₁ is a single bond or a substituted or unsubstituted (C6-C20)arylene; When n is 0, L ₁ is substituted or unsubstituted (C6-C20)aryl.

According to another aspect of the present invention, in Formula 1, Ar ₁ and Ar ₂ are each independently (C1-C6)alkyl or (C6-C12)aryl substituted or unsubstituted (C6-C20)aryl; Or (C6-C12) aryl substituted or unsubstituted (5-20 membered) heteroaryl; X is -O-, -S- or -C(R ₅ )(R ₆ )-; R ₁ to R ₄ may each independently be hydrogen or -NR ₇ R _8, or may be connected to an adjacent substituent to form a (C6-C20) monocyclic unsubstituted aromatic ring; R ₅ to R ₈ are each independently unsubstituted (C1-C6)alkyl, or unsubstituted (C6-C20)aryl, or is linked to an adjacent substituent to (C3-C30) monocyclic or polycyclic substituted or unsubstituted Can form an alicyclic or aromatic ring; when n is 1 or 2, L ₁ is unsubstituted (C6-C20)arylene; When n is 0, L ₁ is unsubstituted (C6-C20)aryl.

In the organic electroluminescent material of the present invention, it is considered that if the molecular weight is too large, thermal decomposition is likely to be accompanied during sublimation deposition, and the molecular weight is preferably 1000 or less, more preferably 950 or less, and even more preferably 925 or less. , More preferably 900 or less.

In addition, for excellent thermal stability, the glass transition temperature is preferably 90°C or higher, and more preferably 110°C or higher.

The organic electroluminescent compound of Formula 1 may be more specifically exemplified as the following compounds, but is not limited thereto.

The organic electroluminescent compound according to the present invention can be prepared by a synthetic method known to those skilled in the art, for example, can be prepared as shown in the following scheme.

[Scheme 1]

In Reaction Scheme 1, R ₁ to R ₄ , X, Ar ₁ , Ar ₂ , L ₁ , n and a to d are the same as defined in Formula 1, and Hal is halogen.

In addition, the present invention provides an organic electroluminescent material comprising the organic electroluminescent compound of Formula 1 and an organic electroluminescent device comprising the material.

The material may be composed of the organic electroluminescent compound of the present invention alone, or may further include conventional materials included in the organic electroluminescent material.

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 organic electroluminescent compounds of Formula 1 above.

One of the first electrode and the second electrode may be an anode and the other may be a cathode. The organic material layer includes an emission 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 organic electroluminescent compound of the present invention may be included in at least one of the emission layer and the hole transport layer. When used in the hole transport layer, the organic electroluminescent compound of the present invention may be included as a hole transport material. When used in the light emitting layer, the organic electroluminescent compound of the present invention may be included as a host material.

The organic electroluminescent device including the organic electroluminescent compound of the present invention may further include one or more other compounds other than the organic electroluminescent compound of the present invention as a host material, and may further include one or more dopants.

When the organic electroluminescent compound of the present invention is included as the host material (first host material) of the light emitting layer, other compounds other than that may be included as the second host material. In this case, the weight ratio of the first host material and the second host material is in the range of 1:99 to 99:1.

The host material of a compound other than the organic electroluminescent compound of the present invention may be any known phosphorescent host, but in terms of luminous efficiency, it is specifically selected from the group consisting of compounds represented by the following Formulas 11 to 13 desirable.

[Formula 11]

[Formula 12]

[Formula 13]

In Formulas 11 to 13,

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 (3-30 membered) Heteroaryl or R ₂₅ R ₂₆ R ₂₇ Si-, and 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, a substituted or unsubstituted (C6-C30) arylene, or a substituted or unsubstituted (5-30 membered) heteroarylene; M is a substituted or unsubstituted (C6-C30)aryl, or a 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 a substituted or unsubstituted (C1-C30) alkyl, a substituted or unsubstituted (C6-C30) aryl, a substituted or unsubstituted (5-30 membered) heteroaryl, and 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, p and q are each independently an integer of 0 to 4, when h, i, j, k, p or q is an integer of 2 or more, each (Cz-L ₄ ), each (Cz), each R ₂₁ , each R ₂₂ , each R ₂₃ or each R ₂₄ may be the same or different.

Specifically, preferred examples of the host material are as follows.

As the dopant included in the organic electroluminescent device of the present invention, at least one phosphorescent dopant is preferable. The phosphorescent dopant material applied to the organic electroluminescent device of the present invention is not particularly limited, but a complex compound of metal atoms selected from iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt) is preferred. And, an ortho-metallized complex compound of a metal atom selected from iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt) is more preferable, and an ortho-metalized iridium complex compound is even more preferable.

The phosphorescent dopant is preferably selected from the group consisting of compounds represented by the following Chemical Formulas 101 to 103.

[Formula 101] [Formula 102] [Formula 103]

In Formulas 101 to 103, 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, substituted or unsubstituted (C1-C30)alkoxy, Or a substituted or unsubstituted (C3-C30)cycloalkyl; R ₁₂₀ to R ₁₂₃ may be connected to an adjacent substituent to form a (3-30 membered) monocyclic or polycyclic alicyclic or aromatic ring (eg, quinoline); R ₁₂₄ to R ₁₂₇ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, or substituted or unsubstituted (C6-C30)aryl; When R ₁₂₄ to R ₁₂₇ are an aryl group, they may be connected to an adjacent group to form a (3-30 membered) monocyclic or polycyclic alicyclic or aromatic ring (eg, fluorene); R ₂₀₁ to R ₂₁₁ are each independently hydrogen, deuterium, halogen, or halogen-substituted or unsubstituted (C1-C30)alkyl; r and s are each independently an integer of 1 to 3, and when r or s are each an integer of 2 or more, each of R ₁₀₀ may be the same or different from each other; e is an integer of 1 to 3.

Specific examples of the phosphorescent dopant material are as follows.

The present invention provides a composition for manufacturing an organic electroluminescent device as a further aspect. The composition contains the compound of the present invention as a host material or a hole transport layer material.

In addition, the organic electroluminescent device of 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, the organic material layer including an emission layer, and the emission layer may include the composition for an organic electroluminescent device of the present invention.

The organic electroluminescent device of the present invention may include the organic electroluminescent compound of Formula 1, and at the same time include at least one compound selected from the group consisting of an arylamine-based compound or a styrylarylamine-based compound.

In addition, in the organic electroluminescent device of the present invention, in the organic material layer, in addition to the organic electroluminescent compound of Formula 1, a group 1, group 2, period 4, period 5 transition metal, a lanthanide metal, and an organic metal of a d-transition element One or more metals or complex compounds selected from the group may be further included, and further, the organic material layer may further include an emission layer and a charge generation layer.

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

In the organic electroluminescent device of the present invention, on at least one inner surface of a pair of electrodes, a single layer selected from a chalcogenide layer, a metal halide layer, and a metal oxide layer (hereinafter referred to as “surface layer”) It is preferable to arrange the above. Specifically, it is preferable to arrange a chalcogenide (including oxide) layer of metals 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 surface of the cathode on the side of the light-emitting medium layer. Do. This makes it possible to achieve stabilization of driving. Preferred examples of the chalcogenide include SiO _X (1≤X≤2), AlO _X (1≤X≤1.5), SiON or SiAlON, and preferred examples of the metal halide include LiF, MgF ₂ , CaF ₂ , fluoride Rare earth metals and the like, and preferred examples of metal oxides include Cs ₂ O, Li ₂ O, MgO, SrO, BaO, CaO, and the like.

In addition, in the organic electroluminescent device of the present invention, it is also possible to arrange a mixed region of an electron transport compound and a reducing dopant or a mixed region of a hole transport compound and an oxidizing dopant on at least one surface of the pair of electrodes thus prepared. desirable. In this way, since the electron transfer compound is reduced to an anion, it becomes easy to inject and transfer electrons from the mixed region to the light emitting medium. Further, since the hole transport compound is oxidized to become a cation, it becomes easy to inject and transfer holes from the mixed region to the light emitting medium. Preferred oxidizing dopants include various Lewis acids and acceptor compounds, and preferable 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 the reducing dopant layer as a charge generating layer.

The formation of each layer of the organic electroluminescent device of the present invention is any one of a dry film deposition method such as vacuum deposition, sputtering, plasma, ion plating, or a wet film deposition method such as spin coating, dip coating, and flow coating. Can be applied.

In the case of wet film formation, a thin film is formed by dissolving or dispersing the material forming each layer in an appropriate solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc., and the solvent is dissolved or dispersed in the material forming each layer. It can be made, and any one may be used as long as there is no problem with the film forming property.

Hereinafter, for a detailed understanding of the present invention, an organic electroluminescent compound according to the present invention, a method of manufacturing the same, and luminescence characteristics of the device will be described with reference to the representative compound of the present invention.

[ Example 1] Preparation of compound C-6

Preparation of compound 1-1

Dibenzofuran (30 g, 178 mmol) and 500 mL of tetrahydrofuran were added to the reaction vessel, and the temperature was lowered to -78°C after making nitrogen conditions. 71 mL (2.5 M, 178 mmol) of n-butyllithium was slowly added dropwise thereto. After stirring at -78°C for 30 minutes, stirring at room temperature for 3 hours, the temperature was lowered to -78°C again. Thereafter, fluorenone (32 g, 178 mmol) dissolved in 500 mL of tetrahydrofuran was slowly added dropwise. When the dropwise addition was completed, the reaction temperature was gradually raised to room temperature and stirred for 16 hours. An aqueous ammonium chloride solution was added to the reaction solution to complete the reaction, followed by extraction with ethyl acetate. After drying the extracted organic layer with magnesium sulfate, the solvent was removed with a rotary evaporator. Then, it was purified by column chromatography to obtain compound 1-1 (43 g, 70%).

Preparation of compound 1-2

Compound 1-1 (10 g, 28.7 mmol), 4-bromodiphenylamine (7.4 g, 30.1 mmol) and 570 mL of methylene chloride (MC) were added to the reaction vessel, and nitrogen conditions were made. Boron trifluoride diethyl ether (3.8 mL, 30.1 mmol) dissolved in 120 mL of methylene chloride was slowly added dropwise thereto. After stirring at room temperature for 2 hours, ethanol and distilled water were added to terminate the reaction, followed by extraction with methylene chloride. After drying the extracted organic layer with magnesium sulfate, the solvent was removed with a rotary evaporator. After purification by column chromatography, compound 1-2 (15 g, 95%) was obtained.

Preparation of compound 1-3

In the reaction vessel, compound 1-2 (15 g, 26.9 mmol), phenylboronic acid (3.6 g, 29.6 mmol), tetrakis (triphenylphosphine) palladium (1.5 g, 1.34 mmol), potassium carbonate (8.9 g, 64.7) mmol), 160 mL of toluene, 40 mL of ethanol, and 40 mL of distilled water were added, followed by stirring at 120°C for 1 hour. After the reaction was completed, the mixture was washed with distilled water and the organic layer was extracted with ethyl acetate. After drying the extracted organic layer with magnesium sulfate, the solvent was removed with a rotary evaporator. Then, it was purified by column chromatography to obtain compound 1-3 (12.3 g, 80%).

compound C-6 Manufacture of

In the reaction vessel, compound 1-3 (8 g, 13.8 mmol), 4-bromobiphenyl (3.4 g, 14.5 mmol), palladium acetate (0.12 g, 0.55 mmol), S-phos (0.57 g, 1.38 mmol), sodium tert-butoxide (3.3 g, 34.7 mmol) and 70 mL of toluene were added, followed by reflux stirring for 1 hour. Upon completion of the reaction, the mixture was washed with distilled water and the organic layer was extracted with methylene chloride (MC). After drying the extracted organic layer with magnesium sulfate, the solvent was removed with a rotary evaporator. After purification by column chromatography, compound C-6 (8.2 g, 81%) was obtained.

UV: 360 nm (in toluene), PL: 396 nm (in toluene), MP: 270°C, MW: 727.89, Tg: 140°C

[ Example 2] Preparation of compound C-8

Preparation of compound 2-2

Compound 2-1 (30 g, 86.1 mmol), 4-bromotriphenylamine (84 g, 259 mmol) and 600 mL of methylene chloride (MC) were added to the reaction vessel, and nitrogen conditions were made. Then, 3 mL of Eaton's reagent was slowly added dropwise to the mixture. After stirring at room temperature for 2 hours, ethanol and distilled water were added to terminate the reaction, followed by extraction with methylene chloride. After drying the extracted organic layer with magnesium sulfate, the solvent was removed with a rotary evaporator. After purification by column chromatography, compound 2-2 (42 g, 74%) was obtained.

compound C-8 Manufacture of

In the reaction vessel, compound 2-2 (10 g, 26.9 mmol), 2-naphthylboronic acid (3.2 g, 18.4 mmol), tetrakis (triphenylphosphine) palladium (0.7 g, 1.08 mmol), potassium carbonate (5.3 g, 38.3 mmol), 60 mL of toluene, 20 mL of ethanol, and 20 mL of distilled water were added, followed by stirring at 120°C for 3 hours. After the reaction was completed, the mixture was washed with distilled water and the organic layer was extracted with ethyl acetate. After drying the extracted organic layer with magnesium sulfate, the solvent was removed with a rotary evaporator. After purification by column chromatography, compound C-8 (7.7 g, 72%) was obtained.

UV: 324 nm (in toluene), PL: 407 nm (in toluene), MP: 145°C, MW: 701.27, Tg: 134°C

[ Example 3] Preparation of compound C-38

Preparation of compound 3-1

2-bromodibenzothiophene (27 g, 103 mmol) and 340 mL of tetrahydrofuran were added to the reaction vessel, and the temperature was lowered to -78°C after making nitrogen conditions. 33 mL (2.5 M, 82 mmol) of n-butyllithium was slowly added dropwise thereto. After stirring at -78°C for 2 hours, 9H-fluorene-9-one (19 g, 103 mmol) dissolved in 340 mL of tetrahydrofuran was slowly added dropwise. When the dropwise addition was complete, the reaction temperature was gradually raised to room temperature and stirred for 30 minutes. An aqueous ammonium chloride solution was added to the reaction solution to complete the reaction, followed by extraction with ethyl acetate. After drying the extracted organic layer with magnesium sulfate, the solvent was removed with a rotary evaporator. Subsequently, it was purified by column chromatography to obtain compound 3-1 (23 g, 61%).

Preparation of compound 3-2

Compound 3-1 (23 g, 63 mmol) and 4-bromotriphenylamine (41 g, 126 mmol) were dissolved in 315 mL of dichloromethane in a reaction vessel, followed by 1.4 mL of Eaton's reagent (0.9 M, 1.3 mmol). It was added slowly. After stirring at room temperature for 30 minutes, the reaction was terminated with sodium hydrogen carbonate, followed by extraction with ethyl acetate. After drying the organic layer with magnesium sulfate, the solvent was removed with a rotary evaporator. After purification by column chromatography, compound 3-2 (27 g, 65%) was obtained.

compound C-38 Manufacture of

In the reaction vessel, compound 3-2 (10 g, 14.91 mmol), 2-naphthylboronic acid (3.1 g, 17.89 mmol), tetrakis (triphenylphosphine) palladium (0.5 g, 0.45 mmol), sodium carbonate (4 g) , 37.28 mmol), 76 mL of toluene, 19 mL of ethanol, and 19 mL of distilled water were added, followed by stirring at 120°C for 6 hours. When the reaction was over, it was washed with distilled water and extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, the solvent was removed with a rotary evaporator. Subsequently, it was purified by column chromatography to obtain compound C-38 (1.2 g, 11%).

UV: 382 nm (in toluene), PL: 405 nm (in toluene), MP: 230°C, MW: 717.92, Tg: 140°C

[ Example 4] Preparation of compound C-9

Preparation of compound 4-1

Dibenzothiophene (30 g, 163 mmol) and 400 mL of tetrahydrofuran were added to the reaction vessel, and after making nitrogen conditions, the temperature was lowered to -78°C. 65 mL (2.5 M, 163 mmol) of n-butyllithium was slowly added dropwise thereto. After stirring at -78°C for 2 hours, 9H-fluoren-9-one (29 g, 163 mmol) dissolved in 400 mL of tetrahydrofuran was slowly added dropwise. When the dropwise addition was complete, the reaction temperature was gradually raised to room temperature and stirred for 30 minutes. An aqueous ammonium chloride solution was added to the reaction solution to complete the reaction, followed by extraction with ethyl acetate. After drying the extracted organic layer with magnesium sulfate, the solvent was removed with a rotary evaporator. Subsequently, it was purified by column chromatography to obtain compound 4-1 (20 g, 34%).

Preparation of compound 4-2

Compound 4-1 (7 g, 19 mmol) and 4-bromotriphenylamine (16 g, 48 mmol) were dissolved in 96 mL of dichloromethane in a reaction vessel, and 0.5 mL (0.9 M, 0.4 mmol) of Eaton's reagent was added. It was added slowly. After stirring at room temperature for 30 minutes, the reaction was terminated with sodium hydrogen carbonate, followed by extraction with ethyl acetate. After drying the organic layer with magnesium sulfate, the solvent was removed with a rotary evaporator. Then, it was purified by column chromatography to obtain compound 4-2 (8 g, 62%).

compound C-9 Manufacture of

In the reaction vessel, compound 4-2 (8 g, 11.93 mmol), 2-naphthylboronic acid (2.5 g, 14.31 mmol), tetrakis (triphenylphosphine) palladium (0.4 g, 0.36 mmol), sodium carbonate (3.2 g) , 29.83 mmol), 60 mL of toluene, 15 mL of ethanol, and 15 mL of distilled water were added, followed by stirring at 120°C for 6 hours. When the reaction was over, it was washed with distilled water and extracted with ethyl acetate. After drying the organic layer with magnesium sulfate, the solvent was removed with a rotary evaporator. After purification by column chromatography, compound C-9 (4.3 g, 50%) was obtained.

UV: 390 nm (in toluene), PL: 407 nm (in toluene), MP: 215°C, MW: 717.92, Tg: 151°C

[ Example 5] Preparation of compound C-78

compound C-78 Manufacture of

In the reaction vessel, compound 1-3 (5.6 g, 9.72 mmol), 2-bromo-9,9-dimethylfluorene (2.9 g, 10.7 mmol), palladium acetate (0.08 g, 0.38 mmol), S-phos (0.39 g, 0.97 mmol), sodium tert-butoxide (2.3 g, 24.3 mmol), and 50 mL of toluene were added, followed by reflux stirring for 1 hour. Upon completion of the reaction, the mixture was washed with distilled water and the organic layer was extracted with methylene chloride (MC). After drying the extracted organic layer with magnesium sulfate, the solvent was removed by a rotary evaporator. After purification by column chromatography, compound C-78 (6.2 g, 83%) was obtained.

UV: 322 nm (in toluene), PL: 398 nm (in toluene), MP: 242°C, MW: 767.95, Tg: 151°C

[ Example 6] Preparation of compound C-12

Preparation of compound 5-2

Compound 1-1 (10 g, 28.7 mmol), diphenylamine (14 g, 86.1 mmol) and 570 mL of methylene chloride (MC) were added to the reaction vessel, and nitrogen conditions were made. Boron trifluoride diethyl ether (3.8 mL, 30.1 mmol) dissolved in 120 mL of methylene chloride was slowly added dropwise thereto. After stirring at room temperature for 2 hours, ethanol and distilled water were added to terminate the reaction, followed by extraction with methylene chloride. After drying the extracted organic layer with magnesium sulfate, the solvent was removed with a rotary evaporator. After purification by column chromatography, compound 5-2 (11 g, 78%) was obtained.

compound C-12 Manufacture of

In the reaction vessel, compound 5-2 (11 g, 22.1 mmol), 2-bromo-9,9-dimethylfluorene (6.6 g, 24.4 mmol), palladium acetate (0.19 g, 0.88 mmol), S-phos (0.91 g, 2.21 mmol), sodium tert-butoxide (5.3 g, 55.4 mmol), and 110 mL of toluene were added, followed by reflux stirring for 1 hour. Upon completion of the reaction, the mixture was washed with distilled water and the organic layer was extracted with methylene chloride (MC). After drying the extracted organic layer with magnesium sulfate, the solvent was removed with a rotary evaporator. After purification by column chromatography, compound C-12 (12 g, 79%) was obtained.

UV: 344 nm (in toluene), PL: 387 nm (in toluene), MP: 225°C, MW: 691.86, Tg: 137°C

[ Example 7] Preparation of compound C-79

compound C-79 Manufacture of

In the reaction vessel, compound 2-2 (6.7 g, 10.2 mmol), 4-biphenylboronic acid (2.4 g, 12.2 mmol), tetrakis (triphenylphosphine) palladium (0.47 g, 0.41 mmol), potassium carbonate (3.5 g, 25.5 mmol), 45 mL of toluene, 15 mL of ethanol, and 15 mL of distilled water were added, followed by stirring at 120°C for 3 hours. After the reaction was completed, the mixture was washed with distilled water and the organic layer was extracted with ethyl acetate. After drying the extracted organic layer with magnesium sulfate, the solvent was removed with a rotary evaporator. After purification by column chromatography, compound C-79 (5.0 g, 67%) was obtained.

UV: 344 nm (in toluene), PL: 397 nm (in toluene), MP: 255°C, MW: 727.29, Tg: 141°C

[ Example 8] Preparation of compound C-81

Preparation of compound 6-1

2-bromo-9,9'-dimethylfluorene (40 g, 146 mmol) and 500 mL of tetrahydrofuran were added to the reaction vessel, and nitrogen conditions were made, and the temperature was lowered to -78°C. 60 mL (2.5 M, 146 mmol) of n-butyllithium was slowly added dropwise thereto. After stirring at -78°C for 90 minutes, fluorenone (26 g, 146 mmol) dissolved in 500 mL of tetrahydrofuran was slowly added dropwise. When the dropwise addition was completed, the reaction temperature was gradually raised to room temperature and stirred for 16 hours. An aqueous ammonium chloride solution was added to the reaction solution to complete the reaction, followed by extraction with ethyl acetate. After drying the extracted organic layer with magnesium sulfate, the solvent was removed with a rotary evaporator. Then, purified by column chromatography to obtain compound 6-1 (41 g, 72%).

compound C-81 Manufacture of

Compound 6-1 (10 g, 26.7 mmol), compound 6-2 (CAS number: 122215-84-3) (10.6 g, 26.7 mmol) and 134 mL of methylene chloride (MC) were added to the reaction vessel, and nitrogen conditions were made. Thereafter, 0.6 mL of Eaton's reagent was slowly added dropwise. After stirring at room temperature for 2 hours, ethanol and distilled water were added to terminate the reaction, followed by extraction with methylene chloride. After drying the extracted organic layer with magnesium sulfate, the solvent was removed with a rotary evaporator. Then, purified by column chromatography to obtain compound C-81 (17 g, 85%).

UV: 378 nm (in toluene), PL: 395 nm (in toluene), MP: 178°C, MW: 753.34, Tg: 143°C

[Device Example 1] Fabrication of an OLED device using the organic electroluminescent compound according to the present invention

An OLED device was manufactured using the light emitting material of the present invention. First, the transparent electrode ITO thin film (10Ω/□) obtained from OLED glass (manufactured by Geomatech) was subjected to ultrasonic cleaning by sequentially using acetone and isopropane alcohol, and then stored in isopropane alcohol and used. Next, after attaching the ITO substrate to the substrate holder of the vacuum evaporation 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) and exhaust until the vacuum degree in the chamber reaches 10 ^-6 torr, and then apply current to the cell. And evaporated to deposit a hole injection layer having a thickness of 60 nm on the ITO substrate. Subsequently, compound C-6 was put into another cell in the vacuum deposition equipment, and a current was applied to the cell to evaporate to deposit a hole transport layer having a thickness of 20 nm on the hole injection layer. After forming the hole injection layer and the hole transport layer, a light emitting layer was deposited thereon as follows. 9-(3-(4,6-diphenyl-1,3,5-triazine-2-yl)phenyl)-9'-phenyl-9H,9'H-3 as a host in one cell within the vacuum deposition equipment ,3'-bicarbazole was added, and compound D-1 as a dopant was respectively added to another cell, and then the two materials were evaporated at different rates to dopant dopant to 15% by weight of the dopant and the entire host. A light emitting layer having a thickness of 30 nm was deposited on the hole transport layer. Then, in one cell as an electron transport layer on the light-emitting layer, 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole Then, lithium quinolate was added to another cell, and then the two materials were evaporated at the same rate and doped with 50% by weight, respectively, to deposit an electron transport layer of 30 nm. Subsequently, lithium quinolate was deposited to a thickness of 2 nm as an electron injection layer, and then an Al cathode was deposited to a thickness of 150 nm using another vacuum deposition equipment to manufacture an OLED device. For each material, each compound was used by vacuum sublimation purification under 10 ^-6 torr.

As a result, a current of 1.9 mA/cm ² flowed, and green light emission of 900 cd/m ² was confirmed.

In addition, the time taken for the light emission to fall to 80% at a luminance of 15000 nit was 250 hours or more.

[Device Example 2] Fabrication of an OLED device using the organic electroluminescent compound according to the present invention

Compound C-9 was deposited to a thickness of 20 nm as a hole transport layer, and 7-(4-([1,1'-biphenyl]-4-yl)quinazolin-2-yl was deposited in one cell in a vacuum deposition equipment as a light emitting layer. )-7H-benzo[c]carbazole was added, and compound D-87 as a dopant was added to another cell, and then the two materials were evaporated at different rates to obtain 3% by weight of the dopant relative to the dopant and the host. An OLED device was manufactured in the same manner as in Device Preparation Example 1, except that a light emitting layer having a thickness of 30 nm was deposited on the hole transport layer by doping with.

As a result, a current of 6.7 mA/cm ² flowed, and red light emission of 1000 cd/m ² was confirmed.

In addition, the time taken for the light emission to fall to 80% at a luminance of 5000 nit was 200 hours or more.

[Device Example 3] Fabrication of an OLED device using the organic electroluminescent compound according to the present invention

An OLED device was manufactured in the same manner as in Device Preparation Example 1, except that Compound C-8 was used as the hole transport layer, and Compound H-1 below was used as a host and Compound FD-1 was used as a dopant.

As a result, a current of 16.3 mA/cm ² flowed, and blue light emission of 800 cd/m ² was confirmed.

In addition, it took 170 hours or more for the light emission to fall to 50% at a luminance of 2000 nit.

[Device Example 4] Fabrication of an OLED device using the organic electroluminescent compound according to the present invention

An OLED device was manufactured in the same manner as in Device Preparation Example 2, except that Compound C-78 was deposited to a thickness of 20 nm as the hole transport layer.

As a result, a current of 11.7 mA/cm ² flowed, and red light emission of 1700 cd/m ² was confirmed.

In addition, it took 210 hours or more for the light emission to fall to 80% at a luminance of 5000 nit.

[Device Example 5] Fabrication of an OLED device using the organic electroluminescent compound according to the present invention

An OLED device was manufactured in the same manner as in Device Preparation Example 1, except that Compound C-79 was deposited to a thickness of 20 nm as the hole transport layer.

As a result, a current of 4.2 mA/cm ² flowed, and green light emission of 3000 cd/m ² was confirmed.

In addition, it took more than 240 hours for the light emission to fall to 80% at a luminance of 15000 nit.

[Device Example 6] Fabrication of an OLED device using the organic electroluminescent compound according to the present invention

An OLED device was manufactured in the same manner as in Device Preparation Example 1, except that Compound C-12 was deposited to a thickness of 20 nm as the hole transport layer.

As a result, a current of 3.2 mA/cm ² flowed, and green light emission of 1500 cd/m ² was observed.

In addition, it took 270 hours or more for the light emission to fall to 80% at a luminance of 15000 nit.

[Device Example 7] Fabrication of an OLED device using the organic electroluminescent compound according to the present invention

An OLED device was manufactured in the same manner as in Device Preparation Example 3, except that Compound C-81 was deposited to a thickness of 20 nm as the hole transport layer.

As a result, a current of 22.6 mA/cm ² flowed, and blue light emission of 1200 cd/m ² was confirmed.

In addition, it took 130 hours or more for the light emission to fall to 50% at a luminance of 2000 nit.

[ Comparative example 1] Conventional organic Electric field Using luminescent compounds OLED Device manufacturing

Device manufacturing except for depositing N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl as a hole transport layer to a thickness of 20 nm An OLED device was manufactured in the same manner as in Example 1.

As a result, a current of 32.6 mA/cm ² flowed, and green light emission of 12000 cd/m ² was confirmed.

In addition, the time taken for the light emission to fall to 80% at a luminance of 15000 nit was 230 hours or more.

[ Comparative example 2] conventional organic Electric field Using luminescent compounds OLED Device manufacturing

Device manufacturing except for depositing N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl as a hole transport layer to a thickness of 20 nm An OLED device was manufactured in the same manner as in Example 3.

As a result, a current of 138.1 mA/cm ² flowed, and blue light emission of 5000 cd/m ² was confirmed.

In addition, the time taken for the light emission to fall to 50% at a luminance of 2000 nit was 130 hours or more.

[ Comparative example 3] conventional organic Electric field Using luminescent compounds OLED Device manufacturing

Device manufacturing except for depositing N,N'-di(4-biphenyl)-N,N'-di(4-biphenyl)-4,4'-diaminobiphenyl as a hole transport layer to a thickness of 20 nm An OLED device was manufactured in the same manner as in Example 2.

As a result, a current of 131.6 mA/cm ² flowed, and red light emission of 10000 cd/m ² was confirmed.

In addition, the time taken for the light emission to fall to 80% at a luminance of 5000 nit was 180 hours or more.

[ Comparative example 4] conventional organic Electric field Using luminescent compounds OLED Device manufacturing

An OLED device in the same manner as in Device Manufacturing Example 1 except that 9,9-dimethyl-N,N-diphenyl-9H-fluoren-2-amine (Tg=43°C) was deposited to a thickness of 20 nm as the hole transport layer. Was prepared.

As a result, a current of 20.8 mA/cm ² flowed, and green light emission of 9000 cd/m ² was confirmed.

In addition, the time taken for the light emission to fall to 80% at a luminance of 15000 nit was 25 hours or more.

It was confirmed that the organic electroluminescent compounds developed in the present invention had a high glass transition temperature and excellent current efficiency compared to the conventional organic electroluminescent compounds. In addition, the device using the organic electroluminescent compound according to the present invention has excellent light-emitting characteristics, in particular, current/power efficiency and lifetime.

Claims (6)

An organic electroluminescent compound represented by the following formula (1).
[Formula 1]

In Formula 1,
Ar ₁ and Ar ₂ are each independently substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (3-30 membered) heteroaryl; It is connected with an adjacent substituent to form a (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring, and the carbon atom of the formed alicyclic or aromatic ring is replaced by one or more heteroatoms selected from nitrogen, oxygen and sulfur. Can be;
X is -O-, -S- or -C(R ₅ )(R ₆ )-;
n is an integer of 0 or 2;
When n is 2, L ₁ is a substituted or unsubstituted (C6-C30) arylene, or a substituted or unsubstituted (3-30 membered) heteroarylene, and 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 (3- 7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30) aryl, substituted or unsubstituted (3-30 membered) heteroaryl, -NR ₇ R ₈ , -SiR ₉ R ₁₀ R ₁₁ , -SR ₁₂ , -OR ₁₃ , -COR ₁₄ or -B(OR ₁₅ )(OR ₁₆ ); It is connected with an adjacent substituent to form a (C3-C30) monocyclic or polycyclic substituted or unsubstituted alicyclic or aromatic ring, and the carbon atom of the formed alicyclic or aromatic ring is selected from nitrogen, oxygen and sulfur. May be replaced by one or more heteroatoms;
When n is 0, L ₁ is a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3-30 membered) heteroaryl, provided that , Substituted or unsubstituted fluorenyl, and not substituted or unsubstituted dibenzofuranyl, 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 (3-7 membered) heterocycloalkyl, substituted or unsubstituted (C6-C30 ) Aryl, substituted or unsubstituted (3-30 membered) heteroaryl, -NR ₇ R ₈ , -SiR ₉ R ₁₀ R ₁₁ , -SR ₁₂ , -OR ₁₃ , -COR ₁₄ or -B(OR ₁₅ )( OR ₁₆ ); It is connected with an adjacent substituent to form a (C3-C30) monocyclic or polycyclic substituted or unsubstituted alicyclic or aromatic ring, and the carbon atom of the formed alicyclic or aromatic ring is selected from nitrogen, oxygen and sulfur. May be replaced by one or more heteroatoms, provided that at least one of R ₁ and R ₂ is necessarily -NR ₇ R ₈ ;
R ₅ to R ₁₆ are each independently a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3-30 membered) heteroaryl; May be connected to adjacent substituents to form a (C3-C30) monocyclic or polycyclic substituted or unsubstituted alicyclic or aromatic ring;
a, b and d are each independently an integer of 1 to 4, and when a, b or d is an integer of 2 or more, each R ₁ , each R ₂ , and each R ₄ may be the same or different;
c is an integer of 1 to 3, and when c is an integer of 2 or more, each R ₃ may be the same or different;
The heterocycloalkyl and heteroaryl (ene) each independently include one or more heteroatoms selected from B, N, O, S, P(=O), Si and P. The method of claim 1, wherein in the Ar ₁ and Ar ₂ , R ₁ to R ₁₆ and L ₁ , substituted (C1-C30)alkyl, substituted (C2-C30)alkenyl, substituted (C2-C30)alkynyl, substituted ( C1-C30)alkoxy, substituted (C3-C30)cycloalkyl, substituted (C3-C30)cycloalkenyl, substituted (3-7 members)heterocycloalkyl, substituted (C6-C30)aryl(ene), substituted (3 The substituents of -30 membered) heteroaryl (ene) and substituted (C6-C30) ar (C1-C30) alkyl are each independently 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, (3-30 membered) unsubstituted or substituted with (C6-C30) aryl ) Heteroaryl, (C6-C30) aryl unsubstituted or substituted with (3-30 membered) heteroaryl, 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, (C1-C30)alkylcarbonyl, (C1-C30)alkoxycarbonyl, (C6-C30)arylcarbonyl, di(C6-C30)arylbo Ronyl, di(C1-C30)alkylboronyl, (C1-C30)alkyl(C6-C30)arylboronyl, (C6-C30)ar(C1-C30)alkyl, (C1-C30)alkyl( C6-C30) At least one selected from the group consisting of aryl, an organic electroluminescent compound. The method of claim 1, wherein Ar ₁ and Ar ₂ are each independently substituted or unsubstituted (C6-C20)aryl, or substituted or unsubstituted (5-20 membered) heteroaryl; X is -O-, -S- or -C(R ₅ )(R ₆ )-; R ₁ to R ₄ are each independently hydrogen or -NR ₇ R _8, or may be connected to an adjacent substituent to form a (C6-C20) monocyclic or polycyclic substituted or unsubstituted alicyclic or aromatic ring; R ₅ to R ₈ are each independently a substituted or unsubstituted (C1-C6) alkyl, or a substituted or unsubstituted (C6-C20) aryl, or is connected to an adjacent substituent to (C3-C30) monocyclic or polycyclic A substituted or unsubstituted alicyclic or aromatic ring may be formed; when n is 2, L ₁ is substituted or unsubstituted (C6-C20)arylene; When n is 0, L ₁ is a substituted or unsubstituted (C6-C20)aryl, provided that it is not a substituted or unsubstituted fluorenyl, an organic electroluminescent compound. The method of claim 1, wherein Ar ₁ and Ar ₂ are each independently (C1-C6)alkyl or (C6-C12)aryl unsubstituted or substituted with (C6-C20)aryl; Or (C6-C12) aryl substituted or unsubstituted (5-20 membered) heteroaryl; X is -O-, -S- or -C(R ₅ )(R ₆ )-; R ₁ to R ₄ may each independently be hydrogen or -NR ₇ R _8, or may be connected to an adjacent substituent to form a (C6-C20) monocyclic unsubstituted aromatic ring; R ₅ to R ₈ are each independently unsubstituted (C1-C6)alkyl, or unsubstituted (C6-C20)aryl, or is linked to an adjacent substituent to (C3-C30) monocyclic or polycyclic substituted or unsubstituted Can form an alicyclic or aromatic ring; when n is 2, L ₁ is unsubstituted (C6-C20)arylene; When n is 0, L ₁ is an unsubstituted (C6-C20)aryl, provided that it is not a substituted or unsubstituted fluorenyl, an organic electroluminescent compound. The organic electroluminescent compound of claim 1, wherein the compound represented by Formula 1 is selected from the following compounds.

An organic electroluminescent device comprising the organic electroluminescent compound of claim 1.