KR102411746B1 - 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 comprising the same. By using the organic electroluminescent compound of the present invention, an organic electroluminescent device having excellent current efficiency and lifespan characteristics can be manufactured.

Description

Organic electroluminescent compound and organic electroluminescent device comprising same

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

Among display devices, an electroluminescent device (EL device) is a self-emission type display device, and has a wide viewing angle, excellent contrast, and fast response speed. In 1987, Eastman Kodak (Eastman Kodak) developed for the first time an organic EL device using a low molecular weight 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 the luminous efficiency in an organic electroluminescent device is a light emitting material. Fluorescent materials have been widely used as luminescent materials so far, but research on the development of phosphorescent luminescent materials has been widely conducted in that phosphorescent luminescent materials can theoretically improve luminous efficiency up to four times compared to fluorescent luminescent materials due to the electroluminescence mechanism. is becoming Until now, the iridium (III) complex series is widely known as a phosphorescent light emitting material, 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)picolinane Materials such as toridium (Firpic) are known.

In the prior art, 4,4'-N,N'-dicarbazole-biphenyl (CBP) was most widely known as a phosphorescent host material. Recently, Bathocuproine (BCP) and aluminum (III) bis (2-methyl-8-quinolinate) (4-phenylphenolate) ( Balq) has been used as a host material to develop high-performance organic electroluminescent devices.

However, conventional materials have advantages in terms of luminescent properties, but have the following disadvantages: (1) Low glass transition temperature and low thermal stability, which deteriorates during a high-temperature deposition process under vacuum, and decreases the lifetime of the device. (2) In an organic electroluminescent device, power efficiency = [(π/voltage) × current efficiency], so power efficiency is inversely proportional to voltage. Organic electroluminescent devices using phosphorescent host materials use fluorescent materials Although the current efficiency (cd/A) is higher than that of the light emitting device, 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, the organic electroluminescent device consists of 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 its efficiency and stability. In this case, selection of a compound included in the hole transport layer is recognized as a means for improving device characteristics such as hole transport efficiency to the light emitting layer, luminous efficiency, and lifetime.

In this regard, copper phthalocyanine (CuPc), 4,4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB), N,N as hole injection and transport 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) has been used, but when such a material is used, the quantum efficiency and lifespan of the organic electroluminescent device are deteriorated. , because thermal stress is generated between the anode and the hole injection layer, and the lifespan of the device is rapidly reduced due to such thermal stress In addition, the organic material used for the hole injection layer has very high hole mobility. For this reason, the hole-electron charge balance is broken, and thus quantum efficiency (cd/A) is lowered.

Therefore, the development of a hole transport layer for improving the durability of the organic electroluminescent device is still required.

Japanese Patent Laid-Open Publication JP2001-196177 discloses a compound in which two benzene rings of fluorene are substituted with diarylamine, respectively, as a compound for an organic electroluminescent device. However, the document does not specifically disclose an organic electroluminescent device using a compound in which one benzene ring of fluorene is substituted with two diarylamines.

Japanese Patent Laid-Open Publication JP2001-196177 (published on July 19, 2001)

An object of the present invention is to provide an organic electroluminescent compound having excellent luminous efficiency and lifespan characteristics.

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

[Formula 1]

In Formula 1,

L ₁ and L ₂ are each independently a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3-30 membered)heteroarylene;

Ar ₁ to Ar ₄ are each independently substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted (3-7 membered)heterocycloalkyl, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (3-30 membered)heteroaryl;

R ₁ and R ₂ are each independently substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted (3-7 membered)heterocycloalkyl, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (3-30 membered)heteroaryl; R ₁ and R ₂ may be connected to each other to form a (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring;

R ₃ is hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (3-30 membered)heteroaryl, substituted or unsubstituted substituted (C3-C30)cycloalkyl, substituted or unsubstituted (3-7 membered)heterocycloalkyl, substituted or unsubstituted (C6-C30)ar(C1-C30)alkyl, -NR ₄ R ₅ , - SiR ₆ R ₇ R ₈ , cyano, nitro or hydroxy; may be linked to adjacent substituents to form a (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring;

R ₄ and R ₅ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (3-30 membered) ) heteroaryl;

R ₆ to R ₈ 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, substituted or unsubstituted (3-7 membered)heterocycloalkyl, or substituted or unsubstituted (C3-C30)cycloalkyl; It may be linked with an adjacent substituent to form a (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring, wherein a carbon atom of the formed alicyclic or aromatic ring is replaced with one or more heteroatoms selected from nitrogen, oxygen and sulfur can be;

a is an integer from 1 to 4, and when an integer of 2 or more, each R ₃ may be the same or different;

The heteroaryl(ene) and heterocycloalkyl 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 the advantage of being able to manufacture an organic electroluminescent device having excellent current efficiency and lifespan characteristics.

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

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

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

As used herein, "(C1-C30)alkyl" means a straight-chain or branched chain alkyl having 1 to 30 carbon atoms, preferably having 1 to 10 carbon atoms, more preferably 1 to 6 carbon atoms. . Specific examples of the alkyl include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl and tert-butyl. As used herein, "(C2-C30) alkenyl" means a straight-chain or branched chain alkenyl having 2 to 30 carbon atoms, preferably 2 to 20 carbon atoms, and more preferably 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" means a straight-chain or branched alkynyl having 2 to 30 carbon atoms, 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" means a monocyclic or polycyclic hydrocarbon having 3 to 30 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 7 carbon atoms. Examples of the cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like. 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, for example, tetrahydrofuran, pyrrolidine, thiolane, tetrahydropyran and the like. As used herein, "(C6-C30) aryl (ene)" refers to a monocyclic or fused-ring radical derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, wherein the ring skeleton preferably has 6 to 20 carbon atoms, and 6 It is more preferable that it is thru|or 15. Examples of the aryl include phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenane threnyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, and the like. As used herein, "(3-30 membered) heteroaryl (ene)" has 3 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 hetero atoms 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 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 , triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, monocyclic heteroaryl such as pyridazinyl, benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, di Benzothiophenyl, benzonaphthothiophenyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl , isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, fused ring heteroaryl such as benzodioxolyl. As used herein, “halogen” includes F, Cl, Br and I atoms.

According to one embodiment of the present invention, the compound represented by Formula 1 may be represented by Formula 2 below.

[Formula 2]

In Formula 2, L ₁ , L ₂ , Ar ₁ to Ar ₄ , R ₁ to R ₃ and a are the same as defined in Formula 1.

In addition, in the description of "substituted or unsubstituted" in the present invention, 'substitution' means that a hydrogen atom in one functional group is replaced by another atom or another functional group (ie, a substituent). In the above L ₁ , L ₂ , Ar ₁ to Ar ₄ , and R ₁ to R ₈ of Formula 1, substituted (C1-C30)alkyl, substituted (C3-C30)cycloalkyl, substituted (3-7 membered)heterocyclo The substituents of alkyl, substituted (C6-C30)aryl(ene), substituted (3-30 membered)heteroaryl(ene) and substituted (C6-C30)ar(C1-C30)alkyl are each independently deuterium, halogen, cyano No, 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)heteroaryl unsubstituted or substituted with C6-C30)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 ) means at least one selected from the group consisting of ar (C1-C30)alkyl and (C1-C30)alkyl (C6-C30)aryl, and each independently (C1-C6)alkyl, (C6-C25)aryl and (5-20 member) It is preferable that at least one selected from the group consisting of heteroaryl.

In Formula 1, L ₁ and L ₂ are each independently a single bond, a substituted or unsubstituted (C6-C30) arylene, or a substituted or unsubstituted (3-30 membered) heteroarylene, preferably A single bond, a substituted or unsubstituted (C6-C12) arylene, or a substituted or unsubstituted (5-20 membered) heteroarylene, more preferably each independently a single bond, an unsubstituted (C6-C12) ) arylene, or unsubstituted (5-20 membered) heteroarylene.

wherein Ar ₁ to Ar ₄ are each independently substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted (3-7 membered)heterocycloalkyl, A substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3-30 membered)heteroaryl, preferably each independently a substituted or unsubstituted (C6-C15)aryl, more preferably are each independently (C1-C6)alkyl, (C6-C15)aryl, or (C6-C15)aryl unsubstituted or substituted with (5-20 membered)heteroaryl.

wherein R ₁ and R ₂ are each independently a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (3-7 membered)heterocycloalkyl, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (3-30 membered)heteroaryl; R ₁ and R ₂ may be connected to each other to form a (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring, preferably each independently substituted or unsubstituted (C1-C6) alkyl, substituted or unsubstituted (C6-C20)aryl, or substituted or unsubstituted (5-20 membered)heteroaryl; R ₁ and R ₂ may be connected to each other to form a (C6-C20) monocyclic or polycyclic alicyclic or aromatic ring, more preferably each independently unsubstituted (C1-C6)alkyl; (C6-C20)aryl unsubstituted or substituted with (C1-C6)alkyl, (C6-C25)aryl, or (5-20 membered)heteroaryl; or (5-20 membered) heteroaryl unsubstituted or substituted with (C6-C12)aryl; R ₁ and R ₂ may be connected to each other to form a (C6-C20) monocyclic or polycyclic aromatic ring.

wherein R ₃ is hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (3-30 membered)heteroaryl, substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted (3-7 membered)heterocycloalkyl, substituted or unsubstituted (C6-C30)ar(C1-C30)alkyl, -NR ₄ R ₅ , -SiR ₆ R ₇ R ₈ , cyano, nitro or hydroxy; It may be linked with an adjacent substituent to form a (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring, preferably hydrogen, substituted or unsubstituted (C6-C12)aryl, substituted or unsubstituted (C5) -C12)cycloalkyl, -NR ₄ R ₅ or -SiR ₆ R ₇ R ₈ ; It may be linked with an adjacent substituent to form a (C6-C12) monocyclic or polycyclic alicyclic or aromatic ring, more preferably hydrogen, unsubstituted (C6-C12)aryl, unsubstituted (C5-C12) cycloalkyl, —NR ₄ R ₅ or —SiR ₆ R ₇ R ₈ ; It may be linked to an adjacent substituent to form a (C6-C12) monocyclic aromatic ring.

wherein R ₄ and R ₅ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (3-30 member) heteroaryl, preferably each independently substituted or unsubstituted (C6-C12)aryl, more preferably each independently unsubstituted (C6-C12)aryl.

wherein R ₆ to R ₈ 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, substituted or unsubstituted (3-7 membered)heterocycloalkyl, or substituted or unsubstituted (C3-C30)cycloalkyl; It may be linked with an adjacent substituent to form a (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring, wherein a carbon atom of the formed alicyclic or aromatic ring is replaced with one or more heteroatoms selected from nitrogen, oxygen and sulfur may be, preferably each independently substituted or unsubstituted (C1-C6)alkyl, more preferably each independently unsubstituted (C1-C6)alkyl.

wherein a is an integer of 1 to 4, preferably an integer of 1 to 2; In the case of an integer of 2 or more, each R ₃ may be the same or different.

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

According to an aspect of the present invention, in Formula 1, L ₁ and L ₂ are each independently a single bond, a substituted or unsubstituted (C6-C12)arylene, or a substituted or unsubstituted (5-20 membered) heteroarylene; Ar ₁ to Ar ₄ are each independently substituted or unsubstituted (C6-C15)aryl; R ₁ and R ₂ are each independently substituted or unsubstituted (C1-C6)alkyl, substituted or unsubstituted (C6-C20)aryl, or substituted or unsubstituted (5-20 membered)heteroaryl; R ₁ and R ₂ may be connected to each other to form a (C6-C20) monocyclic or polycyclic alicyclic or aromatic ring; R ₃ is hydrogen, substituted or unsubstituted (C6-C12)aryl, substituted or unsubstituted (C5-C12)cycloalkyl, —NR ₄ R ₅ or —SiR ₆ R ₇ R ₈ ; may be linked to adjacent substituents to form a (C6-C12) monocyclic or polycyclic alicyclic or aromatic ring; R ₄ and R ₅ are each independently substituted or unsubstituted (C6-C12)aryl; R ₆ to R ₈ are each independently substituted or unsubstituted (C1-C6)alkyl; a is an integer of 1 to 2.

According to another aspect of the present invention, in Formula 1, L ₁ and L ₂ are each independently a single bond, an unsubstituted (C6-C12) arylene, or an unsubstituted (5-20 membered) heteroarylene ego; Ar ₁ to Ar ₄ are each independently (C1-C6)alkyl, (C6-C15)aryl, or (C6-C15)aryl unsubstituted or substituted with (5-20 membered)heteroaryl; R ₁ and R ₂ are each independently an unsubstituted (C1-C6)alkyl; (C6-C20)aryl unsubstituted or substituted with (C1-C6)alkyl, (C6-C25)aryl, or (5-20 membered)heteroaryl; or (5-20 membered) heteroaryl unsubstituted or substituted with (C6-C12)aryl; R ₁ and R ₂ may be connected to each other to form a (C6-C20) monocyclic or polycyclic aromatic ring; R ₃ is hydrogen, unsubstituted (C6-C12)aryl, unsubstituted (C5-C12)cycloalkyl, —NR ₄ R ₅ or —SiR ₆ R ₇ R ₈ ; may be linked to adjacent substituents to form a (C6-C12) monocyclic aromatic ring; R ₄ and R ₅ are each independently unsubstituted (C6-C12)aryl; R ₆ to R ₈ are each independently unsubstituted (C1-C6)alkyl; a is an integer of 1 to 2.

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

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

[Scheme 1]

In Scheme 1, L ₁ , L ₂ , Ar ₁ to Ar ₄ , R ₁ to R ₃ and a are the same as defined in Formula 1.

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

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

An organic electroluminescent device according to the present invention includes a first electrode; a second electrode; and at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer may include at least one organic electroluminescent compound of Formula 1 above.

One of the first and second electrodes may be an anode and the other may be a cathode. The organic material layer includes a light emitting layer, and may further include one or more layers 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 light emitting 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 may be included as the second host material. In this case, the weight ratio of the first host material to the second host material is in the range of 1:99 to 99:1.

As the host material of the compound other than the organic electroluminescent compound of the present invention, any known phosphorescent host can be used. desirable.

[Formula 11]

H-(Cz-L ₄ ) _h -M

[Formula 12]

H-(Cz) _i -L ₄ -M

[Formula 13]

In Formulas 11 to 13,

Cz is the 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 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 simultaneously; 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, b and c are each independently an integer of 0 to 4, when h, i, j, k, b or c 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.

[Here, TPS is triphenylsilyl]

As a 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 a metal atom selected from iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt) is preferable. and more preferably an ortho-metalated complex compound of a metal atom selected from iridium (Ir), osmium (Os), copper (Cu) and platinum (Pt), and even more preferably an ortho-metalated iridium complex compound.

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, substituted or unsubstituted (C1-C30)alkyl, or substituted or unsubstituted (C3-C30)cycloalkyl;

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, substituted or unsubstituted (C6- C30)aryl, or substituted or unsubstituted (C3-C30)cycloalkyl; R ₁₀₆ to R ₁₀₉ may be connected to adjacent substituents to form a substituted or unsubstituted fused ring, for example, fluorene substituted or unsubstituted with alkyl, dibenzothiophene substituted or unsubstituted with alkyl, or It is possible to form dibenzofurans substituted or unsubstituted with alkyl; R ₁₂₀ to R ₁₂₃ may be connected to adjacent substituents to form a substituted or unsubstituted fused ring, for example, it is possible to form a quinoline substituted or unsubstituted with halogen, alkyl or aryl;

R ₁₂₄ to R ₁₂₇ are each independently hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, or substituted or unsubstituted (C6-C30)aryl; R ₁₂₄ to R ₁₂₇ may be connected to adjacent substituents to form a substituted or unsubstituted fused ring, for example, fluorene substituted or unsubstituted with alkyl, dibenzothiophene substituted or unsubstituted with alkyl, or It is possible to form dibenzofurans substituted or unsubstituted with alkyl;

R ₂₀₁ to R ₂₁₁ are each independently hydrogen, deuterium, halogen, halogen-substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C3-C30)cycloalkyl, or substituted or unsubstituted (C6 -C30) aryl, and R ₂₀₈ to R ₂₁₁ may be connected to an adjacent group to form a substituted or unsubstituted fused ring, for example, fluorene substituted or unsubstituted with alkyl, di substituted or unsubstituted with alkyl It is possible to form dibenzofuran unsubstituted or substituted with benzothiophene or alkyl;

f and g are each independently an integer from 1 to 3; When each f or g is an integer of 2 or more, each R ₁₀₀ may be the same as 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 provides a composition for manufacturing an organic electroluminescent device in a further aspect. The composition comprises 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 at least one organic material layer interposed between the first electrode and the second electrode, wherein the organic material layer includes a light emitting layer, and the light emitting layer may include the composition for an organic electroluminescent device of the present invention.

The organic electroluminescent device of the present invention includes the organic electroluminescent compound of Formula 1, and at the same time may 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, Group 1, Group 2, 4th period, 5th period transition metal, a lanthanide series metal, and an organometal of a d-transition element. It may further include one or more metals or complex compounds selected from the group, and further, the organic layer may further include a 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 one or more light emitting layers 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, it may further include a yellow or orange light emitting layer.

In the organic electroluminescent device of the present invention, on the inner surface of at least one of the pair of electrodes, one layer selected from a chalcogenide layer, a metal halide layer and a metal oxide layer (hereinafter, these are 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 surface of the anode on the side of the light emitting medium layer, and a metal halide layer or metal oxide layer on the surface of the cathode on the side of the light emitting medium layer do. Thereby, stabilization of the drive can be obtained. 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 and rare earth metals, and preferred examples of the metal oxide 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, a mixed region of an electron transport compound and a reducing dopant or a mixed region of a hole transport compound and an oxidative dopant is disposed on at least one surface of the pair of electrodes thus manufactured. desirable. In this way, since the electron transport compound is reduced to an anion, it is easy to inject and transfer electrons from the mixed region to the light emitting medium. In addition, since the hole transport compound is oxidized to a cation, it is easy to inject and transport holes from the mixing 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 the reducing dopant layer as a charge generating layer.

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

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

Hereinafter, for a detailed understanding of the present invention, the organic electroluminescent compound according to the present invention, its preparation method, and the light emitting characteristics of the device will be described with reference to the representative compound of the present invention.

[ Example 1] Preparation of compound C-1

Preparation of compound 1-2

In a reaction vessel, 2,4-dichlorophenyl boronic acid (Compound 1-1) (64 g, 335 mmol), methyl 2-bromobenzoate (60 g, 279 mmol), tetrakis(triphenylphosphine)palladium (9.5 g, 8.4 mmol), potassium carbonate (96 g, 698 mmol), toluene 600 mL, and ethanol 300 mL were added, and distilled water 300 mL was added thereto, followed by stirring at 120° C. for 3 hours. Upon completion of the reaction, the mixture was washed with distilled water and the organic layer was extracted with ethyl acetate. The extracted organic layer was dried over magnesium sulfate, and then the solvent was removed using a rotary evaporator. Then, it was purified by column chromatography to obtain compound 1-2 (79 g, 99 %).

Preparation of compound 1-3

Compound 1-2 (79 g, 279 mmol), 110 mL of Eaton's reagent, and 1 L of benzene chloride were placed in a reaction vessel and stirred under reflux overnight. The reaction solution was cooled to room temperature, and the reaction was terminated with water, followed by extraction with methylene chloride (MC). The extracted organic layer was dried over magnesium sulfate, and then the solvent was removed using a rotary evaporator. Then, it was purified by column chromatography to obtain compound 1-3 (49 g, 71 %).

Preparation of compound 1-4

Iodine (18 g, 71 mmol), hypophosphorous acid (35 mL, 315 mmol, 50% aqueous solution) and 1 L of acetic acid were placed in a reaction vessel and stirred at 100° C. for 30 minutes. Compound 1-3 was slowly added dropwise thereto, followed by stirring under reflux overnight. The reaction solution was cooled to room temperature, the precipitated solid was filtered, and washed with a large amount of hexane. The filtrate was diluted with ethyl acetate and washed with water. The extracted organic layer was dried over magnesium sulfate, and then the solvent was removed using a rotary evaporator. Then, it was purified by column chromatography to obtain compound 1-4 (35.7 g, 77 %).

Preparation of compounds 1-5

In a reaction vessel, compound 1-4 (35.5 g, 151 mmol), potassium hydroxide (42 g, 760 mmol), potassium iodide (2.5 g, 15 mmol), benzyltriethylammonium chloride (1.7 g, 7.8 mmol), distilled water 700 mL and 700 mL of dimethyl sulfoxide were added and stirred at room temperature for 15 minutes. Methyl iodide (25 mL, 378 mmol) was added thereto and stirred at room temperature overnight. The reaction solution was diluted with ethyl acetate and washed with distilled water. The extracted organic layer was dried over magnesium sulfate, and then the solvent was removed using a rotary evaporator. Then, it was purified by column chromatography to obtain compound 1-5 (32 g, 81 %).

compound C-1 manufacture of

In a reaction vessel, compound 1-5 (7 g, 26.6 mmol), dibiphenyl-4-ylamine (17 g, 52.9 mmol), tris(dibenzylideneacetone)dipalladium(0) (1.9 g, 2.1 mmol), s-phos (1.1 g, 2.7 mmol), sodium t-butoxide (6.4 g, 67 mmol) and 150 mL of o-xylene were added and stirred under reflux for 1 hour. The reaction solution cooled to room temperature was diluted with ethyl acetate and washed several times with water. After removing moisture with anhydrous magnesium sulfate, distillation under reduced pressure, and purification by column chromatography, compound C-1 (9.6 g, 55 %) was obtained.

[ Example 2] Preparation of compound C-9

Preparation of compound 2-1

Compound 3-1 (20.5 g, 82.3 mol) and 400 mL of tetrahydrofuran were placed in a reaction vessel, the reaction solution was cooled to 0° C., and phenylmagnesium bromide (40 mL, 123 mmol, 3 M diethyl ether solution was slowly added dropwise. The reaction solution was stirred at room temperature for 1 hour.The reaction was terminated with an aqueous solution of ammonium chloride, diluted with ethyl acetate, and washed with water.Moisture was removed with anhydrous magnesium sulfate, distilled under reduced pressure, and the compound was purified by column chromatography. 2-1 (28 g, 99%) was obtained.

Preparation of compound 2-2

Compound 2-1 (15.8 g, 48.3 mmol), 9-phenylcarbazole (17.6 g, 72.5 mmol) and 250 mL of methylene chloride (MC) were placed in a reaction vessel, and nitrogen conditions were created. 1.5 mL of Eaton's reagent was slowly added dropwise to the reaction. After stirring at room temperature for 2 hours, distilled water was added to terminate the reaction, and extraction was performed with methylene chloride. The extracted organic layer was dried over magnesium sulfate, and then the solvent was removed using a rotary evaporator. Then, it was purified by column chromatography to obtain compound 2-2 (13.2 g, 49 %).

compound C-9 manufacture of

In a reaction vessel, compound 2-2 (13 g, 26.6 mmol), diphenylamine (8 g, 47 mmol), tris(dibenzylideneacetone)dipalladium(0) (1.7 g, 1.9 mmol), esphos (0.96) g, 2.35 mmol), sodium t-butoxide (5.6 g, 58.8 mmol) and 120 mL of o-xylene were added and stirred under reflux overnight. The reaction solution cooled to room temperature was diluted with ethyl acetate and washed several times with water. After removing moisture with anhydrous magnesium sulfate, distillation under reduced pressure, and purification by column chromatography, compound C-9 (10 g, 52 %) was obtained.

[device production example 1] Organic according to the present invention electric field using luminescent compounds OLED device manufacturing

An OLED device was manufactured using the light emitting material of the present invention. First, the transparent electrode ITO thin film (10Ω/□) obtained from glass for OLED (Giomatec) was ultrasonically cleaned using acetone and isopropane alcohol sequentially, and then placed in isopropane alcohol and stored before use. Next, after mounting the ITO substrate on the substrate holder of the vacuum deposition equipment, N ⁴ ,N ^{4'-biphenyl-N 4 , N} 4'-bis(9-phenyl-9H-carbazole- 3-yl)-[1,1'-biphenyl]-4,4'-diamine is put and evacuated until the vacuum level in the chamber reaches 10 ^-6 torr A first hole injection layer having a thickness of 80 nm was deposited thereon. Then, 1,4,5,8,9,11-hexaazatriphenylene-hexacarbonitrile (HAT-CN) is put into another cell in the vacuum deposition equipment, and a current is applied to the cell to evaporate and inject the first hole A second hole injection layer having a thickness of 5 nm was deposited on the layer. Then, the following compound T-1 was put into another cell in the vacuum deposition equipment, and the cell was evaporated by applying a current to deposit a first hole transport layer having a thickness of 10 nm on the second hole injection layer. Then, the compound C-1 was put into another cell in the vacuum deposition equipment, and the cell was evaporated by applying an electric current to deposit a second hole transport layer having a thickness of 60 nm on the first hole transport layer. After the hole injection layer and the hole transport layer were formed, a light emitting layer was deposited thereon as follows. After putting the following compound H-1 as a host in one cell of the vacuum deposition equipment, and putting compound D-96 as a dopant in another cell, respectively, the two materials are evaporated at different rates to form a dopant for the dopant and the host. A light emitting layer having a thickness of 40 nm was deposited on the second hole transport layer by doping in an amount of 3 wt%. Then, 2-(4-(9,10-di(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole in one cell as an electron transport layer on the light emitting layer After putting lithium quinolate in another cell, the two materials were evaporated at the same rate and each doped at 50 wt% to deposit an electron transport layer of 35 nm. Then, after depositing lithium quinolate to a thickness of 2 nm as an electron injection layer, an Al cathode was deposited to a thickness of 80 nm using another vacuum deposition equipment to manufacture an OLED device. For each material, each compound was purified by vacuum sublimation under 10 ^-6 torr.

As a result, a current of 2.8 mA/cm ² flowed, and red light emission of 800 cd/m ² was confirmed. As a lifespan characteristic, 800 hours was confirmed as a result of measuring the time to reach 90% of the initial luminance at constant current based on 5,000 nits luminance.

[device production example 2] Organic according to the present invention electric field using luminescent compounds OLED device manufacturing

An OLED device was manufactured in the same manner as in Device Preparation Example 1 except that Compound C-9 was deposited to a thickness of 60 nm as the second hole transport layer.

As a result, a current of 5.2 mA/cm ² flowed, and red light emission of 1500 cd/m ² was confirmed. As a lifespan characteristic, 750 hours was confirmed as a result of measuring the time to reach 90% of the initial luminance at constant current based on 5,000 nits luminance.

[device production example 3] Organic according to the present invention electric field using luminescent compounds OLED device manufacturing

An OLED device was manufactured in the same manner as in Device Preparation Example 1 except that Compound C-67 was deposited to a thickness of 60 nm as the second hole transport layer.

As a result, a current of 4.2 mA/cm ² flowed, and red light emission of 1200 cd/m ² was confirmed. As a lifespan characteristic, 780 hours was confirmed as a result of measuring the time to reach 90% of the initial luminance at a constant current of 5,000 nits luminance standard.

[ comparative example 1] conventional organic electric field using luminescent compounds OLED device manufacturing

An OLED device was manufactured in the same manner as in Device Preparation Example 1 except that the following compound was deposited to a thickness of 60 nm as the second hole transport layer.

As a result, a current of 11.2 mA/cm ² flowed, and red light emission of 2000 cd/m ² was confirmed. As a lifespan characteristic, as a result of measuring the time to reach 90% of the initial luminance at a constant current of 5,000 nits luminance, 67 hours was confirmed.

It was confirmed that the luminescent properties of the organic electroluminescent compounds developed in the present invention were superior to those of conventional materials. In addition, the device using the organic electroluminescent compound according to the present invention has good light emitting characteristics and lifespan characteristics.

Claims (7)

An organic electroluminescent compound for an organic electroluminescent device represented by the following formula (2).
[Formula 2]

In Formula 2,
L ₁ and L ₂ are each independently a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (3-30 membered)heteroarylene;
Ar ₁ to Ar ₄ are each independently substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted (3-7 membered)heterocycloalkyl, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (3-30 membered)heteroaryl;
R ₁ and R ₂ are each independently substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C3-C30)cycloalkyl, substituted or unsubstituted (3-7 membered)heterocycloalkyl, substituted or unsubstituted (C6-C30)aryl, or substituted or unsubstituted (3-30 membered)heteroaryl;
R ₃ is hydrogen, deuterium, halogen, substituted or unsubstituted (C1-C30)alkyl, substituted or unsubstituted (C6-C30)aryl, substituted or unsubstituted (3-30 membered)heteroaryl, substituted or unsubstituted substituted (C3-C30)cycloalkyl, substituted or unsubstituted (3-7 membered)heterocycloalkyl, substituted or unsubstituted (C6-C30)ar(C1-C30)alkyl, -SiR ₆ R ₇ R ₈ , cyano, nitro or hydroxy; may be linked to adjacent substituents to form a (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring;
R ₆ to R ₈ 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, substituted or unsubstituted (3-7 membered)heterocycloalkyl, or substituted or unsubstituted (C3-C30)cycloalkyl; It may be linked with an adjacent substituent to form a (C3-C30) monocyclic or polycyclic alicyclic or aromatic ring, wherein a carbon atom of the formed alicyclic or aromatic ring is replaced with one or more heteroatoms selected from nitrogen, oxygen and sulfur can be;
a is an integer from 1 to 4, and when an integer of 2 or more, each R ₃ may be the same or different;
wherein said heteroaryl, heteroarylene and heterocycloalkyl each independently comprise one or more heteroatoms selected from B, N, O, S, P(=O), Si and P;
However, the following compounds are excluded.

delete _The substituted (C1 _{- C30} )alkyl, the substituted (C3 _{- C30} )cycloalkyl, _the substituted (C1 _{- C30} )alkyl, the substituted ( 3-7 membered)heterocycloalkyl, substituted (C6-C30)aryl, substituted (C6-C30)arylene, substituted (3-30 membered)heteroaryl, substituted (3-30 membered)heteroarylene and 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, (C6-C30)aryl unsubstituted (3-30 membered)heteroaryl, (3-30 membered) 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)aryl Amino, (C1-C30)alkylcarbonyl, (C1-C30)alkoxycarbonyl, (C6-C30)arylcarbonyl, di(C6-C30)arylboronyl, di(C1-C30)alkylboronyl At least one selected from the group consisting of (C1-C30)alkyl (C6-C30)arylboronyl, (C6-C30)ar(C1-C30)alkyl and (C1-C30)alkyl(C6-C30)aryl , organic electroluminescent compounds. The method according to claim 1, wherein L ₁ and L ₂ are each independently a single bond, a substituted or unsubstituted (C6-C12)arylene, or a substituted or unsubstituted (5-20 membered)heteroarylene;
Ar ₁ to Ar ₄ are each independently substituted or unsubstituted (C6-C15)aryl;
R ₁ and R ₂ are each independently substituted or unsubstituted (C1-C6)alkyl, substituted or unsubstituted (C6-C20)aryl, or substituted or unsubstituted (5-20 membered)heteroaryl;
R ₃ is hydrogen, substituted or unsubstituted (C6-C12)aryl, substituted or unsubstituted (C5-C12)cycloalkyl or —SiR ₆ R ₇ R ₈ ; may be linked to adjacent substituents to form a (C6-C12) monocyclic or polycyclic alicyclic or aromatic ring;
R ₆ to R ₈ are each independently substituted or unsubstituted (C1-C6)alkyl;
a is an integer of 1 to 2, an organic electroluminescent compound. The method according to claim 1, wherein L ₁ and L ₂ are each independently a single bond, an unsubstituted (C6-C12)arylene, or an unsubstituted (5-20 membered)heteroarylene;
Ar ₁ to Ar ₄ are each independently (C1-C6)alkyl, (C6-C15)aryl, or (C6-C15)aryl unsubstituted or substituted with (5-20 membered)heteroaryl;
R ₁ and R ₂ are each independently an unsubstituted (C1-C6)alkyl; (C6-C20)aryl unsubstituted or substituted with (C1-C6)alkyl, (C6-C25)aryl, or (5-20 membered)heteroaryl; or (5-20 membered) heteroaryl unsubstituted or substituted with (C6-C12)aryl;
R ₃ is hydrogen, unsubstituted (C6-C12)aryl, unsubstituted (C5-C12)cycloalkyl or —SiR ₆ R ₇ R ₈ ; may be linked to adjacent substituents to form a (C6-C12) monocyclic aromatic ring;
R ₆ to R ₈ are each independently unsubstituted (C1-C6)alkyl;
a is an integer of 1 to 2, an organic electroluminescent compound. The organic electroluminescent compound according to claim 1, wherein the compound represented by Formula 1 is selected from the following compounds.

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