KR20200088704A - Organic compound and organic electroluminescent device comprising the same - Google Patents

Abstract

The present invention relates to a novel organic compound and an organic light emitting device comprising the same. More particularly, the present invention provides an organic electroluminescent device with remarkably improved voltage, luminous efficiency and life characteristics. The compound is represented by chemical formula 1.

Description

Organic compounds and organic electroluminescent devices comprising the same {ORGANIC COMPOUND AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME}

The present invention relates to a novel organic compound and an organic electroluminescent device comprising the same, and more particularly, to an organic compound for a hole transport auxiliary layer of the organic electroluminescent device and an organic electroluminescent device comprising the same.

The organic light emitting device (OLED) has a simple structure and has various advantages in a manufacturing process compared to other flat panel display devices such as a liquid crystal display (LCD), a plasma display panel (PDP), and a field emission display (FED). It has been developed and commercialized to be used as a light source for flat panel displays such as wall-mounted TVs or backlights of lights, lights, and billboards because of its high luminance and viewing angle characteristics, high response speed, and low driving voltage.

The organic EL device was reported by Eastman Kodak's Tang, et al. (CW Tang, SA Vanslyke, Applied Physics Letters, Vol. 51, 913 p. 1987, 1987). When a voltage is applied, holes injected from the anode and electrons injected from the cathode recombine to form an exciton, an electron-hole pair, which is converted into light by transmitting the energy of the exciton to a light emitting material.

More specifically, the organic light emitting device has a structure including a cathode (electron injection electrode) and an anode (hole injection electrode), and at least one organic layer between the two electrodes. At this time, the organic light emitting device is a hole injection layer (HIL, hole injection layer), hole transport layer (HTL, hole transport layer), light emitting layer (EML, light emitting layer), electron transport layer (ETL, electron transport layer) or electrons from the anode It is stacked in the order of the injection layer (EIL, electron injection layer), in order to increase the efficiency of the light emitting layer may further include a hole transport auxiliary layer or a hole blocking layer (HBL, hole blocking layer) before and after each of the light emitting layer.

Here, as a hole injection material or a hole transport material, an organic material that is easily oxidized and has an electrochemically stable state during oxidation is mainly used. As an electron injecting material or an electron transporting material, an organic material that is easily reduced and has an electrochemically stable state during reduction is mainly used.

In general, electrons are transferred from the electron transport layer to the light emitting layer, and holes are transferred from the hole transport layer to the light emitting layer to generate excitons by recombination.

The generated excitons emit light in the light emitting layer. When the light is emitted at the hole transport layer interface due to charge unbalance in the light emitting layer, the color purity and efficiency of the organic electric device decreases and the life span is shortened. In order to solve this, the development of an auxiliary layer capable of blocking hole excitons and helping hole transport between the hole transport layer and the light emitting layer is continuously required.

(Patent Document 1) KR 10-2017-0083765 A1

An object of the present invention is to provide a novel organic compound and an organic electroluminescent device comprising the same.

Another object of the present invention is to provide a novel compound that can be used as a hole transport auxiliary layer material between the first electrode and the light emitting layer as an organic compound having relatively strong hole characteristics.

Another object of the present invention is to increase the mobility and stability of the charge in the light emitting layer and at the same time be used in the hole transport auxiliary layer adjacent to the light emitting layer to prevent the accumulation of holes and/or electrons at the interface between the hole transport layer and the light emitting layer and increase the balance of charges. , It is intended to provide an organic light emitting device having significantly improved the voltage, luminous efficiency and life characteristics.

Another object of the present invention is to provide an organic electroluminescent device suitable for AM-OLED using the organic compound.

In order to achieve the above object, the present invention provides a compound represented by Formula 1 below:

[Formula 1]

here,

n, m, o and q are the same or different from each other, each independently an integer from 0 to 4,

p is an integer from 0 to 5,

L ₁ is a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted group, A cycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms, substituted or unsubstituted carbon having 1 to 20 carbon atoms, Heteroalkylene group, consisting of a substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms, and a substituted or unsubstituted heterocycloalkenylene group having 3 to 20 carbon atoms. Is selected from the group,

L ₂ and L ₃ are the same or different from each other, and each independently a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, a substituted or unsubstituted carbon number 1 to Alkylene group of 20, substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms, substituted or Unsubstituted heteroalkylene group having 1 to 20 carbon atoms, substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms and substituted or unsubstituted 3 to 20 carbon atoms 20 heterocycloalkenylene group,

Ar ₁ is hydrogen, deuterium, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxy group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, Substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl group having 3 to 20 carbon atoms, and substituted or unsubstituted hetero atom having 3 to 20 carbon atoms. Selected from the group consisting of aralkyl groups,

R ₁ to R ₅ are the same or different from each other, and each independently hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted carbon number 2 to 20 alkenyl groups, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl groups having 3 to 20 carbon atoms, substituted or unsubstituted An aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, and a substituted or unsubstituted heteroaralkyl group having 3 to 20 carbon atoms,

The substituents of L ₁ to L ₃ , R ₁ to R ₅ and Ar ₁ are hydrogen, deuterium, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or 2 to 20 carbon atoms. Alkynyl group, heteroalkyl group having 1 to 20 carbon atoms, aralkyl group having 3 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, heteroaryl group having 3 to 30 carbon atoms and heteroaralkyl group having 3 to 20 carbon atoms Substituted with a substituent, and when substituted with a plurality of substituents, they are the same or different from each other.

In addition, the present invention is a first electrode; A second electrode provided opposite to the first electrode; And one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers of the one or more layers includes a compound represented by Chemical Formula 1 above. Provide a device.

For example, the organic EL device may have a structure including a hole injection layer, a hole transport layer, a hole transport auxiliary layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer, and a capping layer. However, the structure of the organic electroluminescent device is not limited to this, and may include fewer organic material layers.

According to a preferred embodiment of the present invention, the organic material layer is a hole transport auxiliary layer, and the hole transport auxiliary layer may be characterized in that it comprises a compound represented by the formula (1).

“Halogen group” in the present specification is fluorine, chlorine, bromine or iodine.

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

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

In the present invention, "alkynyl (alkynyl)" means a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having at least one carbon-carbon triple bond. Examples of this include ethynyl, 2-propynyl, and the like, but are not limited thereto.

"Alkylthio" in the present invention means the alkyl group described above bonded via a sulfur linkage (-S-).

In the present invention, “aryl” refers to a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms in which a single ring or two or more rings are combined. In addition, two or more rings may be simply attached to each other (pendant) or a condensed form. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, fluorenyl, dimethylfluorenyl, and the like.

“Heteroaryl” in the present invention means a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 6 to 30 carbon atoms. At this time, one or more carbons in the ring, preferably 1 to 3 carbons, are substituted with heteroatoms such as N, O, S or Se. In addition, a form in which two or more rings are simply attached to each other or condensed may be included, and condensed form with an aryl group may also be included. Examples of such heteroaryl include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, triazinyl, phenoxathienyl, indolizinyl, and indolyl ( polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, and carbazolyl; and 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, and the like, but are not limited thereto.

In the present invention, "aryloxy" is a monovalent substituent represented by RO-, wherein R means aryl having 6 to 60 carbon atoms. Examples of such aryloxy include phenyloxy, naphthyloxy, diphenyloxy, and the like, but are not limited thereto.

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

In the present invention, “alkoxy” may be straight chain, branched chain or cyclic chain. The number of carbon atoms in the alkoxy is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. It may be, but is not limited to this.

“Aralkyl” in the present invention means an aryl-alkyl group in which aryl and alkyl are as described above. Preferred aralkyls include lower alkyl groups. Non-limiting examples of suitable aralkyl groups include benzyl, 2-phenethyl and naphthalenylmethyl. The binding to the parent moiety is via alkyl.

In the present invention, "arylamino group" means an amine substituted with an aryl group having 6 to 30 carbon atoms.

In the present invention, “alkylamino group” means an amine substituted with an alkyl group having 1 to 30 carbon atoms.

In the present invention, "aralkylamino group" means an amine substituted with an aryl-alkyl group having 6 to 30 carbon atoms.

In the present invention, “heteroarylamino group” means an aryl group having 6 to 30 carbon atoms and an amine group substituted with a heterocyclic group.

In the present invention, “heteroaralkyl group” means an aryl-alkyl group substituted with a heterocyclic group.

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

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

In the present invention, “alkylsilyl” refers to silyl substituted with alkyl having 1 to 40 carbon atoms, and “arylsilyl” refers to silyl substituted with aryl having 6 to 60 carbon atoms.

In the present invention, "arylene group" means that the aryl group has two binding sites, that is, a divalent group. These may be applied to the description of the aryl group described above, except that each is a divalent group. For example, it may be phenylene, biphenylene naphthylene, anthracenylene, or flu orenylene.

In the present invention, "heteroarylene" means a heteroaryl group having two bonding sites, that is, a divalent group. These may be applied to the description of the heteroaryl group described above, except that each is a divalent group.

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

In the present invention, "to form a ring by combining with an adjacent group" means "substituted or unsubstituted aliphatic hydrocarbon ring by combining with an adjacent group"; A substituted or unsubstituted aromatic hydrocarbon ring; A substituted or unsubstituted aliphatic heterocycle; Substituted or unsubstituted aromatic heterocycle; Or it means forming these condensed rings.

In the present specification, “alicyclic compound” has the same meaning as “aliphatic hydrocarbon ring,” and refers to a ring composed of only carbon and hydrogen atoms as a non-aromatic ring.

As used herein, “heteroalicyclic compound” refers to an alicyclic compound containing at least one heteroatom by replacing one or more of the carbons of the “aliphatic hydrocarbon ring” with a hetero atom.

Examples of "aromatic hydrocarbon ring" in the present specification include, but are not limited to, phenyl group, naphthyl group, anthracenyl group, and the like.

As used herein, “aliphatic heterocycle” refers to an aliphatic ring containing one or more of heteroatoms.

As used herein, “aromatic heterocycle” refers to an aromatic ring containing one or more of heteroatoms.

In the present specification, the aliphatic hydrocarbon ring, aromatic hydrocarbon ring, aliphatic heterocyclic ring and aromatic heterocyclic ring may be monocyclic or polycyclic.

In the present specification, "substitution" means that a hydrogen atom bonded to a carbon atom of a compound is replaced with another substituent, and the position to be substituted is not limited to a position where the hydrogen atom is substituted, that is, a position where the substituent is substitutable, and when two or more are substituted , 2 or more substituents may be the same or different from each other. The substituent is hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxy group, alkyl group having 1 to 30 carbon atoms, alkenyl group having 2 to 30 carbon atoms, alkynyl group having 2 to 24 carbon atoms, heteroalkyl group having 2 to 30 carbon atoms, carbon number Aralkyl group of 6 to 30, aryl group of 5 to 30 carbon atoms, heteroaryl group of 2 to 30 carbon atoms, heteroarylalkyl group of 3 to 30 carbon atoms, alkoxy group of 1 to 30 carbon atoms, alkylamino group of 1 to 30 carbon atoms, carbon number It may be substituted with one or more substituents selected from the group consisting of an arylamino group having 6 to 30 carbon atoms, an aralkylamino group having 6 to 30 carbon atoms and a hetero arylamino group having 2 to 24 carbon atoms, but is not limited to the above examples.

The present invention relates to a novel compound that can be used as a hole transport auxiliary layer material between the first electrode and the light emitting layer, and is used as a hole transport auxiliary layer material adjacent to the light emitting layer to increase the mobility and stability of charge in the light emitting layer, the hole transport layer and the light emitting layer It can facilitate hole movement between the particles, block electrons from flowing into the hole transport layer, and increase the balance of charges.

In addition, by providing a hole transport auxiliary layer containing the new compound, it is possible to provide an organic electroluminescent device having significantly improved voltage, luminous efficiency, and life characteristics.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art to which the present invention pertains can easily practice. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein.

The organic compound according to the present invention is a compound having a bipolar property with strong hole characteristics, and is used in the hole transport auxiliary layer adjacent to the light emitting layer while increasing the mobility and stability of charge in the light emitting layer and at the interface between the hole transport layer and the light emitting layer And/or prevent the accumulation of electrons and increase the balance of charges.

Therefore, it is possible to significantly improve the voltage, luminous efficiency and lifetime characteristics of the organic light emitting device.

Specifically, the compound represented by Formula 1 is as follows:

[Formula 1]

here,

n, m, o and q are the same or different from each other, each independently an integer from 0 to 4,

p is an integer from 0 to 5,

L ₁ is a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted group, A substituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms In the group consisting of a alkylene group, a substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms and a substituted or unsubstituted heterocycloalkenylene group having 3 to 20 carbon atoms. Is selected,

L ₂ and L ₃ are the same or different from each other, and each independently a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, a substituted or unsubstituted carbon number 1 to Alkylene group of 20, substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms, substituted or Unsubstituted heteroalkylene group having 1 to 20 carbon atoms, substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms and substituted or unsubstituted 3 to 20 carbon atoms 20 heterocycloalkenylene group,

Ar ₁ is hydrogen, deuterium, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxy group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, Substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl group having 3 to 20 carbon atoms, and substituted or unsubstituted hetero atom having 3 to 20 carbon atoms. Selected from the group consisting of aralkyl groups,

R ₁ to R ₅ are the same or different from each other, and each independently hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted carbon number 2 to 20 alkenyl groups, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl groups having 3 to 20 carbon atoms, substituted or unsubstituted An aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, and a substituted or unsubstituted heteroaralkyl group having 3 to 20 carbon atoms,

The substituents of L ₁ to L ₃ , R ₁ to R ₅ and Ar ₁ are hydrogen, deuterium, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or 2 to 20 carbon atoms. Alkynyl group, heteroalkyl group having 1 to 20 carbon atoms, aralkyl group having 3 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, heteroaryl group having 3 to 30 carbon atoms and heteroaralkyl group having 3 to 20 carbon atoms Substituted with a substituent, and when substituted with a plurality of substituents, they are the same or different from each other.

The L ₃ is selected from the group consisting of a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalene group, and a substituted or unsubstituted biphenylene group, and the substituents of the phenylene group, naphthalene group and biphenylene group are hydrogen. , Deuterium, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, an alkynyl group having 2 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, an aralkyl group having 3 to 20 carbon atoms, It is substituted with a substituent selected from the group consisting of an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms and a heteroaralkyl group having 3 to 20 carbon atoms, and when substituted with a plurality of substituent groups, they are the same or different from each other. Preferably, L ₃ is a phenylene group.

L ₁ is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, and the substituent group of the arylene group is hydrogen, deuterium, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms. , An alkynyl group having 2 to 20 carbon atoms, a heteroalkyl group having 1 to 20 carbon atoms, an aralkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, a heteroaryl group having 3 to 30 carbon atoms, and a heteroaralkyl group having 3 to 20 carbon atoms It is substituted with a substituent selected from the group consisting of, when they are substituted with a plurality of substituents, they are the same or different from each other.

Ar ₁ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted 3 to 3 carbon atoms. 30 heteroaryl group.

More specifically, Ar ₁ is hydrogen, deuterium, substituted or unsubstituted phenyl group, substituted or unsubstituted naphthyl group, substituted or unsubstituted anthracenyl group, substituted or unsubstituted phenanthrenyl group, substituted or unsubstituted fluorenyl group, substituted Or an unsubstituted carbazole (carbazolyl) group, a substituted or unsubstituted dibenzofuran (dibenzofuranyl) group, a substituted or unsubstituted dibenzothiophene (dibenzothiophenyl) group, a substituted or unsubstituted adamantyl group, Substituted or unsubstituted cyclohexane (cyclohexanyl) group, substituted or unsubstituted methyl group, substituted or unsubstituted ethyl group, substituted or unsubstituted propyl group, substituted or unsubstituted butyl group and substituted or unsubstituted ter-butyl group (tert- butyl), phenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, fluorenyl group, carbazole (carbazolyl) group, dibenzofuran (dibenzofuranyl) group, dibenzothiophene Substituents of (dibenzothiophenyl) group, adamantyl group, cytoloic acid (cyclohexanyl) group, methyl group, ethyl group, propyl group, butyl group, ter-butyl group are hydrogen, deuterium, cyano group , Nitro group, halogen group, hydroxy group, alkyl group having 1 to 30 carbon atoms, alkenyl group having 2 to 30 carbon atoms, alkynyl group having 2 to 24 carbon atoms, heteroalkyl group having 2 to 30 carbon atoms, aralkyl group having 6 to 30 carbon atoms, carbon number 3 To 20 cycloalkyl groups, 3 to 20 heterocycloalkyl groups, 6 to 30 aryl groups, 2 to 30 heteroaryl groups, 3 to 30 heteroarylalkyl groups, 1 to 30 alkoxy groups, carbon number It is substituted with a substituent selected from the group consisting of an alkylsilyl group having 1 to 30, an arylsilyl group having 6 to 30 carbon atoms and an aryloxy group having 6 to 30 carbon atoms, and when substituted with a plurality of substituents, they are the same or different from each other.

The compound represented by Formula 1 may be selected from the group consisting of the following compounds:

The compound of Formula 1 of the present invention can be usefully used as a hole transport auxiliary layer material.

Specifically, the organic compound is used as a hole transport auxiliary layer material and is used in the hole transport auxiliary layer adjacent to the light emitting layer to facilitate hole movement between the hole transport layer and the light emitting layer, blocking electrons from falling into the hole transport layer, and increasing the balance of charges. Compound.

The present invention provides an organic electroluminescent device comprising the compound represented by Formula 1 above.

The organic compound of the present invention can be usefully used as a hole transport auxiliary layer material.

In addition, the present invention relates to a material for a hole transport auxiliary layer containing the organic compound.

In addition, the present invention is an organic electroluminescent device in which an organic thin film layer comprising at least one layer or a plurality of layers including at least a light emitting layer is laminated between a cathode and an anode,

The organic thin film layer is a hole transport auxiliary layer between the first electrode and the light emitting layer.

The organic light emitting device may have a structure in which an anode, a hole injection layer, a hole transport layer, a hole transport auxiliary layer, a light emitting layer, an electron transport layer, an electron injection layer, and a cathode are stacked, and a hole blocking layer may be further stacked if necessary. Can be.

Hereinafter, the organic electroluminescent device of the present invention will be described as an example. However, the contents exemplified below do not limit the organic electroluminescent device of the present invention.

The organic electroluminescent device of the present invention has a structure in which an anode (hole injection electrode), a hole injection layer (HIL), a hole transport layer (HTL), a hole transport auxiliary layer, a light emitting layer (EML), and a cathode (electron injection electrode) are sequentially stacked. It may have, and preferably, may further include an electron blocking layer (EBL) between the anode and the light emitting layer, and an electron transport layer (ETL) and an electron injection layer (EIL) between the cathode and the light emitting layer. In addition, a hole blocking layer (HBL) may be further included between the cathode and the light emitting layer.

As a method of manufacturing an organic light emitting device according to the present invention, first, a positive electrode is formed on a surface of a substrate by coating a material for a positive electrode in a conventional manner. At this time, the substrate used is preferably a glass substrate or a transparent plastic substrate having excellent transparency, surface smoothness, ease of handling and waterproofness. In addition, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO2), and zinc oxide (ZnO) may be used as the anode material.

Next, a hole injection layer (HIL) material is vacuum-deposited or spin coated on the anode surface by a conventional method to form a hole injection layer. Such hole injection layer materials include copper phthalocyanine (CuPc), 4,4',4"-tris(3-methylphenylamino)triphenylamine (m-MTDATA), 4,4',4"-tris(3-methylphenyl) Amino) phenoxybenzene (m-MTDAPB), starburst amines 4,4',4"-tri(N-carbazolyl)triphenylamine (TCTA), 4,4',4"-tris Examples include (N-(2-naphthyl)-N-phenylamino)-triphenylamine (2-TNATA) or IDE406 available from Idemitsu.

A hole transport layer (HTL) material is vacuum-deposited or spin coated on the surface of the hole injection layer in a conventional manner to form a hole transport layer. At this time, as the hole transport layer material, bis(N-(1-naphthyl-n-phenyl))benzidine (α-NPD), N,N'-di(naphthalen-1-yl)-N,N'-biphenyl -Benzidine (NPB) or N,N'-biphenyl-N,N'-bis(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD).

A hole transport auxiliary layer is formed by vacuum-depositing the compound of the present invention on the surface of the hole transport layer.

A light emitting layer (EML) material is vacuum-deposited or spin coated on the surface of the hole transport auxiliary layer in a conventional manner to form a light emitting layer. In this case, tris(8-hydroxyquinolinolato)aluminum (Alq ₃ ) or the like may be used as the sole light emitting material or the light emitting host material among the light emitting layer materials used, and in the case of blue, the compound of the present invention is preferable. Can be used.

In the case of a dopant (dopant) that can be used together with a light emitting host among the light emitting layer materials, IDE102, IDE105, available from Idemitsu, and tris(2-phenylpyridine)iridium(III) (as a phosphorescent dopant) Ir(ppy)3), iridium(III)bis[(4,6-difluorophenyl)pyridinato-N,C-2']picolinate (FIrpic) (Chihaya Adachi et al., Appl. Phys. Lett., 2001, 79, 3082-3084]), platinum(II) octaethyl porphyrin (PtOEP), TBE002 (Cobion Co.), etc. may be used.

An electron transport layer (ETL) material is vacuum-deposited or spin coated on the surface of the light emitting layer in a conventional manner to form an electron transport layer. In this case, the electron transport layer material used is not particularly limited, and preferably tris(8-hydroxyquinolinolato)aluminum (Alq ₃ ) can be used.

Optionally, by forming a hole blocking layer (HBL) between the light emitting layer and the electron transport layer and using a phosphorescent dopant in the light emitting layer together, it is possible to prevent the phenomenon of triplet excitons or holes from diffusing into the electron transport layer. .

The hole blocking layer may be formed by vacuum thermal evaporation and spin coating of the hole blocking layer material in a conventional manner, and the hole blocking layer material is not particularly limited, but preferably (8-hydroxyquinolinola) Lithium (Liq), bis(8-hydroxy-2-methylquinolinolnato)-aluminum biphenoxide (BAlq), bathocuproine (BCP), LiF, and the like can be used.

An electron injection layer (EIL) material is vacuum-deposited or spin coated on the surface of the electron transport layer in a conventional manner to form an electron injection layer. At this time, as the electron injection layer material used, materials such as LiF, Liq, Li ₂ O, BaO, NaCl, and CsF may be used.

A negative electrode is formed on the surface of the electron injection layer by vacuum thermal vapor deposition of a material for a negative electrode in a conventional manner.

At this time, the negative electrode material used is lithium (Li), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium (Mg), magnesium-indium (Mg-In), magnesium-silver (Mg-Ag) and the like can be used. In addition, in the case of a front emission organic electroluminescent device, a transparent cathode through which light can pass may be formed using indium tin oxide (ITO) or indium zinc oxide (IZO).

A capping layer (CPL) may be formed on the surface of the cathode by the composition for forming a capping layer of the present invention.

Hereinafter, a method for synthesizing the compounds will be described below as a representative example. However, the method for synthesizing the compounds of the present invention is not limited to the methods exemplified below, and the compounds of the present invention can be prepared by the methods exemplified below and methods known in the art.

<Synthesis Example 1: Preparation of Compound 1>

1) Preparation of Intermediate 1-1

(3-(9H-carbazol-9-yl)phenyl)boronic acid (50.0 g, 174.1 mmol), 4-bromoaniline (32.95 g, 191.6 mmol), potassium triphosphate (92.41) in a 1000 mL flask under a nitrogen stream. g, 435.3 mmol), palladium(II) acetate (1.17 g, 5.22 mmol), 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (4.29 g, 10.45 mmol), toluene (500 mL) And H ₂ O (50 mL) was added and stirred to reflux. After completion of the reaction, the toluene layer was extracted using toluene and water. The extracted solution was treated with MgSO ₄ to remove residual moisture, concentrated under reduced pressure, and purified by column chromatography to obtain 38.5 g of Compound 1-1 in 66.1% yield.

2) Preparation of Intermediate 1-2

9-bromophenanthrene (40.0 g, 155.6 mmol) in a 1000 mL flask under a stream of nitrogen. (4-Chlorophenyl)boronic acid (26.76 g, 171.1 mmol), potassium carbonate 43.0 g, 311.1 mmol), tetrakis(triphenylphosphine)palladium(0) (5.39 g, 4.67 mmol), toluene (300 mL) , EtOH (100 mL) and H ₂ O (100 mL) were added and refluxed while stirring. After completion of the reaction, the toluene layer was extracted using toluene and water. The extracted solution was treated with MgSO ₄ to remove residual moisture, concentrated under reduced pressure, and purified by column chromatography to obtain 38.5 g of Compound 1-2 in 85.7% yield.

3) Preparation of Intermediate 1-3

9-(4-chlorophenyl)phenanthrene (30.0 g, 103.9 mmol), 3'-(9H-carbazole-9-yl)-[1,1'-biphenyl]-4 in a 1000 mL flask under nitrogen stream -Amine (38.22 g, 114.3 mmol), sodium tert butoxide (19.97 g, 207.8 mmol), tris(dibenzylideneacetone)dipalladium(0) (1.90 g, 2.08 mmol), 2-dicyclohexylphosphino- 2′,6′-dimethoxybiphenyl (1.71 g, 4.16 mmol) and 300 mL of toluene were added and refluxed with stirring. After completion of the reaction, a toluene layer was extracted using 200 mL of water. The extracted solution was treated with MgSO ₄ to remove residual moisture, concentrated under reduced pressure, and purified using a column chromatography method, and recrystallized with dichloromethane/methanol to obtain 43.3 g of Compound 1-3 in 71.0% yield.

4) Preparation of compound 1

3'-(9H-carbazole-9-yl)-N-(4-(phenanthrene-9-yl)phenyl)-[1,1'-biphenyl]-4-amine in a 250 mL flask under nitrogen stream (8.0 g, 13.63 mmol), 4-bromo-1,1'-biphenyl (3.50 g, 15.00 mmol), sodium tert butoxide (2.62 g, 27.27 mmol), tris(dibenzylideneacetone)dipalladium ( 0) (0.25 g, 0.27 mmol), 2-dicyclohexylphosphino-2',6'-dimethoxybiphenyl (0.22 g, 0.54 mmol) and 100 mL of toluene were added and refluxed with stirring.

After completion of the reaction, a toluene layer was extracted using 50 mL of water. The extracted solution was treated with MgSO ₄ to remove residual moisture, concentrated under reduced pressure, and purified using a column chromatography method, and recrystallized from dichloromethane/methanol to obtain 5.6 g of compound 1 in 55.6% yield.

<Synthesis Example 2: Preparation of compound 19>

Same method as compound 1 except using 4-bromo-1,1':4',1''-terphenyl (4.64 g, 15.00 mmol) instead of 4-bromo-1,1'-biphenyl It was synthesized and purified by to obtain a compound 19 6.1 g, 54.9% yield.

<Synthesis Example 3: Preparation of compound 25>

Synthesis and purification in the same manner as in Compound 1 , except that 1-(4-bromophenyl)naphthalene (4.25 g, 15.00 mmol) was used instead of 4-bromo-1,1'-biphenyl, compound 5.2 5.2 g , Obtained in 48.3% yield.

<Synthesis Example 4: Preparation of Compound 31>

4-bromo-1,1'-biphenyl instead of 2- (4-bromophenyl) naphthalene except for the use of (4.25 g, 15.00 mmol) synthesized in the same manner as Compound 1, to give compound 31 5.5 g , 51.1% yield.

<Synthesis Example 5: Preparation of compound 49>

<Synthesis Example 6: Preparation of Compound 2>

1) Preparation of Intermediate 2-1

Synthesis and purification in the same manner as in Compound 1-2 , except that (3-chlorophenyl)boronic acid (26.76 g, 171.1 mmol) was used instead of (4-chlorophenyl)boronic acid, 3-2 g of compound 2-1 , 72.4 % Yield.

2) Preparation of Intermediate 2-2

Compound 2-2 was synthesized and purified in the same manner as in Compound 1-3, except that 9-(3-chlorophenyl)phenanthrene (30.0 g, 103.9 mmol) was used instead of 9-(4-chlorophenyl)phenanthrene. Obtained in 36.8 g, 60.4% yield.

3) Preparation of compound 2

3'-(9H- instead of 3'-(9H-carbazole-9-yl)-N-(4-(phenanthrene-9-yl)phenyl)-[1,1'-biphenyl]-4-amine Carbazole-9-yl)-N-(3-(phenanthrene-9-yl)phenyl)-[1,1'-biphenyl]-4-amine (8.0 g, 13.63 mmol) was used It was synthesized and purified in the same manner as in Compound 1 to obtain Compound 2 in 5.1 g, 50.6% yield.

<Synthesis Example 7: Preparation of compound 20>

3'-(9H- instead of 3'-(9H-carbazole-9-yl)-N-(4-(phenanthrene-9-yl)phenyl)-[1,1'-biphenyl]-4-amine Carbazole-9-yl)-N-(3-(phenanthrene-9-yl)phenyl)-[1,1'-biphenyl]-4-amine (8.0 g, 13.63 mmol) was used, and 4- Same as Compound 1, except using 4-bromo-1,1':4',1''-terphenyl (4.64 g, 15.00 mmol) instead of bromo-1,1'-biphenyl. It was synthesized and purified by a method to obtain a compound 20 in 5.5 g, 49.5% yield.

<Synthesis Example 8: Preparation of compound 26>

3'-(9H-carbazole-9-yl)-N-(3-(phenanthrene-9-yl)phenyl)-[1,1'-biphenyl]-4-amine (8.0 g, 13.63 mmol) mmol) and 1-(4-bromophenyl)naphthalene (4.25 g, 15.00 mmol) were synthesized and purified in the same manner as in Compound 1, except that the compound 26 was obtained in 5.1 g, 47.4% yield.

[Example 1: Preparation of organic electroluminescent device]

An anode was formed of ITO on the substrate on which the reflective layer was formed, and the surface was treated with N2 plasma or UV-ozone. HAT-CN was deposited on the hole injection layer (HIL) to a thickness of 10 nm. Subsequently, N4,N4,N4',N4'-tetra([1,1'-33biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine to a thickness of 120 nm Deposited to form a hole transport layer (HTL).

9,10-Bis (which can form a blue EML as an emission layer (EML) on the hole transport auxiliary layer by forming a hole transport auxiliary layer by vacuum-depositing Compound 1 of the present invention on the hole transport layer to a thickness of 10 nm ( About 2 wt% N1,N1,N6,N6-tetrakis(4-(1-silyl)phenyl)pyrene-1,6-diamine as a dopant while depositing 2-naphthyl)anthraces (ADN) at 20nm Doped.

Anthracene derivatives and LiQ were mixed thereon at a mass ratio of 2:1 to deposit an electron transport layer (ETL) with a thickness of 30 nm, and then, with electron injection layer (EIL), LiQ was deposited to a thickness of 1 nm. Thereafter, a mixture of magnesium and silver (Ag) mixed at a weight ratio of 9:1 as a cathode was deposited to a thickness of 15 nm, and N4,N4'-bis[4-[bis as a capping layer over the cathode. (3-methylphenyl)amino]phenyl]-N4,N4'-diphenyl-[1,1'-biphenyl]-4,4'-diamine (DNTPD) was deposited to a thickness of 60 nm.

On top of that, an organic light emitting device was manufactured by bonding a seal cap containing a moisture absorbent with a UV curable adhesive to protect the organic light emitting device from O ₂ or moisture in the air.

[Examples 2 to 8]

Same as Example 1, except that Compound 2, 19, 20, 25, 26, 31 and 49 synthesized in Synthesis Examples 1 to 8 were used instead of Compound 1 as the hole transport auxiliary layer in Example 1 An organic electroluminescent device was manufactured by the method.

[Comparative Examples 1 to 4]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that NPB and Compounds A to C were used instead of Compound 1 as the hole transport auxiliary layer in Example 1.

[Compound A]

[Compound B]

[Compound C]

[Experimental Example 1: Device performance analysis]

For the organic electroluminescent device manufactured in Examples and Comparative Examples above, the electro-optical characteristics of the device were analyzed under the conditions of constant current of 10mA/cm ² and the lifespan was measured under the driving conditions of 20mA/cm ² , and the results are shown in Table 1 below. Shown.

Hole
Transportation Voltage
(v) Current efficiency
(Cd/A) Light efficiency (lm/W) External quantum efficiency
EQE (%) Color coordinate Lifetime T95(hrs) CIEx CIEy Example 1 Compound 1 4.1 5.8 4.4 11.8 0.141 0.049 215 Example 2 Compound 2 3.85 5.9 4.8 12 0.141 0.047 180 Example 3 Compound 19 4.02 6 4.7 12.5 0.142 0.046 245 Example 4 Compound 20 4.02 6.4 5.0 13 0.141 0.047 205 Example 5 Compound 25 4.12 6.2 4.7 12 0.139 0.052 310 Example 6 Compound 26 3.9 6 4.8 11.9 0.139 0.051 280 Example 7 Compound 31 3.99 5.9 4.6 13 0.144 0.042 210 Example 8 Compound 49 4.1 6.2 4.7 12 0.141 0.049 185 Comparative Example 1 NPB 4.1 4.0 3.0 6.4 0.132 0.061 95 Comparative Example 2 Compound A 3.99 5.9 4.6 12 0.144 0.044 105 Comparative Example 3 Compound B 4.11 5.6 4.3 12.1 0.143 0.043 110 Comparative Example 4 Compound C 4.37 6.4 4.6 12 0.141 0.047 150

As a result of comparing the device of the comparative example and the device of the example, compared with the device of the comparative example using the hole transport auxiliary layer material having a specific structural formula, the voltage and light efficiency characteristics are maintained at the same level or higher, but the lifespan increase phenomenon is remarkable Was confirmed. In particular, it was confirmed that the Examples of the present invention showed a lifespan increase of 2 times or more compared to Comparative Example 1, which is a conventionally used substance.

The preferred embodiments of the present invention have been described in detail above, but the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.

Claims (8)

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

here,
n, m, o and q are the same or different from each other, each independently an integer from 0 to 4,
p is an integer from 0 to 5,
L ₁ is a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, a substituted or unsubstituted alkylene group having 1 to 20 carbon atoms, a substituted or unsubstituted group, A substituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted alkenylene group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl having 1 to 20 carbon atoms In the group consisting of a alkylene group, a substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms and a substituted or unsubstituted heterocycloalkenylene group having 3 to 20 carbon atoms. Is selected,
L ₂ and L ₃ are the same or different from each other, and each independently a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms, a substituted or unsubstituted carbon number 1 to Alkylene group of 20, substituted or unsubstituted cycloalkylene group having 3 to 20 carbon atoms, substituted or unsubstituted alkenylene group having 2 to 20 carbon atoms, substituted or unsubstituted cycloalkenylene group having 3 to 20 carbon atoms, substituted or Unsubstituted heteroalkylene group having 1 to 20 carbon atoms, substituted or unsubstituted heterocycloalkylene group having 3 to 20 carbon atoms, substituted or unsubstituted heteroalkenylene group having 1 to 20 carbon atoms and substituted or unsubstituted 3 to 20 carbon atoms 20 heterocycloalkenylene group,
Ar ₁ is hydrogen, deuterium, cyano group, trifluoromethyl group, nitro group, halogen group, hydroxy group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, Substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted cycloalkenyl group having 3 to 20 carbon atoms, and substituted or unsubstituted hetero atom having 3 to 20 carbon atoms. Selected from the group consisting of aralkyl groups,
R ₁ to R ₅ are the same or different from each other, and each independently hydrogen, deuterium, substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, substituted or unsubstituted carbon number 2 to 20 alkenyl groups, substituted or unsubstituted alkynyl groups having 2 to 20 carbon atoms, substituted or unsubstituted heteroalkyl groups having 1 to 20 carbon atoms, substituted or unsubstituted aralkyl groups having 3 to 20 carbon atoms, substituted or unsubstituted An aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, and a substituted or unsubstituted heteroaralkyl group having 3 to 20 carbon atoms,
The substituents of L ₁ to L ₃ , R ₁ to R ₅ and Ar ₁ are hydrogen, deuterium, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or 2 to 20 carbon atoms. Alkynyl group, heteroalkyl group having 1 to 20 carbon atoms, aralkyl group having 3 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, heteroaryl group having 3 to 30 carbon atoms and heteroaralkyl group having 3 to 20 carbon atoms Substituted with a substituent, and when substituted with a plurality of substituents, they are the same or different from each other. According to claim 1,
The L ₃ is a compound selected from the group consisting of a substituted or unsubstituted phenylene group, a substituted or unsubstituted naphthalene group, and a substituted or unsubstituted biphenylene group. According to claim 1,
The L ₁ is a substituted or unsubstituted arylene group having 6 to 30 carbon atoms. According to claim 1,
Ar ₁ is a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, and a substituted or unsubstituted 3 to 3 carbon atoms. A compound selected from the group consisting of 30 heteroaryl groups. According to claim 1,
The compound represented by Formula 1 is a compound selected from the group consisting of the following compounds:

A first electrode; A second electrode opposed to the first electrode; It includes at least one organic material layer interposed between the first electrode and the second electrode,
The at least one organic layer comprises at least one compound according to claim 1
Organic electroluminescent device. The method of claim 6,
The organic layer is selected from the group consisting of a hole injection layer, a hole transport layer, a hole transport auxiliary layer, a light emitting layer, a hole blocking layer, an electron transport layer, an electron injection layer and a capping layer
Organic electroluminescent device. The method of claim 6,
The organic material layer is a hole transport auxiliary layer between the first electrode and the light emitting layer.
Organic electroluminescent device.