KR20220004520A - 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 including the same. More particularly, the present invention provides an organic electroluminescent device having significantly improved luminous efficiency and lifespan. In order to achieve the above object, the present invention provides a compound represented by chemical formula 1.

Description

Organic compound and organic electroluminescent device comprising the same

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

Organic light emitting diodes (OLEDs) have a simpler structure than other flat panel display devices such as liquid crystal displays (LCDs), plasma display panels (PDPs), and field emission displays (FEDs), and have various advantages in manufacturing processes. It has excellent high luminance and viewing angle characteristics, fast response speed, and low driving voltage, so it is being actively developed and commercialized to be used as a light source for flat panel displays such as wall-mounted TVs, backlights of displays, lighting, and billboards.

The first organic EL device was reported (CW Tang, SA Vanslyke, Applied Physics Letters, Vol. 51 p. 913, 1987) by CW Tang of Eastman Kodak Co., Ltd., and its light emitting principle is generally, When a voltage is applied, holes injected from the anode and electrons injected from the cathode recombine to form excitons, which are electron-hole pairs, which are converted into light by transferring the energy of the excitons to the light emitting material.

More specifically, the organic electroluminescent device has a structure including a cathode (electron injection electrode), an anode (hole injection electrode), and one or more organic layers between the two electrodes. At this time, the organic electroluminescent device is a hole injection layer (HIL, hole injection layer), a hole transport layer (HTL, hole transport layer), a light emitting layer (EML, light emitting layer), an electron transport layer (ETL, electron transport layer) or electrons from the anode. It is laminated in the order of the injection layer (EIL, electron injection layer), and in order to increase the efficiency of the light emitting layer, a hole transport auxiliary layer or a hole blocking layer (HBL) may be additionally included before and after the light emitting layer, respectively.

A material used as an organic layer in an organic electric device may be classified into a light emitting material and a charge transport material, for example, a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. according to their function.

Lifespan and efficiency are the most problematic in organic electroluminescent devices, and as displays become larger, these problems of efficiency and lifespan must be solved.

Efficiency, lifespan, and driving voltage are related to each other, and when the efficiency is increased, the driving voltage is relatively decreased. It shows a tendency to increase the lifespan.

However, the efficiency cannot be maximized by simply improving the organic material layer. This is because, when the energy level and T1 value between each organic material layer, and the intrinsic properties (mobility, interfacial properties, etc.) of materials are optimally combined, long lifespan and high efficiency can be achieved at the same time.

In addition, in order to solve the light emitting problem in the hole transport layer in recent organic electroluminescent devices, a light emitting auxiliary layer must exist between the hole transport layer and the light emitting layer, and each light emitting layer (R, G, B) supports different light emission. It is time for layer development.

In general, electrons are transferred from the electron transport layer to the emission layer, and holes are transferred from the hole transport layer to the emission layer, and excitons are generated by recombination.

However, most of the materials used for the hole transport layer have a low T1 value because they should have a low HOMO value. As a result, excitons generated in the emission layer are transferred to the hole transport layer, resulting in charge unbalance in the emission layer. This results in light emission at the hole transport layer interface.

When light is emitted at the hole transport layer interface, the color purity and efficiency of the organic electric device are lowered and the lifespan is shortened. Therefore, it is urgently required to develop a light emitting auxiliary layer having a high T1 value and having a HOMO level between the HOMO energy level of the hole transport layer and the HOMO energy level of the light emitting layer.

KR 10-2014-0133572 A1

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

Another object of the present invention is to provide a novel compound that can be used as a material for a hole transport auxiliary layer of an organic electroluminescent device having a HOMO energy level for easy hole transport and excellent hole transport properties to the light emitting layer.

Another object of the present invention is to achieve a charge balance between holes and electrons while having a high T1 value and a deep HOMO energy level by using a hole transport auxiliary layer including a novel organic compound, and a light emitting layer that is not an interface of a hole transport layer An object of the present invention is to provide an organic electroluminescent device in which light is emitted from the inside and thus luminous efficiency and lifespan characteristics are remarkably improved.

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 the following formula (1):

[Formula 1]

here,

m and n are the same as or different from each other, and are each independently an integer of 0 or 1,

m+n ≥ 1,

o and p are the same as or different from each other, and are each independently an integer of 0 to 3,

Ad is a substituted or unsubstituted adamantyl group,

X ₁ is selected from the group consisting of C(R ₃ )(R ₄ ), N(R ₅ ), O, S and Si(R ₆ )(R _{7 ),}

X ₂ is selected from the group consisting of a single bond, C(R ₈ )(R ₉ ), O and S,

L ₁ to L ₃ are the same or different from each other, and each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted C 2 to 10 alkylene group, substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, substituted or unsubstituted cycloalkenylene group having 3 to 10 carbon atoms, substituted or unsubstituted C2 to 10 heteroalkylene group, a substituted or unsubstituted heterocycloalkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 2 to 10 carbon atoms, and a substituted or unsubstituted heterocycloalkenylene group having 2 to 10 carbon atoms selected from the group,

Ar ₁ and Ar ₂ are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. , a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, It is selected from the group consisting of a substituted or unsubstituted cycloalkenyl group having 1 to 20 carbon atoms and a substituted or unsubstituted heteroalkenyl group having 1 to 20 carbon atoms,

R ₁ to R ₉ are the same as or different from each other, and each independently represent hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, substituted or unsubstituted A substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 24 alkynyl group, substituted or An unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms Alkyl group, substituted or unsubstituted C1-C30 alkoxy group, substituted or unsubstituted C1-C30 alkylamino group, substituted or unsubstituted C6-C30 arylamino group, substituted or unsubstituted C6-C30 of an aralkylamino group, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted It is selected from the group consisting of a cyclic aryloxy group having 6 to 30 carbon atoms, and may form a substituted or unsubstituted ring by combining adjacent groups with each other.

In addition, the present invention is a first electrode; a second electrode provided to face 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 one or more organic material layers includes the compound represented by Chemical Formula 1 above. provide a component.

For example, the organic electroluminescent device may have a structure including a hole injection layer, a hole transport layer, a hole transport auxiliary layer, a light emitting layer, an electron transport auxiliary layer, an electron transport auxiliary layer, an electron injection layer, and the like. However, the structure of the organic electroluminescent device is not limited thereto and may include a smaller number of organic material layers.

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

As used herein, the “halogen group” is fluorine, chlorine, bromine or iodine.

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

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

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

In the present invention, "alkylthio" refers to the above-described alkyl group bonded through 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 condensed form may be included. Examples of such aryl include, but are not limited to, phenyl, naphthyl, phenanthryl, anthryl, fluorenyl, dimethylfluorenyl, and the like.

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

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

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

In the present invention, “alkoxy” may be a straight chain, branched chain or cyclic chain. Although the number of carbon atoms of alkoxy is not particularly limited, it is preferably from 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. may be, but is not limited thereto.

As used herein, "aralkyl" refers to an aryl-alkyl group wherein 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. Binding to the parent moiety is through an alkyl.

In the present invention, “arylamino group” refers to an amine substituted with an aryl group having 6 to 30 carbon atoms.

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

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

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

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

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

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

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, the term "arylene group" refers to a divalent group having two bonding positions in an aryl group. Except that each of these is a divalent group, the description of the aryl group described above may be applied. For example, it may be phenylene, biphenylene, naphthylene, anthracenylene, or fluorenylene.

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

In the present invention, 　 "adjacent 　 groups are combined with each other to form a ring" means 　 adjacent 　 groups are bonded to each other to form a substituted or unsubstituted aliphatic hydrocarbon ring; A substituted or unsubstituted aromatic hydrocarbon ring; substituted or unsubstituted aliphatic heterocycle; substituted or unsubstituted aromatic heterocycle; Or it means to form a condensed ring thereof.

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

As used herein, the term “heteroalicyclic compound” refers to an alicyclic compound including at least one hetero atom in which one or more carbons of the “aliphatic hydrocarbon ring” are substituted with a hetero atom.

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

As used herein, the term “aliphatic heterocycle” refers to an aliphatic ring including one or more heteroatoms.

As used herein, the term “aromatic heterocycle” refers to an aromatic ring including one or more heteroatoms.

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

As used herein, "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 as long as the position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, is not limited, and when two or more are substituted , two or more substituents may be the same as or different from each other. The substituent is hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxy group, an alkyl group having 1 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, an alkynyl group having 2 to 24 carbon atoms, a heteroalkyl group having 2 to 30 carbon atoms, a carbon number An aralkyl group having 6 to 30 carbon atoms, an aryl group having 5 to 30 carbon atoms, a heteroaryl group having 2 to 30 carbon atoms, a heteroarylalkyl group having 3 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, an alkylamino group having 1 to 30 carbon atoms, a 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 heteroarylamino group having 2 to 24 carbon atoms, but is not limited thereto.

The present invention is a novel organic compound with a high T1 value and a deep HOMO energy level, in which holes and electrons achieve a charge balance, and light is emitted inside the light emitting layer rather than the hole transport layer interface. Life characteristics can be significantly improved.

Hereinafter, embodiments of the present invention will be described in detail so that those of ordinary skill in the art can easily carry out the present invention. However, the present invention may be embodied in several different forms and is not limited to the embodiments described herein.

A material used as an organic layer in an organic electric device may be classified into a light emitting material and a charge transport material, for example, a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. according to their function.

Lifespan and efficiency are the most problematic in organic electroluminescent devices, and as the display area becomes larger, it is necessary to solve the problems of efficiency or lifespan.

Efficiency, lifespan, and driving voltage are related to each other, and when the efficiency is increased, the driving voltage is relatively decreased. Lifespan can be increased.

However, it is impossible to maximize the efficiency by simply improving the organic material layer, and the energy level and T1 value between each organic material layer, and the intrinsic properties (mobility, interfacial properties, etc.) of the material must be optimally combined to achieve the goal to be achieved before. This is possible.

In addition, recent organic light emitting devices use an auxiliary layer between the hole transport layer and the light emitting layer to solve the light emission problem in the hole transport layer, and it is necessary to use different auxiliary layers according to each light emitting layer (R, G, B). .

The novel organic compound of the present invention has a high T1 value, and has a high T1 value, so as to prevent the light emission problem at the hole transport layer interface, to prevent the problem of lowering the color purity and efficiency of the organic electroluminescent device, and to exhibit the characteristics of a long life It is characterized in that it can be used as a material for the auxiliary layer having a HOMO level between the HOMO energy level and the HOMO energy level of the light emitting layer.

The organic compound according to the present invention is specifically a compound represented by the following formula (1):

[Formula 1]

here,

m and n are the same as or different from each other, and are each independently an integer of 0 or 1,

m+n ≥ 1,

o and p are the same as or different from each other, and are each independently an integer of 0 to 3,

Ad is a substituted or unsubstituted adamantyl group,

X ₁ is selected from the group consisting of C(R ₃ )(R ₄ ), N(R ₅ ), O, S and Si(R ₆ )(R _{7 ),}

X ₂ is selected from the group consisting of a single bond, C(R ₈ )(R ₉ ), O and S,

L ₁ to L ₃ are the same or different from each other, and each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted C 2 to 10 alkylene group, substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, substituted or unsubstituted cycloalkenylene group having 3 to 10 carbon atoms, substituted or unsubstituted C2 to 10 heteroalkylene group, a substituted or unsubstituted heterocycloalkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 2 to 10 carbon atoms, and a substituted or unsubstituted heterocycloalkenylene group having 2 to 10 carbon atoms selected from the group,

Ar ₁ and Ar ₂ are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. , a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, It is selected from the group consisting of a substituted or unsubstituted cycloalkenyl group having 1 to 20 carbon atoms and a substituted or unsubstituted heteroalkenyl group having 1 to 20 carbon atoms,

R ₁ to R ₉ are the same as or different from each other, and each independently represent hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, substituted or unsubstituted A substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 24 alkynyl group, substituted or An unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms Alkyl group, substituted or unsubstituted C1-C30 alkoxy group, substituted or unsubstituted C1-C30 alkylamino group, substituted or unsubstituted C6-C30 arylamino group, substituted or unsubstituted C6-C30 of an aralkylamino group, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted It is selected from the group consisting of a cyclic aryloxy group having 6 to 30 carbon atoms, and may form a substituted or unsubstituted ring by combining adjacent groups with each other.

Wherein X ₁ is O or S, and X ₂ may be a single bond, but is not limited to the above example, and can be used as a material of the auxiliary layer without limitation.

L _{1 To} L _{3 Are} the same or different from each other, and each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms Can be selected from the group consisting of have.

Specifically, L ₁ to L ₃ may be the same or different from each other, and each independently may be selected from the group consisting of a single bond, a substituted or unsubstituted phenylene group, and a substituted or unsubstituted biphenylene group, but in the example It is not limited and can be selected without limitation.

Wherein Ar ₁ and Ar ₂ are the same as or different from each other, and each may be independently selected from the group consisting of the following Chemical Formulas 2 to 6:

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

here,

* means the part to be joined,

q and s are the same as or different from each other, and are each independently an integer of 0 to 5,

r is an integer from 0 to 7,

t, v, x and y are the same as or different from each other, and are each independently an integer of 0 to 4,

u is an integer from 0 to 3,

X ₃ is selected from the group consisting of C(R ₁₈ )(R ₁₉ ), N(R ₂₀ ), O and S,

R ₁₀ to R ₂₀ are the same as or different from each other, and each independently represent hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxyl group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted A substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 24 alkynyl group, substituted or An unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms Alkyl group, substituted or unsubstituted C1-C30 alkoxy group, substituted or unsubstituted C1-C30 alkylamino group, substituted or unsubstituted C6-C30 arylamino group, substituted or unsubstituted C6-C30 of an aralkylamino group, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted It is selected from the group consisting of a cyclic aryloxy group having 6 to 30 carbon atoms, and may form a substituted or unsubstituted ring by combining adjacent groups with 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 may be usefully used as a hole transport auxiliary layer material.

As the compound of the present invention is used as a material for the hole transport auxiliary layer in the organic light emitting device, it is possible to increase the HOMO in the compound and fine-tune it so that the hole mobility can be optimally adjusted according to the electron mobility injected into the light emitting layer. It contains substituents.

Due to these characteristics, when the organic compound is used as a material for an organic light emitting device, it can exhibit equal or superior characteristics in most device characteristics such as luminous efficiency and lifespan.

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 material for a hole transport auxiliary layer.

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

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

The organic electroluminescent 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 if necessary, an electron transport auxiliary layer is further can be stacked.

Hereinafter, the organic electroluminescent device of the present invention will be described by way of example. However, the contents exemplified below are not intended to 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 may have, and preferably, may further include a hole transport auxiliary layer 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, an electron transport auxiliary layer may be further included between the cathode and the light emitting layer.

In the method of manufacturing an organic light emitting diode according to the present invention, first, a material for an anode is coated on the surface of a substrate in a conventional manner to form an anode. In this case, the substrate used is preferably a glass substrate or a transparent plastic substrate excellent in transparency, surface smoothness, handling and waterproofing properties. In addition, as the material for the anode, indium tin oxide (ITO), indium zinc oxide (IZO), tin oxide (SnO ₂ ), zinc oxide (ZnO), etc., which are transparent and have excellent conductivity, may be used.

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

A hole transport layer is formed by vacuum thermal evaporation or spin coating of the hole injection layer material on the surface of the hole injection layer by a conventional method.

A hole transport auxiliary layer is formed by vacuum thermal evaporation or spin coating of the compound of the present invention on the surface of the hole transport layer.

The light emitting layer is formed by vacuum thermal evaporation or spin coating of the light emitting layer (EML) material on the surface of the hole transport auxiliary layer in a conventional manner. In this case, as the light emitting material or the light emitting host material used in the light emitting layer, tris (8-hydroxyquinolinolato) aluminum (Alq3), etc. may be used in the case of green, and Alq3 and CBP (4,4') in the case of blue. -N,N'-dicabazole-biphenyl, 4,4'-N,N'-dicarbazole-biphenyl), PVK (poly(n-vinylcabazole), poly (n-vinylcarbazole)), ADN (9, 10-di(naphthalene-2-yl)anthracene, 9,10-di(naphthalen-2-yl)anthracene), TCTA, TPBI(1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene, 1 ,3,5-tris(N-phenylbenzimidazol-2-yl)benzene), TBADN (3-tert-butyl-9,10-di(naphth-2-yl) anthracene, 3-tert-butyl-9 ,10-di(naphth-2yl)anthracene), E3, DSA (distyrylarylene, distyrylarylene), or a mixture of two or more thereof may be used, but is not limited thereto.

In the case of a dopant that can be used together with a light emitting host among the light emitting layer materials, IDE102 and IDE105 available from Idemitsu, and as a phosphorescent dopant, tris (2-phenylpyridine) iridium (III) ( Ir(ppy)3), iridium(III)bis[(4,6-difluorophenyl)pyridinato-N,C-2′]picolinic acid salt (FIrpic) (Chihaya Adachi et al., Appl.

An electron transport layer (ETL) is formed on the surface of the light emitting layer by vacuum thermal evaporation or spin coating of an electron transport layer (ETL) material in a conventional manner. In this case, the material for the electron transport layer used is not particularly limited, and tris(8-hydroxyquinolinolato)aluminum (Alq ₃ ) may be preferably used.

Optionally, by additionally 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 diffusion of triplet excitons or holes into the electron transport layer. .

The formation of the hole blocking layer can be carried out 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 Earth) lithium (Liq), bis(8-hydroxy-2-methylquinolinolnato)-aluminum biphenoxide (BAlq), bathocuproine (BCP), LiF, and the like may be used.

An electron injection layer is formed by vacuum thermal evaporation or spin coating of an electron injection layer (EIL) material on the surface of the electron transport layer in a conventional manner. In this case, as the electron injection layer material used, a material such as LiF, Liq, Li ₂ O, BaO, NaCl, CsF, etc. may be used.

A cathode is formed by vacuum thermal evaporation of a material for a cathode on the surface of the electron injection layer in a conventional manner.

At this time, as the material for the anode used, 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 top emission organic electroluminescent device, indium tin oxide (ITO) or indium zinc oxide (IZO) may be used to form a transparent cathode through which light can pass.

A capping layer (CPL) may be formed on the surface of the negative electrode by the composition for forming a capping layer.

Hereinafter, a method for synthesizing the compounds will be described below with representative examples. 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 may be prepared by the methods illustrated below and methods known in the art.

<Synthesis Example 1 - Synthesis of compound 337>

1-A) Synthesis of Intermediate 1-A

에서 교반하며 반응을 진행하였다. 반응이 완료되면 메탄올에 넣어 침전시킨 후 생성된 고체를 필터한 뒤 실리카겔 컬럼(silicagel column) 및 재결정 방법으로 정제하여 화합물 1-A 100.5 g (수율: 81%)을 제조하였다. 1-(4'-bromo-[1,1'-biphenyl]-4-yl)adamantane (1-(4'-bromo-[1,1'-biphenyl] -4-yl)adamantane, 100.0 g, 272.2 mmol), [1,1'-biphenyl]-4-amine ([1,1'-biphenyl]-4-amine, 50.68 g, 299.5 mmol), Pd ₂ (dba) ₃ (4.99 g, 5.44 mmol), t-BuONa (52.33 g, 544.5 mmol), 50% t-Bu ₃ P solution (5.12 mL, 21.78 mmol) and toluene (1500 mL) were added to 100

The reaction proceeded with stirring. After the reaction was completed, the resultant solid was filtered and purified by a silica gel column and recrystallization method to prepare 100.5 g of Compound 1-A (yield: 81%).

1-B) Synthesis of compound 337

에서 교반하며 반응을 진행하였다. 반응이 완료되면 메탄올에 넣어 침전시킨 후 침전물을 필터한 뒤 실리카겔 컬럼(silicagel column) 및 재결정 방법으로 정제하여 화합물 337 8.87 g (수율: 65%)을 제조하였다.Compound 1-A (10 g, 21.95 mmol), 3-bromodibenzofuran (3-bromodibenzofuran, 5.97 g, 24.14 mmol), Pd ₂ (dba) ₃ (0.40 g, 0.44 mmol) in a round-bottom flask under a nitrogen stream. , t-BuONa (4.22 g, 43.89 mmol), 50% t-Bu ₃ P solution (0.41 mL, 1.76 mmol) and toluene (150 mL) were added to 100

The reaction proceeded with stirring. After completion of the reaction, it was put in methanol to precipitate, and the precipitate was filtered and purified by a silica gel column and recrystallization method to prepare 8.87 g of compound 337 (yield: 65%).

<Synthesis Example 2 - Synthesis of compound 340>

Compound 340 8.46 g (Yield: 62%) was prepared.

<Synthesis Example 3 - Synthesis of compound 974>

It was synthesized and purified in the same manner as in the synthesis method of compound 337 except for using 3-bromodibenzothiophene (6.35 g, 24.14 mmol) instead of 3-bromodibenzofuran, and 974 9.24 g (yield) : 66%) was prepared.

<Synthesis Example 4 - Synthesis of compound 977>

It was synthesized and purified in the same manner as in the synthesis of compound 337 except for using 2-bromodibenzothiophene (6.35 g, 24.14 mmol) instead of 3-bromodibenzofuran, and 8.40 g of compound 977 (yield) : 60%) was prepared.

<Synthesis Example 5 - Synthesis of compound 424>

5-A) Synthesis of intermediate 5-A

3-bromodibenzofuran (100 g, 404.7 mmol) and (4-chlorophenyl)boronic acid, 75.94 g, 485.7 mmol), K ₂ CO ₃ ( 111.9 g, 809.4 mmol), Pd(PPh3)4 (18.71 g, 16.19 mmol), toluene (900 mL), ethanol (300 mL) and water (300 mL) were added and refluxed with stirring. After completion of the reaction, the organic layer was extracted using toluene and water. The extracted organic layer was _{treated with MgSO 4} to remove residual moisture, concentrated under reduced pressure, and purified by a silica gel column and recrystallization method to prepare 94.49 g of compound 5-A (yield: 83%).

5-B) Synthesis of compound 424

에서 교반하며 반응을 진행하였다. 반응이 완료되면 메탄올에 넣어 침전시킨 후 생성된 고체를 필터한 뒤 실리카겔 컬럼(silicagel column) 및 재결정 방법으로 정제하여 화합물 424 10.42 g (수율: 68%)을 제조하였다.Compound 1-A (10 g, 21.95 mmol), compound 5-A (6.73 g, 24.14 mmol), Pd ₂ (dba) ₃ (0.40 g, 0.44 mmol), t-BuONa (4.22) in a round bottom flask under a nitrogen stream g, 43.89 mmol), sphos (0.36 g, 0.88 mol) and toluene (150 mL) were added to 100

The reaction proceeded with stirring. After completion of the reaction, the resultant solid was filtered and purified by a silica gel column and recrystallization method to prepare 10.42 g (yield: 68%) of compound 424 after precipitation in methanol.

<Synthesis Example 6 - Synthesis of compound 427>

6-A) Synthesis of intermediate 6-A

Except for using 2-bromodibenzofuran (2-bromodibenzofuran, 100 g, 404.7 mmol) instead of 3-bromodibenzofuran, it was synthesized and purified in the same manner as in the synthesis method of Compound 5-A, and was purified to Compound 6-A 92.22 g (yield: 81%) was prepared.

6-B) Synthesis of compound 427

Compound 427 was synthesized and purified in the same manner as in the synthesis method of Compound 424 except for using Compound 6-A (6.73 g, 24.14 mmol) instead of Compound 5-A to prepare 10.1 g of Compound 427 (yield: 66%).

<Synthesis Example 7 - Synthesis of compound 1058>

7-A) Synthesis of intermediate 7-A

Except for using 3-bromodibenzothiophene (3-bromodibenzothiophene, 100 g, 380.0 mmol) instead of 3-bromodibenzofuran, the compound 7-A was synthesized and purified in the same manner as in the synthesis method of compound 5-A. 87.66 g (yield: 82%) was prepared.

7-B) Synthesis of compound 1058

9.96 g (yield: 65%) of compound 1058 was prepared by synthesis and purification in the same manner as in the synthesis of compound 424, except that compound 7-A (7.12 g, 24.14 mmol) was used instead of compound 5-A.

<Synthesis Example 8 - Synthesis of compound 1061>

8-A) Synthesis of Intermediate 8-A

Except for using 2-bromodibenzothiophene (100 g, 380.0 mmol) instead of 3-bromodibenzofuran, the compound 8-A was synthesized and purified in the same manner as in the synthesis method of compound 5-A. 89.80 g (yield: 84%) was prepared.

8-B) Synthesis of compound 1061

Compound 1061 10.42 g (yield: 68%) was prepared by synthesis and purification in the same manner as in the synthesis of compound 424, except that compound 8-A (7.12 g, 24.14 mmol) was used instead of compound 5-A.

<Synthesis Example 9 - Synthesis of compound 346>

9-A) Synthesis of intermediate 9-A

Compound 1 except for using 4-(naphthalen-1-yl)aniline (4-(naphthalen-1-yl)aniline, 65.67 g, 299.5 mmol) instead of [1,1′-biphenyl]-4-amine Compound 9-A 96.75 g (yield: 78%) was prepared by synthesis and purification in the same manner as in the synthesis method of -A.

9-B) Synthesis of compound 346

Compound 346 was synthesized and purified in the same manner as in the synthesis of Compound 337 except for using Compound 9-A (11.1 g, 21.95 mmol) instead of Compound 1-A to prepare 9.00 g of Compound 346 (yield: 61%).

<Synthesis Example 10 - Synthesis of compound 983>

Compound 9-A (11.1 g, 21.95 mmol) and 3-bromodibenzothiophene (6.35 g, 24.14 mmol) were synthesized and purified in the same manner as in the synthesis of compound 337, except that 9.51 g of compound 983 (yield) : 63%) was prepared.

<Synthesis Example 11 - Synthesis of compound 436>

Compound 436 10.84 g (yield: 66 %) was prepared.

<Synthesis Example 12 - Synthesis of Compound 1070>

Compound 1070 10.06 g (yield: 60 %) was prepared.

<Synthesis Example 13 - Synthesis of Compound 1067>

Compound 9-A (11.1 g, 21.95 mmol) and compound 7-A (7.12 g, 24.14 mmol) were synthesized and purified in the same manner as in the synthesis of compound 424, except that compound 1067 10.9 g (yield: 65 %) was prepared.

<Synthesis Example 14 - Synthesis of compound 355>

14-A) Synthesis of intermediate 14-A

Synthesis in the same manner as in the synthesis of Compound 1-A except for using 4-(naphthalen-2-yl)aniline (65.67 g, 299.5 mmol) instead of [1,1'-biphenyl]-4-amine; Purification was performed to prepare 99.24 g of compound 14-A (yield: 80%).

14-B) Synthesis of compound 355

Compound 355 was synthesized and purified in the same manner as in the synthesis of Compound 337 except for using Compound 14-A (11.1 g, 21.95 mmol) instead of Compound 1-A to prepare 9.88 g of Compound 355 (yield: 67%).

<Synthesis Example 15 - Synthesis of compound 992>

Compound 992 9.21 g (9.21 g ( Yield: 65%).

<Synthesis Example 16 - Synthesis of compound 442>

11.16 g of compound 442 (yield: 68 %) was prepared.

<Synthesis Example 17 - Synthesis of compound 445>

Compound 445 10.18 g (yield: 62 %) was prepared.

<Synthesis Example 18 - Synthesis of Compound 1079>

Compound 1079 10.57 g (yield: 63 %) was prepared.

<Synthesis Example 19 - Synthesis of compound 364>

19-A) Synthesis of intermediate 19-A

Compound except for using 4-(phenanthren-9-yl)aniline (4-(phenanthren-9-yl)aniline, 80.66 g, 299.5 mmol) instead of [1,1'-biphenyl]-4-amine Compound 19-A 116.5 g (yield: 77%) was prepared by synthesis and purification in the same manner as in the synthesis method of 1-A.

19-B) Synthesis of compound 364

Compound 364 9.51 g (yield: 60%) was prepared by synthesis and purification in the same manner as in the synthesis of Compound 337, except that Compound 19-A (12.2 g, 21.95 mmol) was used instead of Compound 1-A.

<Synthesis Example 20 - Synthesis of compound 1001>

Compound 1001 9.88 g (compound 1001 9.88 g ( Yield: 61%) was prepared.

<Synthesis Example 21 - Synthesis of compound 395>

21-A) Synthesis of intermediate 21-A

9,9-dimethyl-9H-fluoren-2-amine (9,9-dimethyl-9H-fluoren-2-amine, 62.67 g, 299.5 mmol) was used instead of [1,1'-biphenyl]-4-amine Compound 21-A 122.6 g (yield: 81%) was prepared by synthesis and purification in the same manner as in the synthesis of Compound 1-A except for use.

21-B) Synthesis of compound 395

Compound 395 9.69 g (yield: 66%) was prepared by synthesis and purification in the same manner as in the synthesis of compound 337, except that compound 21-A (11.0 g, 22.19 mmol) was used instead of compound 1-A.

<Synthesis Example 22 - Synthesis of Compound 1029>

Compound 1029 9.40 g (9.40 g ( Yield: 64%) was prepared.

<Synthesis Example 23 - Synthesis of compound 471>

Compound 471 10.97 g (yield: 67) was synthesized and purified in the same manner as in the synthesis of compound 424, except that compound 21-A (11.0 g, 22.19 mmol) and compound 6-A (6.80 g, 24.41 mmol) were used. %) was prepared.

<Synthesis Example 24 - Synthesis of compound 1113>

Compound 1113 10.04 g (yield: 60 %) was prepared.

<Synthesis Example 25 - Synthesis of compound 339>

25-A) Synthesis of Intermediate 25-A

Using [1,1'-biphenyl]-2-amine ([1,1'-biphenyl]-2-amine, 50.68 g, 299.5 mmol) instead of [1,1'-biphenyl]-4-amine Compound 25-A 90.55 g (yield: 73%) was prepared by synthesis and purification in the same manner as in the synthesis method of Compound 1-A, except that.

25-B) Synthesis of compound 339

Compound 339 was synthesized and purified in the same manner as in the synthesis method of Compound 337 except for using Compound 25-A (10.0 g, 21.95 mmol) instead of Compound 1-A to prepare 7.92 g of Compound 339 (yield: 58%).

<Synthesis Example 26 - Synthesis of compound 1011>

26-A) Synthesis of Intermediate 26-A

Instead of [1,1'-biphenyl]-4-amine, [1,1':3',1''-terphenyl]-4'-amine ([1,1':3',1''-terphenyl ]-4'-amine, 73.47 g, 299.5 mmol) was synthesized and purified in the same manner as in the synthesis of Compound 1-A, except that Compound 26-A 108.6 g (yield: 75%) was prepared.

26-B) Synthesis of compound 1011

Compound 1011 9.01 g (Yield: 61 %) was prepared.

<Synthesis Example 27 - Synthesis of compound 748>

27-A) Synthesis of intermediate 27-A

1- (4'-bromo-[1,1'-biphenyl] -4-yl) instead of 1- (4-bromophenyl) adamantane (1- (4-bromophenyl) adamantane, 80.0 g, 274.7 mmol) was synthesized and purified in the same manner as in the synthesis of Compound 1-A, except that Compound 27-A 75.07 g (yield: 72%) was prepared.

27-B) Synthesis of compound 748

Compound 748 9.92 g (yield: 59 %) was prepared.

<Synthesis Example 28 - Synthesis of compound 695>

28-A) Synthesis of intermediate 28-A

1-(4-Bromophenyl)adamantane (80.0 g, 274.7 mmol) and 1,1':4',1''-terphenyl]-4-amine (1,1':4',1' '-terphenyl]-4-amine (74.13 g, 302.2 mmol) was synthesized and purified in the same manner as in the synthesis method of compound 1-A, except that compound 28-A 72.98 g (yield: 70%) was prepared did

28-B) Synthesis of compound 695

Compound 695 8.96 g ( 8.96 g ( Yield: 64%) was obtained.

<Synthesis Example 29 - Synthesis of compound 104>

29-A) Synthesis of intermediate 29-A

Compound 29-A 87.99 g (Yield: 78%) was prepared.

29-B) Synthesis of compound 104

Compound 104 8.42 g (yield: 55 %) was prepared.

<Synthesis Example 30-Synthesis of Compound 867>

30-A) Synthesis of Intermediate 30-A

1-(4-bromophenyl)adamantane (60.0 g, 206.0 mmol) and 4-(naphthalen-2-yl)aniline (4-(naphthalen-2-yl)aniline, 49.70 g, 226.6 mmol) were used. Compound 30-A 66.38 g (yield: 75%) was prepared by synthesis and purification in the same manner as in the synthesis method of compound 1-A, except that.

30-B) Synthesis of Intermediate 30-B

Synthesized in the same manner as in the synthesis of compound 5-A, except that 2-bromodibenzothiophene (50.0 g, 190.0 mmol) and (3-chlorophenyl)boronic acid (35.65 g, 228.0 mmol) were used, Purification was carried out to prepare compound 30-B 37.07 g (yield: 70%).

30-C) Synthesis of compound 867

Compound 867 8.33 g (yield: 52 %) was prepared.

<Synthesis Example 31 - Synthesis of compound 385>

31-A) Synthesis of intermediate 31-A

[1,1'-biphenyl] The compound was synthesized and purified in the same manner as in the synthesis method of Compound 1-A except that diphenzofuran-3-amine (38.4 g, 209.6 mmol) was used instead of [1,1'-biphenyl]-4-amine 31-A 72.49 g (yield: 81%) was prepared.

31-B) Synthesis of compound 385

Compound 385 was synthesized and purified in the same manner as in the synthesis of Compound 337, except that Compound 31-A (10.0 g, 21.29 mmol) was used instead of Compound 1-A to prepare 8.94 g of Compound 385 (yield: 66%).

<Synthesis Example 32 - Synthesis of compound 398>

Synthesis and purification were carried out in the same manner as in the synthesis of compound 337, except that compound 31-A (10.0 g, 21.29 mmol) and 2-bromo-9-phenyl-9H-carbazole (7.55 g, 23.42 mmol) were used. 8.63 g (yield: 57%) of compound 398 was prepared.

<Synthesis Example 33 - Synthesis of compound 476>

Compound 476 9.55 g (yield: 63 %) was prepared.

<Synthesis Example 34 - Synthesis of compound 485>

34-A) Synthesis of intermediate 34-A

[1,1'-biphenyl] -4-amine instead of dibenzothiophen-3-amine (41.77 g, 209.6 mmol) was synthesized and purified in the same manner as in the synthesis method of Compound 1-A, except that 76.82 g of compound 9-A (yield: 83%) was prepared.

34-B) Synthesis of compound 485

Compound 485 8.99 g (yield: 60 %) was prepared.

<Synthesis Example 35 - Synthesis of Compound 1120>

Compound 1120 8.89 g (yield: 58 %) was prepared.

<Synthesis Example 36-Synthesis of Compound 158>

36-A) Synthesis of Intermediate 36-A

Synthesis and purification in the same manner as in the synthesis of Compound 5-A, except that 4-bromoaniline (50.0 g, 290.6 mmol) and dibenzofuran-2-ylboronic acid (73.94 g, 348.8 mmol) were used. to prepare compound 36-A 60.29 g (yield: 80%).

36-B) Synthesis of Intermediate 36-B

1-(4-bromophenyl)adamantane (60.0 g, 206.0 mmol) and compound 36-A (58.77 g, 226.6 mmol) were synthesized in the same manner as in the synthesis of compound 1-A, except that Purification was performed to prepare 72.57 g of compound 36-B (yield: 75%).

36-C) Synthesis of compound 158

Compound 158 8.47 g (8.47 g ( Yield: 61%) was prepared.

<Synthesis Example 37-Synthesis of Compound 159>

Compound 159 9.55 g (yield: 63 %) was prepared.

<Synthesis Example 38 - Synthesis of compound 167>

Compound 167 9.10 g (yield: 60 %) was prepared.

<Synthesis Example 39 - Synthesis of compound 189>

Synthesis and purification in the same manner as in the synthesis of compound 337, except that compound 36-B (10.0 g, 21.29 mmol) and 2-bromo-9-phenyl-9H-carbazole (7.55 g, 23.42 mmol) were used. 8.78 g (yield: 58%) of compound 189 was prepared.

<Synthesis Example 40 - Synthesis of compound 192>

40-A) Synthesis of intermediate 40-A

Except for using 3-bromo-9-phenyl-9H-carbazole (60.0 g, 186.2 mmol) instead of 3-bromodibenzofuran, it was synthesized and purified in the same manner as in the synthesis method of Compound 5-A to compound 40 -A 52.71 g (yield: 80%) was prepared.

40-B) Synthesis of compound 192

Compound 192 9.39 g (yield: 62 %) was prepared.

[Example 1-1: Organic electroluminescent device manufacturing]

An anode was formed with 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 thereon to a thickness of 10 nm as a hole injection layer (HIL). Then, N4,N4,N4',N4'-tetra([1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4'-diamine was deposited to a thickness of 100 nm to form a hole transport layer (HTL) was formed.

The compound 337 of the present invention was vacuum deposited on the hole transport layer to a thickness of 85 nm to form a hole transport auxiliary layer, and 4,4'-N,N'-dicarbazole-biphenyl as a light emitting layer (EML) on the hole transport auxiliary layer While (CBP) was deposited at 35 nm, about 3% of (piq)2Ir(acac) [bis-(1-phenylisoquinolyl)iridium(III)acetylacetonate] was doped as a dopant.

An anthracene derivative and LiQ were mixed in a 1:1 ratio to deposit an electron transport layer (ETL) to a thickness of 30 nm, and LiQ was deposited to a thickness of 1 nm as an electron injection layer (EIL) thereon. Then, a mixture of magnesium and silver (Ag) in a ratio of 1:4 as a cathode was deposited to a thickness of 16 nm, and N4,N4'-bis[4-[bis() 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, a seal cap containing a desiccant with UV-curable adhesive

cap) to _{protect the organic EL device from O 2} or moisture in the atmosphere, thereby manufacturing an organic EL device.

[Examples 2 to 40]

Compounds 340, 974, 977, 424, 427, 1058, 1061, 346, 983, 436, 1070, 1067, 355, 922, 442, 445, 1079, 364 in the hole transport auxiliary layer in Example 1 instead of compound 337 , 1001, 395, 1029, 471, 1113, 339, 1011, 748, 695, 104, 867, 385, 398, 476, 485, 1120, 158, 159, 167, 189, 192 An organic electroluminescent device was manufactured in the same manner as in 1.

[Comparative Examples 1 to 3]

An organic electroluminescent device was prepared in the same manner as in Example 1, except that NPB, Compound A, and Compound B were used as the hole transport auxiliary layer in Example 1 instead of Compound 337.

[Compound A]

[Compound B]

[Experimental Example 1: Device Performance Analysis]

The electroluminescent characteristics when driven with a current of ^{10 mA/cm 2} were confirmed for the organic light emitting diodes prepared in Examples 1 to 40 and Comparative Examples 1 to 3 above.

The results are shown in Table 1 below.

hole transport auxiliary layer Driving voltage (V) efficiency color Cd/A lm/W CIEx CIEy Example 1 compound 337 4.44 40.9 28.9 0.688 0.312 Example 2 compound 340 4.39 41.0 29.4 0.690 0.310 Example 3 compound 974 4.28 35.8 26.3 0.693 0.307 Example 4 compound 977 4.26 35.6 26.3 0.693 0.307 Example 5 compound 424 4.49 42.1 29.4 0.688 0.312 Example 6 compound 427 4.44 42.2 29.9 0.691 0.309 Example 7 compound 1058 4.33 36.9 26.7 0.693 0.307 Example 8 compound 1061 4.31 39.4 28.7 0.680 0.320 Example 9 compound 346 4.46 41.6 29.3 0.690 0.310 Example 10 compound 983 4.30 36.4 26.6 0.693 0.307 Example 11 compound 436 4.41 41.7 29.7 0.690 0.310 Example 12 compound 1070 4.28 36.2 26.6 0.692 0.308 Example 13 compound 1067 4.34 36.9 26.7 0.692 0.308 Example 14 compound 355 4.45 40.9 28.9 0.693 0.307 Example 15 compound 922 4.29 35.8 26.2 0.690 0.310 Example 16 compound 442 4.50 42.1 29.4 0.689 0.311 Example 17 compound 445 4.45 42.2 29.8 0.690 0.310 Example 18 compound 1079 4.32 36.6 26.7 0.688 0.312 Example 19 compound 364 4.56 39.4 27.1 0.689 0.311 Example 20 compound 1001 4.40 34.5 24.6 0.690 0.310 Example 21 compound 395 4.24 37.3 27.6 0.676 0.323 Example 22 compound 1029 4.12 36.4 27.7 0.676 0.323 Example 23 compound 471 4.27 40.2 29.6 0.679 0.321 Example 24 compound 1113 4.19 37.4 28.0 0.679 0.321 Example 25 compound 339 4.31 36.3 26.5 0.673 0.327 Example 26 compound 1011 4.27 38.2 28.1 0.673 0.327 Example 27 compound 748 4.46 42.0 29.5 0.688 0.312 Example 28 compound 695 4.30 36.1 26.4 0.693 0.307 Example 29 compound 104 4.42 36.8 26.1 0.688 0.312 Example 30 compound 867 4.26 32.2 23.7 0.690 0.310 Example 31 compound 385 4.68 31.9 21.4 0.673 0.327 Example 32 compound 398 4.65 34.3 23.2 0.673 0.327 Example 33 compound 476 4.73 31.8 21.1 0.670 0.328 Example 34 compound 485 4.70 34.2 22.8 0.670 0.328 Example 35 compound 1120 4.51 29.8 20.7 0.688 0.312 Example 36 compound 158 4.65 34.3 23.2 0.670 0.328 Example 37 compound 159 4.71 34.5 23.0 0.673 0.327 Example 38 compound 167 4.67 34.7 23.5 0.682 0.316 Example 39 compound 189 4.63 34.4 23.3 0.670 0.328 Example 40 compound 192 4.66 34.6 23.3 0.673 0.327 Comparative Example 1 NPB 5.15 25.0 15.3 0.682 0.316 Comparative Example 2 compound A 4.50 27.1 20.9 0.677 0.321 Comparative Example 3 compound B 4.80 27.9 20.9 0.674 0.325

When the compound of the present invention is used as a material for the hole transport auxiliary layer, it was confirmed that the compound of Comparative Example exhibits an excellent effect in efficiency while exhibiting the same or lower driving voltage as compared to the compound of Comparative Example.

Although preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements by those skilled in the art using the basic concept of the present invention as defined in the following claims are also provided. is within the scope of the

Claims (7)

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

here,
m and n are the same as or different from each other, and are each independently an integer of 0 or 1,
m+n ≥ 1,
o and p are the same as or different from each other, and are each independently an integer of 0 to 3,
Ad is a substituted or unsubstituted adamantyl group,
X ₁ is selected from the group consisting of C(R ₃ )(R ₄ ), N(R ₅ ), O, S and Si(R ₆ )(R _{7 ),}
X ₂ is selected from the group consisting of a single bond, C(R ₈ )(R ₉ ), O and S,
L ₁ to L ₃ are the same or different from each other, and each independently a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms, a substituted or unsubstituted C 2 to 10 alkylene group, substituted or unsubstituted cycloalkylene group having 3 to 10 carbon atoms, substituted or unsubstituted alkenylene group having 2 to 10 carbon atoms, substituted or unsubstituted cycloalkenylene group having 3 to 10 carbon atoms, substituted or unsubstituted C2 to 10 heteroalkylene group, a substituted or unsubstituted heterocycloalkylene group having 2 to 10 carbon atoms, a substituted or unsubstituted heteroalkenylene group having 2 to 10 carbon atoms, and a substituted or unsubstituted heterocycloalkenylene group having 2 to 10 carbon atoms selected from the group,
Ar ₁ and Ar ₂ are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms, or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms. , a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms, a substituted or unsubstituted heteroalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted heterocycloalkyl group having 1 to 20 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 20 carbon atoms, It is selected from the group consisting of a substituted or unsubstituted cycloalkenyl group having 1 to 20 carbon atoms and a substituted or unsubstituted heteroalkenyl group having 1 to 20 carbon atoms,
R ₁ to R ₉ are the same as or different from each other, and each independently represent hydrogen, deuterium, cyano group, nitro group, halogen group, hydroxyl group, substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, substituted or unsubstituted A substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 24 alkynyl group, substituted or An unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms Alkyl group, substituted or unsubstituted C1-C30 alkoxy group, substituted or unsubstituted C1-C30 alkylamino group, substituted or unsubstituted C6-C30 arylamino group, substituted or unsubstituted C6-C30 of an aralkylamino group, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted It is selected from the group consisting of a cyclic aryloxy group having 6 to 30 carbon atoms, and may form a substituted or unsubstituted ring by combining adjacent groups with each other. According to claim 1,
Wherein X ₁ is O or S
compound. According to claim 1,
Wherein L _{1 To} L _{3 Are} the same as or different from each other, and each independently selected from the group consisting of a single bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms and a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms
compound. According to claim 1,
Wherein Ar ₁ And Ar _{2 Are} the same as or different from each other, and each independently selected from the group consisting of Formulas 2 to 6
compound:
[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

[Formula 6]

here,
* means the part to be joined,
q and s are the same as or different from each other, and are each independently an integer of 0 to 5,
r is an integer from 0 to 7,
t, v, x and y are the same as or different from each other, and are each independently an integer of 0 to 4,
u is an integer from 0 to 3,
X ₃ is selected from the group consisting of C(R ₁₈ )(R ₁₉ ), N(R ₂₀ ), O and S,
R ₁₀ to R ₂₀ are the same as or different from each other, and each independently represent hydrogen, deuterium, a cyano group, a nitro group, a halogen group, a hydroxyl group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, a substituted or unsubstituted A substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 3 to C 20 cycloalkyl group, a substituted or unsubstituted C 2 to C 30 alkenyl group, a substituted or unsubstituted C 2 to C 24 alkynyl group, substituted or An unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group having 6 to 30 carbon atoms Alkyl group, substituted or unsubstituted C1-C30 alkoxy group, substituted or unsubstituted C1-C30 alkylamino group, substituted or unsubstituted C6-C30 arylamino group, substituted or unsubstituted C6-C30 of an aralkylamino group, a substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, and a substituted or unsubstituted It is selected from the group consisting of a cyclic aryloxy group having 6 to 30 carbon atoms, and may form a substituted or unsubstituted ring by combining adjacent groups with each other. a first electrode; a second electrode opposite to the first electrode; At least one organic material layer interposed between the first electrode and the second electrode,
The at least one organic material layer comprises at least one compound according to claim 1
organic electroluminescent device. 6. The method of claim 5,
The organic material 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, an electron transport auxiliary layer, an electron transport layer and an electron injection layer.
organic electroluminescent device. 6. The method of claim 5,
The organic layer is a hole transport auxiliary layer
organic electroluminescent device.