KR20190048115A - Carbazole derivative and organic light emitting device comprising the same - Google Patents

Abstract

The present invention relates to a carbazole derivative represented by chemical formula 1, a coating composition comprising the same, and an organic light-emitting device using the same. The carbazole derivative according to an embodiment of the present invention may be used as the material of an organic material layer of an organic light-emitting device, thereby improving the efficiency, lowering the driving voltage, and/or improving lifetime characteristics of the organic light-emitting device.

Description

TECHNICAL FIELD [0001] The present invention relates to a carbazole derivative and an organic light emitting device including the same. BACKGROUND ART [0002]

The present disclosure relates to carbazole derivatives, coating compositions comprising the carbazole derivatives, And an organic light emitting device formed using the coating composition.

In general, organic light emission phenomenon refers to a phenomenon in which an organic material is used to convert electric energy into light energy. An organic light emitting device using an organic light emitting phenomenon generally has a structure including an anode, a cathode, and an organic material layer therebetween. Here, in order to increase the efficiency and stability of the organic light emitting device, the organic material layer may have a multi-layer structure composed of different materials and may include a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer. When a voltage is applied between the two electrodes in the structure of such an organic light emitting device, holes are injected in the anode, electrons are injected into the organic layer in the cathode, excitons are formed when injected holes and electrons meet, When it falls back to the ground state, the light comes out.

Development of new materials for such organic light emitting devices has been continuously required.

U.S. Patent Application Publication No. 2004-0251816

The present invention provides a carbazole derivative and an organic light emitting device comprising the same.

According to one embodiment of the present invention, there is provided a carbazole derivative represented by the following general formula (1).

 [Chemical Formula 1]

In Formula 1,

R 1 to R 6 are the same or different from each other and each independently represents hydrogen, deuterium, a halogen group, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, A substituted silyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

L 1 and L 2 are the same or different from each other and are each independently a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group,

L3 is a substituted or unsubstituted alkylene group,

Y1 to Y4 are the same or different and each independently represents a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group

Ar 1 to Ar 4 are the same or different from each other and are independently a substituted or unsubstituted alkenyl group, a substituted or unsubstituted amine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, or a thermosetting group Or photocurable group,

a and b each represent an integer of 0 to 6;

When a is 2 or more, R5 are the same or different from each other,

When b is 2 or more, R6 are the same or different from each other.

The present specification also provides a coating composition comprising a carbazole derivative represented by the above formula (1).

Finally, this specification discloses a plasma display panel comprising a first electrode; A second electrode facing the first electrode; And at least one organic compound layer disposed between the first electrode and the second electrode, wherein at least one of the organic compound layers includes the coating composition or a cured product thereof .

The carbazole derivative according to one embodiment of the present invention can be used as a material of an organic material layer of an organic light emitting device, and by using it, it is possible to improve the efficiency, the driving voltage and / or the lifetime characteristics of the organic light emitting device.

In the conventional deposition process, silicon atoms are not preferred because they have lower thermal stability than carbon. However, unlike the deposition process, soluble OLEDs, which have low process temperatures, inhibit intermolecular aggregation, It can contribute to increase the solubility and can be advantageous to the solution process.

1 shows an organic light emitting device according to an embodiment of the present invention.
2 shows the MS data of the intermediate 2.
3 is MS data of Compound 1. Fig.
4 is MS data of compound 2. Fig.
5 is the MS data of compound 3. Fig.

Hereinafter, the present invention will be described in more detail.

The present invention provides a carbazole derivative represented by the above formula (1).

In this specification, when a part is referred to as " including " an element, it is to be understood that it may include other elements as well, without departing from the other elements unless specifically stated otherwise.

In this specification, when a member is located on another member, it includes not only the case where the member is in contact with the other member but also the case where another member exists between the two members.

Examples of substituents in the present specification are described below, but are not limited thereto.

The term " substituted " means that the hydrogen atom bonded to the carbon atom of the compound is replaced with another substituent, and the position to be substituted is not limited as long as the substituent is a substitutable position, , Two or more substituents may be the same as or different from each other.

As used herein, the term " substituted or unsubstituted " A nitrile group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted aryl group; And a substituted or unsubstituted heterocyclic group, or that at least two of the substituents exemplified above are substituted with a substituent to which they are linked, or have no substituent. For example, the "substituent group to which at least two substituents are connected" may be an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heterocyclic group substituted with an aryl group, an aryl group substituted with an alkyl group, or the like.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec- N-pentyl, 3-dimethylbutyl, 2-ethylbutyl, heptyl, n-hexyl, Cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl and the like.

In the present specification, the cycloalkyl group is not particularly limited, but is preferably a group having 3 to 30 carbon atoms. Specific examples thereof include cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, But are not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, isobutyl, sec-butyl, It is not.

In the present specification, the silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, However, the present invention is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 30 carbon atoms. Specific examples of the monocyclic aryl group include a phenyl group, a biphenyl group, a terphenyl group, and the like, but are not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. And preferably 10 to 30 carbon atoms. Specific examples of the polycyclic aryl group include naphthyl, anthracenyl, phenanthryl, triphenyl, pyrenyl, phenalenyl, perylenyl, no.

In the present specification, the fluorenyl group may be substituted, and adjacent groups may combine with each other to form a ring.

,

,

,

,

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등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

,

,

And

And the like. However, the present invention is not limited thereto.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group having at least two aryl groups may contain a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time. For example, the aryl group in the arylamine group may be selected from the examples of the aryl group described above.

In the present specification, the aryl group in the aryloxy group, the N-arylalkylamine group, and the N-arylheteroarylamine group is the same as the aforementioned aryl group. Specific examples of the aryloxy group include a phenoxy group, a p-tolyloxy group, a m-tolyloxy group, a 3,5-dimethyl-phenoxy group, a 2,4,6- trimethylphenoxy group, a p- Naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryloxy group , 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group, 9-phenanthryloxy group and the like.

In the present specification, the heteroaryl group includes at least one non-carbon atom and at least one hetero atom. Specifically, the hetero atom may include one or more atoms selected from the group consisting of O, N, Se and S, and the like. The number of carbon atoms is not particularly limited, but is preferably 2 to 30 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include a thiophene group, a furanyl group, a pyrrolyl group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, A substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted heterocyclic group, , An isoquinolinyl group, an indolyl group, a carbazolyl group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, a benzocarbazolyl group, a benzothiophene group, a dibenzothiophene group, a benzofuranyl group, Phenanthroline, isoxazolyl group, thiadiazolyl group, phenothiazinyl group, and dibenzofuranyl group, but the present invention is not limited thereto.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroarylamine group having two or more heteroaryl groups may include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group at the same time. For example, the heteroaryl group in the heteroarylamine group may be selected from the examples of the above-mentioned heteroaryl group.

In the present specification, examples of the heteroaryl group in the N-arylheteroarylamine group and the N-alkylheteroarylamine group are the same as the examples of the above-mentioned heteroaryl group.

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

(2)

In Formula 2,

R 1 to R 6, Ar 1 to Ar 4, L 1 to L 3, Y 1 to Y 4, a and b are as defined in formula (1).

According to one embodiment of the present invention, R1 to R4 are the same or different from each other and each independently represent hydrogen, deuterium, a halogen group, a nitrile group, a substituted or unsubstituted straight or branched alkyl group, A linear or branched alkenyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group.

According to one embodiment of the present invention, R 1 to R 4 are the same or different and each independently represents a substituted or unsubstituted, straight or branched chain alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted straight-chain Or a branched chain alkenyl group, or a substituted or unsubstituted alkoxy group having 1 to 10 carbon atoms.

According to one embodiment of the present invention, R1 to R4 are the same or different and each independently represents a straight or branched alkyl group having 1 to 10 carbon atoms.

According to one embodiment of the present invention, R 1 to R 4 are the same or different and each independently represents a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a n-butyl group, A pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, or a decyl group.

According to one embodiment of the present invention, R1 to R4 are methyl groups.

According to one embodiment of the present disclosure, R5 and R6 are hydrogen.

According to one embodiment of the present invention, L1 and L2 are the same or different from each other, and each independently is a direct bond, an arylene group having 6 to 20 carbon atoms, or a heteroarylene group having 3 to 20 carbon atoms.

According to one embodiment of the present invention, L1 and L2 are the same or different from each other, and are a direct bond, a monocyclic arylene group having 6 to 20 carbon atoms, a polycyclic arylene group having 10 to 20 carbon atoms, a monocyclic A heteroarylene group, or a polycyclic heteroarylene group having 3 to 20 carbon atoms.

According to one embodiment of the present disclosure, L1 and L2 are direct bonds.

According to one embodiment of the present invention, L1 and L2 are the same or different and each is a monocyclic arylene group having 6 to 20 carbon atoms or a polycyclic arylene group having 10 to 20 carbon atoms.

According to one embodiment of the present invention, L1 and L2 are the same or different from each other and are a phenylene group, a biphenylene group, a terphenylene group, a naphthylene group, an anthracenylene group, or a phenanthrenylene group.

According to one embodiment of the present invention, L1 and L2 are the same or different and are a phenylene group.

According to one embodiment of the present invention, L1 and L2 are the same or different and are heteroarylene groups containing monocyclic N, O, or S of 3 to 20 carbon atoms.

According to one embodiment of the present invention, L1 and L2 are the same or different and are a polycyclic heteroarylene group containing N, O, or S having 3 to 20 carbon atoms.

According to one embodiment of the present invention, L3 is a substituted or unsubstituted alkylene group having 1 to 10 carbon atoms.

According to one embodiment of the present invention, L3 is a substituted or unsubstituted methylene group, a substituted or unsubstituted ethylene group, a substituted or unsubstituted propylene group, a substituted or unsubstituted butylene group, a substituted or unsubstituted pentyl A substituted or unsubstituted heptylene group, a substituted or unsubstituted octylene group, a substituted or unsubstituted nonylene group, or a substituted or unsubstituted decylene group.

According to one embodiment of the present invention, L3 is an ethylene group, a butylene group, or a hexylene group.

According to one embodiment of the present invention, Y1 to Y4 are the same or different and each independently represents a direct bond, a substituted or unsubstituted arylene group having 6 to 20 carbon atoms, a substituted or unsubstituted C3 to C20 Lt; / RTI >

According to one embodiment of the present invention, Y1 to Y4 are direct bonds.

According to one embodiment of the present invention, Y1 to Y4 are the same or different, and independently of each other, a substituted or unsubstituted monocyclic C6-C20 arylene group.

According to one embodiment of the present invention, Y1 to Y4 are the same or different and each independently represents a phenylene group, a biphenylene group, a terphenylrenylene group, a naphthylenylene group, an anthracenylene group, or a phenanthrenyl group It is a stove.

According to one embodiment of the present invention, Y1 to Y4 are phenylene groups.

According to one embodiment of the present invention, Y1 to Y4 are the same or different and each independently represent a substituted or unsubstituted polycyclic arylene group having 10 to 20 carbon atoms.

According to one embodiment of the present invention, Y 1 to Y 4 are the same or different and each independently a substituted or unsubstituted monocyclic heteroarylene group having 3 to 20 carbon atoms.

According to one embodiment of the present invention, Y1 to Y4 are the same or different and each independently a substituted or unsubstituted C3-C20 polycyclic heteroarylene group.

According to one embodiment of the present invention, Ar 1 to Ar 4 are the same or different and each independently represents a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, a substituted or unsubstituted amine group, An aryl group having 6 to 20 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms, or a thermosetting group or a photocurable group.

According to one embodiment of the present invention, Ar 1 to Ar 4 are the same or different and are each independently a substituted or unsubstituted, linear or branched alkenyl group having 1 to 10 carbon atoms.

According to one embodiment of the present invention, Ar1 to Ar4 are vinyl groups.

According to one embodiment of the present invention, Ar 1 to Ar 4 are the same or different and each independently represent a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

According to one embodiment of the present invention, Ar1 to Ar4 are the same or different, and each independently represents a substituted or unsubstituted monocyclic aryl group having 6 to 20 carbon atoms.

According to one embodiment of the present invention, Ar 1 to Ar 4 are the same or different and each independently a substituted or unsubstituted, C 6 -C 10 aryl group.

According to one embodiment of the present invention, Ar1 to Ar4 are the same or different, and each independently represents a monocyclic or polycyclic C6-C20 aryl group substituted or unsubstituted with an alkyl group or an alkenyl group.

According to one embodiment of the present invention, Ar 1 to Ar 4 are the same or different and each independently represents a substituted or unsubstituted aryl group, or an amine group substituted or unsubstituted with a heteroaryl group.

According to one embodiment of the present invention, Ar 1 to Ar 4 are the same or different and each independently represents a substituted or unsubstituted aryl group having 6 to 20 carbon atoms or a substituted or unsubstituted heteroaryl group having 3 to 20 carbon atoms Amine group.

According to one embodiment of the present invention, Ar 1 to Ar 4 are the same or different and each independently represents a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 20 carbon atoms or a monocyclic or polycyclic Or an amine group substituted or unsubstituted with a heteroaryl group.

According to one embodiment of the present invention, Ar 1 to Ar 4 are the same or different and each independently represents a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 20 carbon atoms or a monocyclic or polycyclic Substituted or unsubstituted amine group containing a heteroaryl group containing N, O, or S.

According to one embodiment of the present invention, Ar 1 to Ar 4 are the same or different and each independently represents a phenyl group, a biphenyl group, a naphthyl group, an anthracene group, a phenanthrene group, a pyrenylene group, or a dimethyl A substituted or unsubstituted amine group by a fluorene group.

According to one embodiment of the present invention, Ar 1 to Ar 4 are the same or different and are each independently an unsubstituted or substituted phenyl group, biphenyl group, naphthyl group, or amine substituted or unsubstituted with a dimethylfluorene group .

According to one embodiment of the present invention, Ar1 to Ar4 are the same or different from each other, and are each independently a thermosetting group or a photocurable group.

According to one embodiment of the present invention, Ar1 to Ar4 are the same or different from each other, and each independently is a thermosetting group or a photocurable group represented by any one of the following structural formulas.

In the above formula,

Ri to Riv are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

Rv is O, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkoxysilyl group, or a substituted or unsubstituted arylene group,

r is an integer of 0 to 4,

When r is plural, Riv is the same or different from each other,

s is an integer of 0 to 5,

When s is plural, Riii are the same or different from each other.

According to one embodiment of the present invention, Ar1 and Ar3 are the same or different from each other, and each independently is a thermosetting group or a photocurable group.

According to one embodiment of the present invention, any one of Ar1 and Ar3 is a styrene group.

According to one embodiment of the present invention, Ar2 and Ar4 are the same or different from each other, and each independently is a thermosetting group or a photocurable group.

According to one embodiment of the present invention, any one of Ar2 and Ar4 is a styrene group.

According to another embodiment of the present invention, the carbazole derivative of Formula 1 may be represented by the following structural formulas.

According to one embodiment of the present invention, the carbazole derivative of Formula 1 may be prepared according to the following reaction scheme, but is not limited thereto. In the following reaction formula, the kind and number of substituents can be variously synthesized by appropriately selecting starting materials known to those skilled in the art. The type of reaction and the reaction conditions may be those known in the art.

[General Production Method of Chemical Formula 1]

(C) can be prepared through a C-N coupling reaction using an aryl halide (A) containing a silicon atom and a primary amine (B) containing a curing unit.

In the above production process, the aryl halide (A) can be represented by the following structural formula, but is not limited thereto.

In the case of using the material represented by the above structural formula, it is advantageous to use a linking group containing a silicon atom to synthesize a polymerizable dimer-type curing monomolecule easily.

All of the compounds of formula (1) described in this specification can be prepared by appropriately combining the above-described preparation methods described in the examples of the present specification and the intermediates based on common technical knowledge.

In one embodiment of the present disclosure, there is provided a coating composition comprising a carbazole derivative as described above.

In one embodiment of the present disclosure, the coating composition comprises the carbazole derivative and a solvent.

In one embodiment of the present invention, the coating composition may further comprise a polymer compound. When the coating composition further comprises a polymer compound, the ink property of the coating composition can be enhanced. That is, the coating composition further comprising the polymer compound may provide a suitable viscosity for coating or ink jetting.

In one embodiment of the present disclosure, the viscosity of the coating composition is from 1 cP to 25 cP.

In one embodiment of the present disclosure, the viscosity of the coating composition is between 2 cP and 15 cP. When having a viscosity in the above range, it is easy to manufacture the device.

In one embodiment of the present invention, the molecular weight of the carbazole derivative is 50 g / mol to 10,000 g / mol.

In one embodiment of the present invention, the molecular weight of the carbazole derivative is 100 g / mol to 1,000 g / mol.

In one embodiment of the present invention, the carbazole derivative may further include a thermosetting group or a photocurable group.

In one embodiment of the present disclosure, the coating composition may be in a liquid phase. The " liquid phase " means that the liquid phase is at normal temperature and pressure.

Further, the organic light emitting device according to the present invention includes a first electrode; A second electrode facing the first electrode; And one or two or more organic layers disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes the coating composition or a cured product thereof.

In one embodiment of the present invention, the organic material layer includes a hole injecting layer, a hole transporting layer, or a layer simultaneously injecting and transporting holes; The hole injecting layer, the hole transporting layer, or the layer simultaneously injecting and transporting the hole may include the coating composition or a cured product thereof.

In one embodiment of the present invention, the organic material layer includes at least one of an electron injecting layer, an electron transporting layer, and a layer simultaneously performing electron injection and electron transporting, and at least one of the layers is a carbazole derivative . ≪ / RTI >

In one embodiment of the present invention, the organic layer includes a light-emitting layer, and the light-emitting layer may include a carbazole derivative of the general formula (1).

The organic light emitting device of the present invention can be manufactured by a conventional method and material for manufacturing an organic light emitting device, except that one or more organic compound layers are formed using the above-described compounds.

The organic material layer of the organic light emitting device of the present invention may have a single layer structure, but may have a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injecting layer, a hole transporting layer, a light emitting layer, an electron transporting layer, and an electron injecting layer as an organic material layer. However, the structure of the organic light emitting device is not limited thereto, and may include a smaller number of organic layers. In addition, the organic material layer may include at least one of an electron transporting layer, an electron injecting layer, and a layer that simultaneously performs electron transport and electron injection, and at least one of the layers may include the compound.

The organic material layer including the carbazole derivative of Formula 1 may have a multi-layer structure including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer, but is not limited thereto and may have a single layer structure. The organic material layer may be formed using a variety of polymeric materials by a method such as a solvent process such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, Layer.

For example, the structure of the organic light emitting device of the present invention may have a structure as shown in FIG. 1, but the present invention is not limited thereto.

1 illustrates a structure of an organic light emitting device in which a first electrode 2, an organic material layer 3, a light emitting layer 4 and a second electrode 5 are sequentially stacked on a substrate 1. In FIG.

For example, the organic light emitting device according to the present invention may be formed by using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation to form a metal oxide or a metal oxide having conductivity on the substrate, A hole injection layer, a hole transport layer, a light emitting layer, an organic material layer including an electron transporting layer, and an organic material layer including a carbazole derivative of the above formula 1 are formed on the anode, Followed by deposition. In addition to such a method, an organic light emitting device may be formed by sequentially depositing a cathode material, an organic material layer, and a cathode material on a substrate.

As the anode material, a material having a large work function is preferably used so that hole injection can be smoothly conducted into the organic material layer. Specific examples of the cathode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO: Al or SnO _2: a combination of a metal and an oxide such as Sb; Conductive polymers such as poly (3-methyl compounds), poly [3,4- (ethylene-1,2-dioxy) compounds] (PEDT), polypyrrole and polyaniline.

The negative electrode material is preferably a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead or alloys thereof; Layer structure materials such as LiF / Al or LiO ₂ / Al, but are not limited thereto.

As the hole injecting material, it is preferable that the highest occupied molecular orbital (HOMO) of the hole injecting material is between the work function of the anode material and the HOMO of the surrounding organic layer. Specific examples of the hole injecting material include metal porphyrine, oligothiophene, arylamine-based organic materials, hexanitrile hexaazatriphenylene-based organic materials, quinacridone-based organic materials, perylene , An anthraquinone, and a conductive polymer of polyaniline and a poly-compound, but the present invention is not limited thereto.

As the hole transporting material, a material capable of transporting holes from the anode or the hole injecting layer to the light emitting layer and having high mobility to holes is suitable. Specific examples include arylamine-based organic materials, conductive polymers, and block copolymers having a conjugated portion and a non-conjugated portion together, but are not limited thereto.

The light emitting material is preferably a material capable of emitting light in the visible light region by transporting and receiving holes and electrons from the hole transporting layer and the electron transporting layer, respectively, and having good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compounds; Compounds of the benzoxazole, benzothiazole and benzimidazole series; Polymers of poly (p-phenylenevinylene) (PPV) series; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The light emitting layer may include a host material and a dopant material. The host material is a condensed aromatic ring derivative or a heterocyclic compound. Specific examples of the condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds. Examples of the heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

When the organic light emitting diode includes a plurality of organic layers, the organic layers may be formed of the same material or different materials.

The organic light emitting device of the present invention can be manufactured by materials and methods known in the art except that at least one layer of the organic material layer is formed using a coating composition comprising the carbazole derivative.

The present disclosure also provides a method of manufacturing an organic light emitting device formed using the coating composition.

Specifically, in one embodiment of the present disclosure, there is provided a method comprising: preparing a substrate; Forming a cathode or an anode on the substrate; Forming at least one organic material layer on the cathode or the anode; And forming an anode or a cathode on the organic material layer, wherein at least one of the organic material layers is formed using the coating composition or a cured product thereof.

The step of forming at least one layer of the organic material layer using the coating composition may include a coating step followed by a drying step. If necessary, the drying step may include a curing step.

In one embodiment of the present invention, the organic layer formed using the coating composition is formed using spin coating.

In another embodiment, the organic layer formed using the coating composition is formed by a printing method.

In the state of the present specification, the printing method includes, but is not limited to, ink jet printing, nozzle printing, offset printing, transfer printing, or screen printing.

Since the coating composition according to one embodiment of the present invention has a structural characteristic and is suitable for a solution process, the coating composition can be formed by a printing method, so that there is an economical effect in time and cost in manufacturing a device.

In one embodiment of the present disclosure, the step of forming the organic layer formed using the coating composition includes heat treatment or vacuum drying. The residual solvent is removed through the heat treatment or the vacuum drying step.

In one embodiment of the present disclosure, the step of heat-treating or vacuum-drying may comprise a curing step.

In one embodiment of the present invention, the coating composition containing the carbazole derivative may be a coating composition in which a polymer binder is mixed and dispersed.

In one embodiment of the present invention, the polymer binder is preferably one that does not extremely inhibit charge transport, and that does not strongly absorb visible light. Examples of the polymeric binder include poly (N-vinylcarbazole), polyaniline and derivatives thereof, polythiophene and derivatives thereof, poly (p-phenylenevinylene) and derivatives thereof, poly (2,5-thienylenevinylene) A derivative thereof, a polycarbonate, a polyacrylate, polymethyl acrylate, polymethyl methacrylate, polystyrene, polyvinyl chloride, polysiloxane and the like.

In addition, the carbazole derivative according to one embodiment of the present invention includes a fluorene and an amine group, so that the carbazole derivative alone may be included in the organic material layer, or the coating composition containing the carbazole derivative may be thinned through heat treatment or light treatment Or may be incorporated as a copolymer using coating compositions mixed with other monomers. In addition, it can be incorporated as a copolymer or as a mixture using a coating composition mixed with another polymer.

Examples of the dopant material include aromatic amine derivatives, styrylamine compounds, boron complexes, fluoranthene compounds, and metal complexes. Specific examples of the aromatic amine derivatives include condensed aromatic ring derivatives having substituted or unsubstituted arylamino groups, and examples thereof include pyrene, anthracene, chrysene, and peripherrhene having an arylamino group. Examples of the styrylamine compound include substituted or unsubstituted Wherein at least one aryl vinyl group is substituted with at least one aryl vinyl group, and at least one substituent selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group and an arylamino group is substituted or unsubstituted. Specific examples thereof include, but are not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like. Examples of the metal complex include iridium complex, platinum complex, and the like, but are not limited thereto.

The electron transporting material is a layer that transports electrons from the electron injecting layer to the electron transporting layer and transports electrons from the electron injecting layer to the light emitting layer. The electron transporting material is a material capable of transferring electrons from the cathode to the light emitting layer. Is suitable. Specific examples include an Al complex of 8-hydroxyquinoline; Complexes containing Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transporting layer can be used with any desired cathode material as used according to the prior art. In particular, an example of a suitable cathode material is a conventional material having a low work function followed by an aluminum layer or a silver layer. Specifically cesium, barium, calcium, ytterbium and samarium, in each case followed by an aluminum layer or a silver layer.

The electron injection layer is a layer for injecting electrons from an electrode and has an ability to transport electrons and has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, A compound which prevents migration to a layer and is excellent in a thin film forming ability is preferable. Specific examples thereof include fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, A complex compound and a nitrogen-containing five-membered ring derivative, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8- Tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8- hydroxyquinolinato) gallium, bis (10- Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8- quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) (2-naphtholato) gallium, and the like, But is not limited thereto.

The hole blocking layer is a layer which prevents the cathode from reaching the hole, and can be generally formed under the same conditions as the hole injecting layer. Specific examples thereof include, but are not limited to, oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complexes and the like.

The organic light emitting device according to the present invention may be of a top emission type, a back emission type, or a both-side emission type, depending on the material used.

In one embodiment of the present invention, the carbazole derivative may be included in an organic solar cell or an organic transistor in addition to an organic light emitting device.

The process for preparing the carbazole derivative of Formula 1 and the preparation of the organic light emitting device using the same will be described in detail in the following Examples. However, the following examples are intended to illustrate the present invention and the scope of the present invention is not limited thereto.

[Preparation Example 1] Preparation of intermediate 1

1,4-dibromobenzene (4.71 g, 20.0 mmol) was dissolved in tetrahydrofuran (THF), and the temperature was adjusted to -78 ° C. N-butyllithium (4.4 mL, 11.0 mmol) was added thereto, followed by stirring for 30 minutes. 1,2-bis (chlorodimethylsilyl) ethane (2.15 g, 10.0 mmol) was added to the reaction mixture, and the mixture was stirred at room temperature for 3 hours. Ammonium chloride was complete the reaction with _{(NH 4 Cl, ammonium chloride)} , was carried out with ethyl acetate (EA) and the organic layer was extracted and dried after removal of the water to magnesium sulfate (MgSO ₄₎ was purified by column chromatography (column chromatography) to. And then vacuum-recrystallized with acetone to obtain Intermediate 1.

1 H NMR (CDCl 3, 500 MHz):? = 7.46 (d, 4H), 7.30 (d,

[ Manufacturing example  2] Preparation of intermediate 2

(3-bromo-6- (4-vinylphenyl) -9H-carbazole (3.6 g, 10.34 mmol), (4- (1,1'-biphenyl- 30 ml of toluene, 10 ml of ethanol and 10 ml of water were added to a solution of potassium carbonate (5.72 g, 41.36 mmol), potassium carbonate (5.97 g, 12.40 mmol) Lt; RTI ID = 0.0 > 90 C. < / RTI > Pd (PPh ₃₎ to put ₄ (0.6g, 0.51mmol) was reacted for about 24 hours at 90 ℃. The organic layer was extracted with ethyl acetate (EA), dried over magnesium sulfate (MgSO ₄ ), dried and then subjected to column chromatography.

2 shows the MS data of the intermediate 2.

[ Manufacturing example  3] Preparation of compound 1

Intermediate 1 (0.67 g, 1.47 mmol), Intermediate 2 (2.09 g, 2.96 mmol), NaOtBu (1.14 g, 11.84 mmol) and Pd (PtBu ₃ ) ₂ (0.07 g, 0.148 mmol) were dissolved in 10 ml of toluene. The reaction temperature was raised to 90 캜 and stirred for about 24 hours. After lowering the temperature to room temperature and precipitating in ethanol, the insoluble portion was worked up with water and EA. The organic layer was extracted, dried over MgSO ₄ , adsorbed onto palladium using charcoal, and then filtered through celite and silica, respectively. The solution was concentrated and subjected to flash column chromatography to obtain Compound 1.

3 is MS data of Compound 1. Fig.

[ Manufacturing example  4] Preparation of intermediate 3

1,4-dibromobenzene (4.71 g, 20.0 mmol) was dissolved in tetrahydrofuran (THF), and the temperature was adjusted to -78 ° C. N-butyllithium (4.4 mL, 11.0 mmol) was added thereto, followed by stirring for 30 minutes. 1,6-bis (chlorodimethylsilyl) butane (2.43 g, 10.0 mmol) was added thereto, and the mixture was stirred at room temperature for 3 hours. Ammonium chloride was complete the reaction with _{(NH 4 Cl, ammonium chloride)} , was carried out with ethyl acetate (EA) and the organic layer was extracted and dried after removal of the water to magnesium sulfate (MgSO ₄₎ was purified by column chromatography (column chromatography) to. And then vacuum-recrystallized with acetone to obtain Intermediate 3.

1 H NMR (CDCl 3, 500 MHz):? = 7.46 (d, 4H), 7.30 (d, 4H)

[ Manufacturing example  5] Preparation of intermediate 4

1,4-dibromobenzene (4.71 g, 20.0 mmol) was dissolved in tetrahydrofuran (THF), and the temperature was adjusted to -78 ° C. N-butyllithium (4.4 mL, 11.0 mmol) was added thereto, followed by stirring for 30 minutes. 1,6-bis (chlorodimethylsilyl) hexane (2.71 g, 10.0 mmol) was added thereto, followed by stirring at room temperature for 3 hours. Ammonium chloride was complete the reaction with _{(NH 4 Cl, ammonium chloride)} , was carried out with ethyl acetate (EA) and the organic layer was extracted and dried after removal of the water to magnesium sulfate (MgSO ₄₎ was purified by column chromatography (column chromatography) to. Vacuum recrystallization with acetone gave Intermediate 4.

(D, 4H), 1.43 (t, 4H), 1.29-1.23 (m, 8H), 0.25 (s, 12H)

[ Manufacturing example  6] Preparation of compound 2

The compound 2 can be prepared by using Intermediate 3 instead of Intermediate 1 in Preparative Example 3.

4 is MS data of compound 2. Fig.

 [ Manufacturing example  7] Preparation of Compound 3

The above-mentioned compound 3 can be produced by using Intermediate 4 instead of Intermediate 1 in Preparative Example 3.

5 is the MS data of compound 3. Fig.

 [ Experimental Example  1] Solubility experiment

Example  1-1.

Compound 1 was dissolved in toluene to measure its solubility.

Example  1-2.

Compound 2 was dissolved in toluene to measure its solubility.

Example  1-3.

Compound 3 was dissolved in toluene to measure its solubility.

Comparative Example  1-1.

Compound A was dissolved in toluene to measure its solubility.

[Compound A]

Solubility (wt%) Example 1-1 > 10 Examples 1-2 > 10 Example 1-3 > 10 Comparative Example 1-1 3

According to the results shown in Table 1, when p-phenylene was used as a linker instead of a silyl linker, the solubility was reduced.

Experimental Example 2: Fabrication of organic light emitting device

Example 2-1

The glass substrate coated with ITO at a thickness of 1,500 A was immersed in distilled water containing detergent and washed with ultrasonic waves. As a detergent, a product of Fisher Co. was used, and as distilled water, distilled water which was filtered by a secondary filter with a filter of Millipore Co. was used. The ITO was washed for 30 minutes and then washed twice with distilled water and ultrasonically cleaned for 10 minutes. After the distilled water was washed, it was ultrasonically washed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Further, the substrate was cleaned using oxygen plasma for 5 minutes, and then the substrate was transported by a vacuum evaporator.

A composition prepared by mixing VNPB and p-dopant (Formula 6) at a weight ratio of 0.8: 0.2 was coated on the prepared ITO transparent electrode and cured under a nitrogen atmosphere on a hot plate at 220 ° C for 30 minutes to form a 400- To form an injection layer.

A solution of Compound 1 dissolved in toluene was spin-coated on the hole injection layer thus formed and cured on a hot plate at 200 ° C. for 30 minutes to form a hole transport layer having a thickness of 200 Å.

The following compound C was dissolved in toluene on the thus-formed hole transport layer, spin-coated, and heat-treated at 180 ° C for 30 minutes to form a light emitting layer having a thickness of 550 Å.

This was introduced into a vacuum deposition apparatus, and when the base pressure reached 2 x 10 < ^-5 > Pa or less, LiF (10A) and Al (1,000A) were deposited in order to produce an organic light emitting device. In this process, the deposition rate of LiF was 0.01 to 0.05 nm / s, and the deposition rate of materials other than LiF was 0.1 to 0.5 nm / s.

[VNPB] [Formula 6]

 [Compound C]

Example 2-2

An organic light emitting device was fabricated in the same manner as in Example 2-1 except that Compound 2 was used instead of Compound 1 in Example 2-1.

Example 2-3

An organic light emitting device was fabricated in the same manner as in Example 2-1 except that Compound 3 was used instead of Compound 1 in Example 2-1.

Comparative Example 2-1

An organic light emitting device was fabricated in the same manner as in Example 2-1 except that Compound A was used instead of Compound 1 in Example 2-1.

device The driving voltage (V) Current efficiency
(cd / A) QE (%) Luminance
(Cd / m ² ) Lifetime T90
(10 mA / cm ² ) Example 2-1 4.17 6.16 6.64 616 65.5 Example 2-2 4.49 6.44 6.92 644 80.7 Example 2-3 3.62 5.43 5.87 543 82.3 Comparative Example 2-1 5.75 3.03 2.69 303 23.8

1: substrate
2: first electrode
3: organic layer
4: light emitting layer
5: Second electrode

Claims (9)

A carbazole derivative represented by the following formula (1): < EMI ID =
[Chemical Formula 1]

In Formula 1,
R 1 to R 6 are the same or different from each other and each independently represents hydrogen, deuterium, a halogen group, a nitrile group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkoxy group, A substituted silyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,
L 1 and L 2 are the same or different from each other and are each independently a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group,
L3 is a substituted or unsubstituted alkylene group,
Y1 to Y4 are the same or different and each independently represents a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group
Ar 1 to Ar 4 are the same or different from each other and each independently represents a substituted or unsubstituted alkenyl group, a substituted or unsubstituted amine group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group, Or photocurable group,
a and b each represent an integer of 0 to 6;
When a is 2 or more, R5 are the same or different from each other,
When b is 2 or more, R6 are the same or different from each other. The carbazole derivative according to claim 1, wherein the compound represented by Formula 1 is represented by Formula 2:
(2)

In Formula 2,
R 1 to R 6, Ar 1 to Ar 4, L 1 to L 3, Y 1 to Y 4, a and b are as defined in formula (1). The carbazole derivative according to claim 1, wherein Ar 1 to Ar 4 are the same or different and each independently is a thermosetting group or a photocurable group represented by any one of the following structural formulas:

In the above formula,
Ri to Riv are the same or different from each other, and each independently hydrogen; heavy hydrogen; A halogen group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
Rv is O, a substituted or unsubstituted alkylene group, a substituted or unsubstituted alkoxysilyl group, or a substituted or unsubstituted arylene group,
r is an integer of 0 to 4,
When r is plural, Riv is the same or different from each other,
s is an integer of 0 to 5,
When s is plural, Riii are the same or different from each other. The carbazole derivative according to claim 1, wherein Y1 to Y4 are the same or different from each other, and each independently is a monocyclic arylene group having 6 to 20 carbon atoms or a polycyclic arylene group having 10 to 20 carbon atoms. The carbazole derivative according to claim 1, wherein the formula (1) is any one of the following compounds:

A coating composition comprising a carbazole derivative according to any one of claims 1 to 5. A first electrode; A second electrode facing the first electrode; And one or more organic layers disposed between the first electrode and the second electrode, wherein at least one of the organic layers includes the coating composition of claim 6 or a cured product thereof. Light emitting element. The organic light emitting device according to claim 7, wherein the organic layer includes a light emitting layer, and the light emitting layer comprises the coating composition or a cured product thereof. The organic electroluminescent device of claim 7, wherein the organic material layer includes a hole injection layer, a hole transport layer, or a layer simultaneously injecting and transporting holes, wherein the hole injection layer, the hole transport layer, Wherein the organic light emitting device includes a light emitting layer.

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