KR102171941B1 - Novel compound and organic light emitting device comprising same - Google Patents

Abstract

The present specification provides a novel compound and an organic light-emitting device including the same.

Description

A novel compound and an organic light-emitting device comprising the same TECHNICAL FIELD [NOVEL COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING SAME}

The present specification relates to a novel compound and an organic light emitting device including the same.

In general, the organic light emission phenomenon refers to a phenomenon in which electrical energy is converted into light energy using an organic material. An organic light emitting device using the organic light emitting phenomenon has a structure including an anode, a cathode, and an organic material layer therebetween. Here, the organic material layer is often made of a multi-layered structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device.For example, it may be formed of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, and the like. In the structure of such an organic light-emitting device, when a voltage is applied between the two electrodes, holes are injected from the anode and electrons from the cathode are injected into the organic material layer, and excitons are formed when the injected holes and electrons meet. It glows when it falls back to the ground.

Development of a new material for the organic light emitting device as described above is continuously required.

Korean Patent Application Publication No. 2017-0001552

In the present specification, a novel compound and an organic light emitting device including the same are described.

An exemplary embodiment of the present specification may provide a compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

L is a direct bond; Or a substituted or unsubstituted arylene group,

Ar is represented by the following formula (2),

[Formula 2]

In Formula 2,

Any one of X1 to X4 is C,

The rest are each independently CR; Or N,

X5 to X8 are each independently CR' or N,

R and R'are hydrogen; Cyano group; Halogen group; Or a substituted or unsubstituted aryl group,

At least two or more of X1 to X8 are N.

Further, in the exemplary embodiment of the present specification, an organic light emitting device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers May provide an organic light-emitting device including the compound according to an exemplary embodiment of the present specification.

The compound described herein can be used as a material for an organic material layer of an organic light emitting device. The compound according to at least one exemplary embodiment may improve efficiency, low driving voltage, and/or improve life characteristics in an organic light emitting device. In particular, the compounds described in the present specification may be used as a hole injection, hole transport, hole injection and hole transport, electron suppression, light emission, hole suppression, electron transport, or electron injection material.

More specifically, the compound according to an exemplary embodiment of the present invention has a structure having a high electron-accepting capacity and has excellent heat resistance, so that an appropriate deposition temperature can be maintained when fabricating an organic light-emitting device. In addition, the sublimation temperature is high, so it is possible to achieve high purity by a sublimation purification method, and does not cause contamination of the deposition apparatus or the organic light emitting device when manufacturing the organic light emitting device.

1 shows an example of an organic light-emitting device comprising a substrate 1, an anode 2, a light-emitting layer 3, and a cathode 4.
FIG. 2 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7 and a cathode 4 I did it.

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

An exemplary embodiment of the present specification provides a compound represented by Chemical Formula 1.

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

In the present specification, the term "substituted or unsubstituted" refers to deuterium; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester group; Imide group; Amino group; Phosphine oxide group; Alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Arylsulfoxy group; Silyl group; Boron group; Alkyl group; Cycloalkyl group; Alkenyl group; Aryl group; Aralkyl group; Aralkenyl group; Alkylaryl group; Alkylamine group; Aralkylamine group; Heteroarylamine group; Arylamine group; Arylphosphine group; And substituted or unsubstituted with one or more substituents selected from the group consisting of a heterocyclic group, or substituted or unsubstituted with two or more substituents connected among the aforementioned substituents. For example, "a substituent to which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.

In this specification, "adjacent" The group may refer to a substituent substituted on an atom directly connected to the atom where the corresponding substituent is substituted, a substituent positioned three-dimensionally closest to the corresponding substituent, or another substituent substituted on an atom where the corresponding substituent is substituted. For example, two substituents substituted with an ortho position in a benzene ring and two substituents substituted with the same carbon in an aliphatic ring may be interpreted as "adjacent" to each other. Alternatively, a substituent substituted for N in carbazole and a substituent on carbon 1 or 8 of carbazole may be interpreted as "adjacent group".

In the present specification, examples of the halogen group include fluorine, chlorine, bromine or iodine.

In the present specification, the number of carbon atoms of the carbonyl group is not particularly limited, but it is preferably 1 to 40 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the ester group oxygen may be substituted with a C 1 to C 40 linear, branched or cyclic chain alkyl group or a C 6 to C 30 aryl group. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the number of carbon atoms of the imide group is not particularly limited, but it is preferably 1 to 25 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the silyl group may be represented by the formula of -SiR _a R _b R _c , wherein R _a , R _b and R _c are each hydrogen; A substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. 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, a phenylsilyl group, etc., but is not limited thereto. Does not.

In the present specification, the boron group may be represented by the formula of -BR _a R _b R _c , wherein R _a , R _b and R _c are each hydrogen; A substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. The boron group specifically includes a trimethyl boron group, a triethyl boron group, a t-butyldimethyl boron group, a triphenyl boron group, and a phenyl boron group, but is not limited thereto.

In the present specification, the alkyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 40. According to an exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 6 carbon atoms. Specific examples of the alkyl group include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n -Pentyl, isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl , n-heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2 -Dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, and the like, but are not limited thereto.

In the present specification, the alkoxy group may be linear, branched or cyclic. The number of carbon atoms of the alkoxy group is not particularly limited, but it is preferably 1 to 40 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.

Substituents including an alkyl group, an alkoxy group and other alkyl group moieties described in the present specification include all of the straight chain or branched form.

In the present specification, the alkenyl group may be a linear or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 40. According to an exemplary embodiment, the alkenyl group has 2 to 20 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 10 carbon atoms. According to another exemplary embodiment, the alkenyl group has 2 to 6 carbon atoms. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( Naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, stilbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to an exemplary embodiment, the cycloalkyl group has 3 to 40 carbon atoms. According to another exemplary embodiment, the number of carbon atoms of the cycloalkyl group is 3 to 20. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3, 4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like, but are not limited thereto.

In the present specification, the number of carbon atoms in the alkylamine group is not particularly limited, but is preferably 1 to 40. Specific examples of the alkylamine group include a methylamine group, a dimethylamine group, an ethylamine group, and a diethylamine group, but are 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 including two or more aryl groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.

Specific examples of the aryl amine group include phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 3-methyl-phenylamine group, 4-methyl-naphthylamine group, 2-methyl-biphenylamine Group, 9-methyl-anthracenylamine group, diphenylamine group, phenyl naphthylamine group, ditolylamine group, phenyl tolylamine group, carbazole, and triphenylamine group, but are 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 heteroaryl group in the heteroarylamine group may be a monocyclic heterocyclic group or a polycyclic heterocyclic group. The heteroarylamine group including two or more heterocyclic groups may include a monocyclic heterocyclic group, a polycyclic heterocyclic group, or a monocyclic heterocyclic group and a polycyclic heterocyclic group at the same time.

In the present specification, an arylheteroarylamine group means an amine group substituted with an aryl group and a heterocyclic group.

In the present specification, examples of the arylphosphine group include a substituted or unsubstituted monoarylphosphine group, a substituted or unsubstituted diarylphosphine group, or a substituted or unsubstituted triarylphosphine group. The aryl group in the arylphosphine group may be a monocyclic aryl group or a polycyclic aryl group. The arylphosphine group including two or more aryl groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time.

In the present specification, the aryl group is not particularly limited, but is preferably 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but the monocyclic aryl group is not limited thereto. The polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthryl group, a pyrenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, and the like, but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.

,

등의 스피로플루오레닐기,

(9,9-디메틸플루오레닐기), 및

(9,9-디페닐플루오레닐기) 등의 치환된 플루오레닐기가 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

Spirofluorenyl groups such as,

(9,9-dimethylfluorenyl group), and

It may be a substituted fluorenyl group such as (9,9-diphenylfluorenyl group). However, it is not limited thereto.

In the present specification, the heterocyclic group is a heterocyclic group including at least one of N, O, P, S, Si and Se as a hetero atom, and the number of carbon atoms is not particularly limited, but is preferably 1 to 60 carbon atoms. According to an exemplary embodiment, the number of carbon atoms of the heterocyclic group is 1 to 30. Examples of heterocyclic groups include pyridyl group, pyrrole group, pyrimidyl group, pyridazinyl group, furanyl group, thiophenyl group, imidazole group, pyrazole group, oxazole group, isoxazole group, thiazole group, isothiazole group, Triazole group, oxadiazole group, thiadiazole group, dithiazole group, tetrazol group, pyranyl group, thiopyranyl group, pyrazinyl group, oxazinyl group, thiazinyl group, dioxynyl group, triazinyl group, tetrazinyl group, qui Nolinyl group, isoquinolinyl group, quinolyl group, quinazolinyl group, quinoxalinyl group, naphthyridinyl group, acridyl group, xanthenyl group, phenanthridinyl group, diazanaphthalenyl group, triazindenyl group, indole group , Indolinyl group, indolizinyl group, phthalazinyl group, pyrido pyrimidinyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, benzothiazole group, benzoxazole group, benzimidazole group, benzothiophene group , Benzofuranyl group, dibenzothiophenyl group, dibenzofuranyl group, carbazole group, benzocarbazole group, dibenzocarbazole group, indolocarbazole group, indenocarbazole group, phenazinyl group, imidazopyridine group, phenoxazinyl group , A phenanthridine group, a phenanthroline group, a phenothiazine group, an imidazopyridine group, an imidazophenanthridine group, and the like, but are not limited thereto.

In the present specification, the number of atoms constituting the ring of the heterocyclic group is 3 to 25. In another embodiment, the number of atoms constituting the ring of the heterocyclic group is 5 to 17.

In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroaryl group is aromatic.

In the present specification, the aryl group in the aryloxy group, arylthioxy group, arylsulfoxy group, arylphosphine group, aralkyl group, aralkylamine group, aralkenyl group, alkylaryl group, arylamine group, and arylheteroarylamine group is described above. A description of an aryl group may apply.

In the present specification, among the alkyl thioxy group, alkyl sulfoxy group, aralkyl group, aralkylamine group, alkylaryl group, and alkylamine group, the above description of the alkyl group may be applied.

In the present specification, the heteroaryl group among the heteroaryl group, the heteroarylamine group, and the arylheteroarylamine group may be described above with respect to the heterocyclic group.

In the present specification, the alkenyl group among the aralkenyl groups may be described above with respect to the alkenyl group.

In the present specification, the description of the aryl group described above may be applied except that the arylene group is a divalent group.

In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroarylene group is a divalent group.

In the present specification, the meaning of forming a ring by bonding with an adjacent group to each other means a substituted or unsubstituted aliphatic hydrocarbon ring by bonding with an adjacent group; A substituted or unsubstituted aromatic hydrocarbon ring; Substituted or unsubstituted aliphatic heterocycle; A substituted or unsubstituted aromatic hetero ring; Or it means to form a condensed ring of these.

In the present specification, the aliphatic hydrocarbon ring is a ring that is not aromatic and refers to a ring consisting only of carbon and hydrogen atoms. Specifically, examples of the aliphatic hydrocarbon ring include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, 1,4-cyclohexadiene, cycloheptane, cycloheptene, cyclooctane, cyclooctene, etc. However, it is not limited to these.

In the present specification, the aromatic hydrocarbon ring refers to an aromatic ring consisting only of carbon and hydrogen atoms. Specifically, examples of the aromatic hydrocarbon ring include benzene, naphthalene, anthracene, phenanthrene, perylene, fluoranthene, triphenylene, phenalene, pyrene, tetracene, chrysene, pentacene, fluorene, indene, acenaph Styrene, benzofluorene, spirofluorene, and the like, but are not limited thereto.

In the present specification, the aliphatic hetero ring means an aliphatic ring containing at least one heteroatom. Specifically, examples of the aliphatic heterocycle include oxirane, tetrahydrofuran, 1,4-dioxane, pyrrolidine, piperidine, morpholine, oxephan, There are azocaine and thiocane, but are not limited to these. In the present specification, the aromatic hetero ring means an aromatic ring containing at least one hetero atom. Specifically, examples of the aromatic heterocycle include pyridine, pyrrole, pyrimidine, pyridazine, furan, thiophene, imidazole, pyrazole, oxazole, isoxazole, thiazole, isothiazole, triazole, oxadiazole , Thiadiazole, dithiazole, tetrazole, pyran, thiopyran, diazine, oxazine, thiazine, dioxin, triazine, tetrazine, isoquinoline, quinoline, quinol, quinazoline, quinoxaline, naphthyridine, a Cridine, phenanthridine, diazanaphthalene, triazainden, indole, indolizine, benzothiazole, benzoxazole, benzimidazole, benzothiophene, benzofuran, dibenzothiophene, dibenzofuran, carbazole , Benzocarbazole, dibenzocarbazole, phenazine, imidazopyridine, phenoxazine, phenanthridine, indolocarbazole, indenocarbazole, and the like, but are not limited thereto.

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

According to an exemplary embodiment of the present specification, L is a direct bond or a substituted or unsubstituted arylene group having 6 to 60 carbon atoms.

According to an exemplary embodiment of the present specification, L is a direct bond or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, L is a direct bond or a substituted or unsubstituted arylene group having 6 to 15 carbon atoms.

According to an exemplary embodiment of the present specification, L is a direct bond or a phenylene group.

In addition, according to an exemplary embodiment of the present specification, any one of X1 to X4 is C, which means a connection site with Formula 1 above.

In addition, according to an exemplary embodiment of the present specification, X2 or X3 is C.

According to an exemplary embodiment of the present specification, any one of X1 to X4 is C, the rest are each independently CR or N, X5 to X8 are each independently CR' or N, and at least two of X1 to X8 are N.

According to an exemplary embodiment of the present specification, X1 and X4 are N.

According to an exemplary embodiment of the present specification, X1 and X2 are N.

According to an exemplary embodiment of the present specification, X1 and X3 are N.

According to an exemplary embodiment of the present specification, X2 and X3 are N.

According to an exemplary embodiment of the present specification, X2 and X4 are N.

According to an exemplary embodiment of the present specification, X3 and X4 are N.

In addition, according to an exemplary embodiment of the present specification, independently of X1 to X4, X5 and X6 are N.

According to an exemplary embodiment of the present specification, X5 and X7 are N.

According to an exemplary embodiment of the present specification, X5 and X8 are N.

According to an exemplary embodiment of the present specification, X6 and X7 are N.

According to an exemplary embodiment of the present specification, X6 and X8 are N.

According to an exemplary embodiment of the present specification, X7 and X8 are N.

In addition, according to an exemplary embodiment of the present specification, independently of X1 to X4, X5 is N.

According to an exemplary embodiment of the present specification, X6 is N.

According to an exemplary embodiment of the present specification, X7 is N.

According to an exemplary embodiment of the present specification, X8 is N.

In addition, according to an exemplary embodiment of the present specification, R and R'are each independently hydrogen; Cyano group; Halogen group; Or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

In addition, according to an exemplary embodiment of the present specification, R and R'are each independently hydrogen; Cyano group; Halogen group; Or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In addition, according to an exemplary embodiment of the present specification, R and R'are each independently hydrogen; Cyano group; Halogen group; Or a substituted or unsubstituted aryl group having 6 to 15 carbon atoms.

Further, according to an exemplary embodiment of the present specification, the halogen group is fluorine.

According to an exemplary embodiment of the present specification, the compound represented by Formula 1 may be represented by the following Formula 3.

[Formula 3]

In Chemical Formula 3, L and X5 to X8 are as defined above.

In an exemplary embodiment of the present invention, the compound of Formula 1 may be any one selected from the following compounds.

In the present invention, compounds having various energy band gaps can be synthesized by introducing various substituents into the core structure as described above. In general, it is easy to adjust the energy bandgap by introducing a substituent into a core structure having a large energy bandgap, but when the energy bandgap is small, it is difficult to greatly adjust the energy bandgap by introducing a substituent. In addition, in the present invention, the HOMO and LUMO energy levels of the compound can be adjusted by introducing various substituents to the core structure of the above structure.

In addition, by introducing various substituents into the core structure of the above-described structure, a compound having the inherent characteristics of the introduced substituent can be synthesized. For example, by introducing a substituent mainly used for the hole injection layer material, the hole transport material, the light emitting layer material and the electron transport layer material used in manufacturing the organic light emitting device into the core structure, it is possible to synthesize a material that satisfies the conditions required by each organic material layer. I can.

Accordingly, the present inventors have found that when the compound of Formula 1 having such characteristics is applied to a material for an organic light-emitting device, particularly a light-emitting layer, it is possible to achieve a lower voltage or longer life of the driving voltage. In addition, compared to a material having a small molecular weight and high sublimation property, such as F4TCNQ, deposition is easy, and a stable interface with an electrode or an adjacent organic material layer can be formed.

The compound of Formula 1 described above can be prepared using materials and reaction conditions known in the art.

In addition, the organic light emitting device according to the present invention is an organic light emitting device comprising a first electrode, a second electrode, and at least one organic material layer disposed between the first electrode and the second electrode, wherein at least one of the organic material layers It characterized in that it contains the compound.

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

The organic material layer of the organic light emitting device of the present specification 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 specification may further include at least one of a hole injection layer, a hole buffer layer, a hole transport layer, an electron suppression layer, a hole suppression layer, an electron transport layer, and an electron injection layer in addition to the emission layer as an organic material layer. have. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic layers.

According to an example, the organic light emitting device may be a normal type organic light emitting device in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate. According to another example, the organic light-emitting device may be an organic light-emitting device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate.

The organic light-emitting device of the present specification may be manufactured by materials and methods known in the art, except that at least one of the organic material layers includes the compound of Formula 1, that is, the compound of Formula 1.

For example, the organic light emitting device of the present specification may be manufactured by sequentially laminating a first electrode, an organic material layer, and a second electrode on a substrate. At this time, using a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, a metal or conductive metal oxide or alloy thereof is deposited on the substrate to form an anode. And, after forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer and an electron transport layer thereon, it can be produced by depositing a material that can be used as a cathode thereon. In addition to this method, an organic light-emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

In addition, the compound of Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

In addition to this method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material from a cathode material on a substrate (International Patent Application Publication No. 2003/012890). However, the manufacturing method is not limited thereto.

In the exemplary embodiment of the present specification, the first electrode is an anode, and the second electrode is a cathode.

In another exemplary embodiment, the first electrode is a cathode, and the second electrode is an anode.

Further, according to the exemplary embodiment of the present specification, the organic material layer includes an emission layer, the emission layer includes a host and a dopant, and the dopant may be a compound represented by Formula 1 above.

In the exemplary embodiment of the present specification, the organic material layer includes an emission layer, the emission layer includes a host, a sensitizer, and a fluorescent emitter, and the sensitizer is a compound represented by Formula 1, and the The sensitizer may have a delayed fluorescence characteristic of less than ΔE _st 0.2 eV. △E _st is a value obtained by measuring the energy of singlet and triplet, respectively, and then calculating the difference. Singlet and triplet can be measured using a fluorescent instrument.

When a fluorescent emitter is further included in the emission layer, since the compound represented by Formula 1 transmits exciton energy to the fluorescent emitter to emit light from the fluorescent emitter, high luminance light emission is possible, and the driving voltage is low. , It is possible to manufacture an organic light emitting device having a long life characteristic. In addition, the content of the fluorescent emitter may be 0 to 10 parts by weight based on 100 parts by weight of the host.

As the fluorescent emitter, a fluorescent material such as an anthracene compound, a pyrene compound, and a boron compound may be used, but is not limited thereto.

Examples of the host material for the light emitting layer include condensed aromatic ring derivatives or heterocyclic compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, and ladders. It may be a furan compound, a pyrimidine derivative, or the like, but is not limited thereto.

The host material of the light emitting layer may be more specifically one of Formulas F-1 to F-4, but is not limited thereto.

[Formula F-1]

In the formula F-1,

Q1 to Q3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

p1 is an integer from 0 to 8, and when p1 is 2 or more, Q1 is the same as or different from each other,

[Formula F-2]

In Formula F-2,

W1 is O or S,

Q4 is hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

p2 is an integer from 0 to 4, and when p2 is 2 or more, Q4 is the same as or different from each other,

Q5 to Q8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group, or adjacent groups are bonded to each other to form a substituted or unsubstituted ring, and two or more of Q5 to Q8 are bonded to each other to form a substituted or unsubstituted ring. To form,

[Formula F-3]

In Formula F-3,

W2 is O, S or NA',

A', Q9 and Q10 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

p3 and p4 are each an integer of 0 to 4, and when p3 and p4 are each 2 or more, the substituents in parentheses are the same as or different from each other,

[Formula F-4]

In the formula F-4,

W3 is O or S,

Q11 to Q13 are hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

p5 is an integer of 0 to 4, and when p5 is 2 or more, Q11 is the same as or different from each other.

According to an exemplary embodiment of the present specification, Q1 is hydrogen.

In the exemplary embodiment of the present specification, Q2 and Q3 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group.

According to another exemplary embodiment, Q2 and Q3 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

In another exemplary embodiment, Q2 and Q3 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

According to another exemplary embodiment, Q2 and Q3 are the same as or different from each other, and are each independently an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with a substituted or unsubstituted heteroaryl group.

According to another exemplary embodiment, Q2 and Q3 are the same as or different from each other, and each independently an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with a heteroaryl group substituted with an aryl group.

In another exemplary embodiment, Q2 and Q3 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with a heteroaryl group substituted with an aryl group.

According to another exemplary embodiment, Q2 and Q3 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with a triazinyl group substituted with an aryl group.

In another exemplary embodiment, Q2 and Q3 are the same as or different from each other, and are each independently a phenyl group unsubstituted or substituted with a diphenyltriazinyl group.

In another exemplary embodiment, any one of Q2 and Q3 is a phenyl group, and the other is a phenyl group substituted with a diphenyltriazinyl group.

According to an exemplary embodiment of the present specification, p1 is 0 or 1.

In the exemplary embodiment of the present specification, p2 is 0 or 1.

According to an exemplary embodiment of the present specification, Q4 is hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted C2 to C60 heterocyclic group.

In another exemplary embodiment, Q4 is hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted C2 to C30 heterocyclic group.

According to another exemplary embodiment, the Q4 is hydrogen; heavy hydrogen; A substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; Or a substituted or unsubstituted carbazole group.

In another exemplary embodiment, Q4 is hydrogen; heavy hydrogen; A phenyl group substituted with a 2-methylpropenyl group; Biphenyl group; Terphenyl group; Or carbazole group.

According to an exemplary embodiment of the present specification, Q5 to Q8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted aryl group, or adjacent groups are bonded to each other to form a substituted or unsubstituted ring, and two or more of Q5 to Q8 are bonded to each other to form a substituted or unsubstituted ring.

In another exemplary embodiment, Q5 to Q8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or adjacent groups are bonded to each other to form a substituted or unsubstituted ring, and two or more of Q5 to Q8 are bonded to each other to form a substituted or unsubstituted ring.

According to another exemplary embodiment, the Q5 to Q8 are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted phenyl group, or adjacent groups are bonded to each other to form a substituted or unsubstituted ring, and two or more of Q5 to Q8 are bonded to each other to form a substituted or unsubstituted ring.

In another exemplary embodiment, Q5 to Q8 are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted phenyl group, or adjacent groups are bonded to each other to form a substituted or unsubstituted heterocycle, and two or more of Q5 to Q8 are bonded to each other to form a substituted or unsubstituted heterocycle.

According to an exemplary embodiment of the present specification, the Q5 and Q6; Q6 and Q7; Or Q7 and Q8 are bonded to each other to form a substituted or unsubstituted aromatic heterocycle, and the remaining substituents are hydrogen; Or a substituted or unsubstituted phenyl group.

According to another exemplary embodiment, the Q5 and Q6; Q6 and Q7; Or Q7 and Q8 are bonded to each other to form a substituted or unsubstituted benzofuran; Or a substituted or unsubstituted benzothiophene is formed, and the remaining substituents are hydrogen; Or a substituted or unsubstituted phenyl group.

In another exemplary embodiment, the Q5 and Q6; Q6 and Q7; Or Q7 and Q8 are bonded to each other to form an aryl group; Or benzofuran unsubstituted or substituted with a heterocyclic group; Or an aryl group; Or a heterocyclic group substituted or unsubstituted benzothiophene is formed, and the remaining substituents are hydrogen; Or a substituted or unsubstituted phenyl group.

According to another exemplary embodiment, the Q5 and Q6; Q6 and Q7; Or Q7 and Q8 are bonded to each other to form a phenyl group substituted with a 2-methylpropenyl group; Biphenyl group; Terphenyl group; Or benzofuran unsubstituted or substituted with a carbazole group; Or a phenyl group substituted with a 2-methylpropenyl group; Biphenyl group; Terphenyl group; Or a carbazole group substituted or unsubstituted benzothiophene is formed, and the remaining substituents are hydrogen; Or a substituted or unsubstituted phenyl group.

In the exemplary embodiment of the present specification, A'is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted C2 to C60 heterocyclic group.

In another exemplary embodiment, A'is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted C2 to C30 heterocyclic group.

According to an exemplary embodiment of the present specification, A'is a substituted or unsubstituted biphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted pyrimidine group; A substituted or unsubstituted dibenzofuran group; Or a substituted or unsubstituted dibenzothiophene group.

In another exemplary embodiment, A'is a biphenyl group unsubstituted or substituted with an aryl group or a heteroaryl group; Terphenyl group unsubstituted or substituted with an aryl group or a heteroaryl group; A pyrimidine group unsubstituted or substituted with an aryl group or a heteroaryl group; A dibenzofuran group unsubstituted or substituted with an aryl group or a heteroaryl group; Or a dibenzothiophene group unsubstituted or substituted with an aryl group or a heteroaryl group.

According to another exemplary embodiment, A'is a biphenyl group unsubstituted or substituted with at least one of a dibenzofuran group, a dibenzothiophene group, a carbazole group, and a dibenzoimidazothiazole group; A terphenyl group unsubstituted or substituted with at least one of carbazole group, dibenzothiophene group and dibenzofuran group; A pyrimidine group unsubstituted or substituted with a carbazole group; A dibenzofuran group unsubstituted or substituted with a dibenzofuran group; Or a dibenzothiophene group unsubstituted or substituted with a dibenzothiophene group.

In the exemplary embodiment of the present specification, p3 and p4 are 0 or 1.

According to an exemplary embodiment of the present specification, Q9 and Q10 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In another exemplary embodiment, Q9 and Q10 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted C2 to C60 heterocyclic group.

According to another exemplary embodiment, the Q9 and Q10 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted C2 to C30 heterocyclic group.

In another exemplary embodiment, Q9 and Q10 are the same as or different from each other, and each independently hydrogen; An aryl group having 6 to 60 carbon atoms unsubstituted or substituted with an aryl group or a heteroaryl group; Or a C2 to C60 heterocyclic group unsubstituted or substituted with an aryl group or a heteroaryl group.

According to another exemplary embodiment, the Q9 and Q10 are the same as or different from each other, and each independently hydrogen; A phenyl group unsubstituted or substituted with an aryl group or a heteroaryl group; A biphenyl group unsubstituted or substituted with an aryl group or a heteroaryl group; Terphenyl group unsubstituted or substituted with an aryl group or a heteroaryl group; A carbazole group unsubstituted or substituted with an aryl group or a heteroaryl group; A dibenzofuran group unsubstituted or substituted with an aryl group or a heteroaryl group; Dibenzothiophene group unsubstituted or substituted with an aryl group or a heteroaryl group; Or the following structure.

"는 결합부를 의미한다.In the above structure, "

"Means a coupling part.

In another exemplary embodiment, Q9 and Q10 are the same as or different from each other, and each independently hydrogen; A phenyl group unsubstituted or substituted with one or more of carbazole group, triphenylenyl group, dibenzothiophene group and dibenzofuran group; A biphenyl group unsubstituted or substituted with one or more of dibenzofuran group and dibenzothiophene group; Carbazole; Dibenzofuran group; Dibenzothiophene group; Or the following structure.

According to an exemplary embodiment of the present specification, p5 is 0 or 1.

In the exemplary embodiment of the present specification, Q11 is hydrogen.

According to an exemplary embodiment of the present specification, Q12 is a substituted or unsubstituted aryl group.

According to another exemplary embodiment, Q12 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

In another exemplary embodiment, Q12 is a substituted or unsubstituted triphenylenyl group.

According to another exemplary embodiment, Q12 is a triphenylenyl group.

In the exemplary embodiment of the present specification, Q13 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted C2 to C60 heterocyclic group.

In another exemplary embodiment, Q13 is an aryl group having 6 to 60 carbon atoms substituted or unsubstituted with a heteroaryl group; Or a C2-C60 heterocyclic group substituted or unsubstituted with an aryl group.

According to another exemplary embodiment, Q13 is a phenyl group unsubstituted or substituted with a heteroaryl group; A dibenzofuran group unsubstituted or substituted with an aryl group; Or a dibenzothiophene group unsubstituted or substituted with an aryl group.

In another exemplary embodiment, Q13 is a phenyl group substituted with a dibenzofuran group or a dibenzothiophene group; Dibenzofuran group; Or a dibenzothiophene group.

According to an exemplary embodiment of the present specification, Formulas F-1 to F-4 may be represented by any one of the following structures.

The organic light-emitting device may have, for example, a stacked structure as described below, but is not limited thereto.

(1) Anode/Hole Transport Layer/Light-Emitting Layer/Anode

(2) Anode/Hole injection layer/Hole transport layer/Light emitting layer/Anode

(3) Anode/hole injection layer/hole buffer layer/hole transport layer/light emitting layer/cathode

(4) Anode/hole transport layer/light-emitting layer/electron transport layer/cathode

(5) Anode/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode

(6) Anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/cathode

(7) Anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/electron injection layer/cathode

(8) Anode/Hole injection layer/Hole buffer layer/Hole transport layer/Light-emitting layer/Electron transport layer//Anode

(9) Anode/Hole injection layer/Hole buffer layer/Hole transport layer/Light emitting layer/Electron transport layer/Electron injection layer/Anode

(10) Anode/hole transport layer/electron suppression layer/light-emitting layer/electron transport layer/cathode

(11) Anode/hole transport layer/electron suppression layer/light emitting layer/electron transport layer/electron injection layer/cathode

(12) Anode/Hole injection layer/Hole transport layer/Electron suppression layer/Light-emitting layer/Electron transport layer/Anode

(13) Anode/hole injection layer/hole transport layer/electron suppression layer/light-emitting layer/electron transport layer/electron injection layer/cathode

(14) Anode/Hole Transport Layer/Light-Emitting Layer/Hole Suppression Layer/Electron Transport Layer/Anode

(15) Anode/Hole Transport Layer/Light-Emitting Layer/Hole Suppression Layer/Electron Transport Layer/Electron Injection Layer/Anode

(16) Anode/Hole injection layer/Hole transport layer/Light-emitting layer/Hole suppression layer/Electron transport layer/Anode

(17) Anode/Hole injection layer/Hole transport layer/Light emitting layer/Hole suppression layer/Electron transport layer/Electron injection layer/Anode

For example, the structure of an organic light emitting device according to an exemplary embodiment of the present specification is illustrated in FIGS. 1 and 2.

1 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a light emitting layer 3, and a cathode 4. In such a structure, the compound may be included in the emission layer.

FIG. 2 shows an example of an organic light emitting device comprising a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7 and a cathode 4 I did it. In such a structure, the compound may be included in the emission layer.

The anode 2 is an electrode for injecting holes, and may be any one of indium tin oxide (ITO), indium zinc oxide (IZO), or zinc oxide (ZnO) having a high work function. In addition, when the anode 2 is a reflective electrode, the anode 2 is a reflective layer made of any one of aluminum (Al), silver (Ag), or nickel (Ni) under a layer made of any one of ITO, IZO, or ZnO. It may further include.

The hole injection layer 5 may play a role of smoothly injecting holes from the anode 2 to the light emitting layer 3. The hole injection layer 5 may exist alone, mixed, or doped with a hole injection layer material known in the art. The thickness of the hole injection layer 5 may be 1 to 150 nm. Here, when the thickness of the hole injection layer 5 is 1 nm or more, there is an advantage of preventing deterioration of the hole injection characteristics, and when the thickness of the hole injection layer 5 is 150 nm or less, the thickness of the hole injection layer 5 is too thick to prevent the movement of holes. There is an advantage of preventing an increase in the driving voltage to improve. In addition, as the material for the hole injection layer, a hole injection material known in the art may be used. For example, in the group consisting of cupper phthalocyanine (CuPc), poly(3,4)-ethylenedioxythiophene (PEDOT), polyaniline (PANI) and NPD (N,N-dinaphthyl-N,N'-diphenyl benzidine) as a hole injection layer material Any one or more selected may be used, but the present invention is not limited thereto.

The hole transport layer 6 may serve to facilitate transport of holes. The hole transport layer 6 may exist alone, mixed, or doped with a hole transport layer material known in the art. In addition, as a material for the hole transport layer, a hole transport material known in the art may be used. For example, the hole transport layer 6 is NPD (N,N-dinaphthyl-N,N'-diphenylbenzidine), TPD (N,N'-bis-(3-methylphenyl)-N,N'-bis-(phenyl)- benzidine), s-TAD, and MTDATA(4,4',4"-Tris(N-3-methylphenyl-N-phenyl-amino)-triphenylamine), but not limited thereto. For example, as a hole transport layer material, triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino substituted chalcone derivatives, oxa And sol derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silasein derivatives, polysilane-based, aniline-based copolymers, and conductive polymer oligomers (especially thiophene oligomers).

A hole buffer layer may be additionally provided between the hole injection layer and the hole transport layer. The hole buffer layer may include a hole injection or transport material known in the art. Even when the hole buffer layer includes the compound of Formula 1, it may also be formed of only the compound of Formula 1, but may be formed in a state in which the compound of Formula 1 is mixed or doped with another host material.

An electron suppressing layer may be provided between the hole transport layer and the light emitting layer, and the compound of Formula 1 or a material known in the art may be used.

A hole inhibiting layer may be provided between the electron transport layer and the light emitting layer, and materials known in the art may be used.

The electron transport layer 7 may play a role of smoothly transporting electrons. Materials known in the art such as Alq ₃ (tris(8-hydroxyquinolino)aluminum), PBD, TAZ, spiro-PBD, BAlq, SAlq may be used. The thickness of the electron transport layer 7 may be 1 to 50 nm. Here, if the thickness of the electron transport layer 7 is 1 nm or more, there is an advantage of preventing deterioration of the electron transport characteristics, and if it is 50 nm or less, the thickness of the electron transport layer 7 is too thick to improve the movement of electrons. There is an advantage in that it is possible to prevent an increase in the dangerous driving voltage.

The electron injection layer may play a role of smoothly injecting electrons. Alq ₃ (tris(8-hydroxyquinolino)aluminum), PBD, TAZ, spiro-PBD, BAlq or SAlq known in the art, such as organic substances or complexes or metal compounds. Metal compounds include metal halides, and storage can be used, for example, can be used LiQ, LiF, NaF, KF, RbF, CsF, FrF, BeF _2, MgF _2, CaF _2, SrF _2, BaF ₂ and RaF ₂ and the like. The thickness of the electron injection layer may be 1 to 50 nm. Here, when the thickness of the electron injection layer is 1 nm or more, there is an advantage of preventing deterioration of the electron injection characteristics, and when the thickness of the electron injection layer is 50 nm or less, the thickness of the electron injection layer is too thick to increase the driving voltage to improve the movement of electrons. There is an advantage that can prevent it from rising.

The cathode 4 is an electron injection electrode, and may be made of magnesium (Mg), calcium (Ca), aluminum (Al), silver (Ag), or an alloy thereof having a low work function. Here, the cathode 4 may be formed to have a thickness thin enough to transmit light when the organic electroluminescent device has a front or double-sided light emitting structure, and when the organic electroluminescent device has a rear light emitting structure, it may reflect light. It can be formed as thick as possible.

According to another exemplary embodiment, the organic material layer may include two or more emission layers, and may include a charge generation layer including the compound of Formula 1 provided between the emission layers of the two layers. In this case, one of the emission layers emits blue light and the other emits yellow light, thereby manufacturing an organic light emitting device that emits white light. One or more organic material layers such as the above-described hole injection layer, hole buffer layer, hole transport layer, electron suppression layer, hole suppression layer, electron transport layer, and electron injection layer are further between the emission layer and the anode or the cathode, and between the emission layer and the charge generation layer. Can be included. 3 includes a substrate 1, an anode 2 and a cathode 4, and between the anode and the cathode, hole injection layers 5a and 5b, hole transport layers 6a and 6b, and light emitting layers 3a and 3b And two units including electron transport layers 8a and 8b, and an example of an organic light-emitting device in which a charge generation layer 9 is provided between the units.

As the light-emitting material, a material capable of emitting light in a visible region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency against fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); Carbazole-based compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compound; Benzoxazole, benzthiazole, and benzimidazole-based compounds; Poly(p-phenylenevinylene) (PPV)-based polymer; Spiro compounds; Polyfluorene, rubrene, and the like, but are not limited thereto.

The organic light emitting device according to the present invention may be a top emission type, a bottom emission type, or a double-sided emission type depending on the material used.

The manufacturing method of the compound of Formula 1 and the manufacturing of an organic light emitting device using the same will be described in detail in the following examples. However, the following examples are for illustrating the present invention, and the scope of the present invention is not limited thereto.

< Manufacturing example >

The method of preparing the material of the present invention starts from a reaction of introducing various types of aryl groups from a heteroaryl group substituted with two chlorine as follows. Selectively introducing arylboronic acid to one of the two chlorines of the heteroaryl group, replacing the aryl group with a linker and introducing biscarbazole to the remaining chlorine, or directly introducing biscarbazole to the chlorine, and finally the compound of the specific example Were synthesized.

Manufacturing example 1-1: Synthesis of compound 1-A

[Reaction Scheme 1-1]

30 g (150.7 mmol) of 2,3-dichloroquinoxaline, 150.7 mmol of phenylboronic acid, 450 mL of tetrahydrofuran, and 150 mL of water were mixed and heated to 60°C. 452.1 mmol of potassium carbonate and 1.5 mmol of tetrakistriphenylphosphine palladium were added, followed by stirring in a reflux state for 3 hours. After the reaction, the reaction solution returned to room temperature was extracted, ethanol was added to the organic layer, and the precipitate was washed sequentially with pure water and ethanol. This solid was recrystallized twice with toluene/hexane to obtain 32.6 g of compound 1-A (yield 90%).

MS[M+H]+ = 241

Manufacturing example 1-2: synthesis of compound 1-B

[Scheme 1-2]

30 g (150.7 mmol) of 2,3-dichloroquinoxaline, 150.7 mmol of (2-cyanophenyl) boronic acid, 450 mL of tetrahydrofuran, 150 mL of water were mixed, and heated to 60°C. 452.1 mmol of potassium carbonate and 1.5 mmol of tetrakistriphenylphosphine palladium were added, followed by stirring in a reflux state for 3 hours. After the reaction, the reaction solution returned to room temperature was extracted, ethanol was added to the organic layer, and the precipitate was washed sequentially with pure water and ethanol. This solid was recrystallized twice from toluene/hexane to obtain 36.8 g of compound 1-B (yield 92%).

MS[M+H]+ = 266

Manufacturing example 1-3: Synthesis of Compound 1-C

[Scheme 1-3]

30 g (150.7 mmol) of 2,3-dichloroquinoxaline, 150.7 mmol of (4-cyanophenyl) boronic acid, 450 mL of tetrahydrofuran, 150 mL of water were mixed, and heated to 60°C. 452.1 mmol of potassium carbonate and 1.5 mmol of tetrakistriphenylphosphine palladium were added, followed by stirring in a reflux state for 3 hours. After the reaction, the reaction solution returned to room temperature was extracted, ethanol was added to the organic layer, and the precipitate was washed sequentially with pure water and ethanol. This solid was recrystallized twice with toluene/hexane to obtain 37.2 g of compound 1-C (yield 93%).

MS[M+H]+ = 266

Manufacturing example 1-4: Synthesis of compound 1-D

[Scheme 1-4]

33.7 g (150.7 mmol) of 2,3-dichloroquinoxaline-6-carbonitrile, 150.7 mmol of (2-cyanophenyl) boronic acid, 450 mL of tetrahydrofuran, 150 mL of water were mixed and heated to 60 °C do. 452.1 mmol of potassium carbonate and 1.5 mmol of tetrakistriphenylphosphine palladium were added, followed by stirring in a reflux state for 3 hours. After the reaction, the reaction solution returned to room temperature was extracted, ethanol was added to the organic layer, and the precipitate was washed sequentially with pure water and ethanol. This solid was recrystallized twice with toluene/hexane to obtain 38.5 g of compound 1-D (yield 88%).

MS[M+H]+ = 291

Manufacturing example 1-5: Synthesis of compound 1-E

[Scheme 1-5]

30.1 g (150.7 mmol) of 2,3-dichloropyrido[2,3-b]pyrazine, 150.7 mmol of phenylboronic acid, 450 mL of tetrahydrofuran, 150 mL of water were mixed, and heated to 60°C. 452.1 mmol of potassium carbonate and 1.5 mmol of tetrakistriphenylphosphine palladium were added, followed by stirring in a reflux state for 3 hours. After the reaction, the reaction solution returned to room temperature was extracted, ethanol was added to the organic layer, and the precipitate was washed sequentially with pure water and ethanol. This solid was recrystallized twice from toluene/hexane to obtain 31.7 g of compound 1-E (yield 87%).

MS[M+H]+ = 242

Manufacturing example 2-1: Synthesis of compound 2-A

[Scheme 2-1]

1-A 16 g (66.5 mmol), 4-fluorophenylboronic acid 66.5 mmol, tetrahydrofuran 210 mL, and water 70 mL were mixed and heated to 60°C. 199.5 mmol of potassium carbonate and 0.6 mmol of tetrakistriphenylphosphine palladium were added, followed by stirring in a reflux state for 3 hours. After the reaction, the reaction solution returned to room temperature was extracted, ethanol was added to the organic layer, and the precipitate was washed sequentially with pure water and ethanol. This solid was recrystallized twice with toluene/hexane to obtain 18.2 g of compound 2-A (yield 91%).

MS[M+H]+ = 301

Manufacturing example 2-2: Synthesis of compound 2-B

[Reaction Scheme 2-2]

1-A 16 g (66.5 mmol), (3-cyano-4-fluorophenyl) boronic acid was mixed with 66.5 mmol, 210 mL of tetrahydrofuran, and 70 mL of water, and heated to 60°C. 199.5 mmol of potassium carbonate and 0.6 mmol of tetrakistriphenylphosphine palladium were added, followed by stirring in a reflux state for 3 hours. After the reaction, the reaction solution returned to room temperature was extracted, ethanol was added to the organic layer, and the precipitate was washed sequentially with pure water and ethanol. This solid was recrystallized twice with toluene/hexane to obtain 19.4 g of compound 2-B (yield 90%).

MS[M+H]+ = 326

Manufacturing example 3-1: Synthesis of compound 9

[Reaction Scheme 3-1]

1-A 10 g (41.5 mmol), 9-phenyl-9H,9'H-3,3'-bicarbazole 41.5 mmol was completely dissolved in 100 mL of toluene, and sodium-tert-butoxide 49.8 mmol was added, After adding 0.41 mmol of tetrakistriphenylphosphine palladium, the mixture was heated and stirred at 80°C for 6 hours. The temperature was lowered to room temperature, filtered to remove salt, concentrated under reduced pressure, and purified by recrystallization with toluene/ethanol (1:1) by column with tetrahydrofuran:hexane = 1:5, and 21.6 g of 9 was obtained (yield 85 %).

MS[M+H]+ = 613

Manufacturing example 3-2: Synthesis of compound 1

[Reaction Scheme 3-2]

1-B 11 g (41.5 mmol), 9-phenyl-9H,9'H-3,3'-bicarbazole 41.5 mmol was completely dissolved in toluene 100 mL, and sodium-tert-butoxide 49.8 mmol was added, After adding 0.41 mmol of tetrakistriphenylphosphine palladium, the mixture was heated and stirred at 80°C for 6 hours. After lowering the temperature to room temperature and filtering to remove salt, it was concentrated under reduced pressure and purified by recrystallization with toluene/ethanol (weight ratio, 1:1) by column with tetrahydrofuran:hexane = 1:5 (weight ratio), and 1 to 21.4 g (yield 81%) was obtained.

MS[M+H]+ = 638

Manufacturing example 3-3: Synthesis of compound 3

[Reaction Scheme 3-3]

1-C 11 g (41.5 mmol), 9-phenyl-9H,9'H-3,3'-bicarbazole 41.5 mmol was completely dissolved in 100 mL of toluene, and sodium-tert-butoxide 49.8 mmol was added, After adding 0.41 mmol of tetrakistriphenylphosphine palladium, the mixture was heated and stirred at 80°C for 6 hours. The temperature was lowered to room temperature, filtered to remove salt, concentrated under reduced pressure, and purified by recrystallization with toluene/ethanol (1:1) by column with tetrahydrofuran:hexane = 1:5, and 23.0 g of 3 was obtained (yield 87 %).

MS[M+H]+ = 638

Manufacturing example 3-4: Synthesis of compound 2

[Scheme 3-4]

1-D 12 g (41.5 mmol), 9-phenyl-9H,9'H-3,3'-bicarbazole 41.5 mmol was completely dissolved in 100 mL of toluene, and sodium-tert-butoxide 49.8 mmol was added, After adding 0.41 mmol of tetrakistriphenylphosphine palladium, the mixture was heated and stirred at 80°C for 6 hours. The temperature was lowered to room temperature, filtered to remove salt, concentrated under reduced pressure, and purified by recrystallization with toluene/ethanol (1:1) by column with tetrahydrofuran:hexane = 1:5, and 22.5 g of 2 was obtained (yield 82 %).

MS[M+H]+ = 663

Manufacturing example 3-5: Synthesis of compound 10

[Scheme 3-5]

1-E 10 g (41.5 mmol), 9-phenyl-9H,9'H-3,3'-bicarbazole 41.5 mmol was completely dissolved in 100 mL of toluene, and sodium-tert-butoxide 49.8 mmol was added, After adding 0.41 mmol of tetrakistriphenylphosphine palladium, the mixture was heated and stirred at 80°C for 6 hours. The temperature was lowered to room temperature, filtered to remove salt, concentrated under reduced pressure, and purified by recrystallization with toluene/ethanol (1:1) by column with tetrahydrofuran:hexane = 1:5, and 20.3 g of 10 was obtained (yield 80 %).

MS[M+H]+ = 614

Manufacturing example 3-6: Synthesis of compound 13

[Scheme 3-6]

2-A 12.5 g (41.5 mmol), 9-phenyl-9H,9'H-3,3'-bicarbazole 41.5 mmol was completely dissolved in 100 mL of toluene, and sodium-tert-butoxide 49.8 mmol was added, After adding 0.41 mmol of tetrakistriphenylphosphine palladium, the mixture was heated and stirred at 80°C for 6 hours. The temperature was lowered to room temperature, filtered to remove salt, concentrated under reduced pressure, and purified by recrystallization from toluene/ethanol (1:1) by column with tetrahydrofuran:hexane = 1:5, and 26.3 g of 13 was obtained (yield 92 %).

MS[M+H]+ = 689

Manufacturing example 3-7: Synthesis of compound 20

[Scheme 3-7]

2-B 13.5 g (41.5 mmol), 9-phenyl-9H,9'H-3,3'-bicarbazole 41.5 mmol was completely dissolved in 100 mL of toluene, and sodium-tert-butoxide 49.8 mmol was added, After adding 0.41 mmol of tetrakistriphenylphosphine palladium, the mixture was heated and stirred at 80°C for 6 hours. The temperature was lowered to room temperature, filtered to remove salt, concentrated under reduced pressure, and purified by recrystallization with toluene/ethanol (1:1) by column with tetrahydrofuran:hexane = 1:5, and 26.9 g of 20 was obtained (yield 91 %).

MS[M+H]+ = 714

In the above reaction scheme, various substituents were introduced in the remaining portions except for 9-phenyl-9H,9'H-3,3'-bicarbazole to synthesize the materials of the specific embodiments.

< Experimental example 1>

In this experimental example, an organic light-emitting device was manufactured by including Formula 1 according to an exemplary embodiment of the present specification in a light emitting layer with a host material (m-CBP) having a triplet value of 2.5 eV or more, and characteristics were evaluated.

A glass substrate coated with a thin film of ITO (indium tin oxide) having a thickness of 1,000Å was put in distilled water dissolved in a detergent and washed with ultrasonic waves. In this case, Fischer Co. product was used as a detergent, and distilled water secondarily filtered with a filter made by Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, it was repeated twice with distilled water to perform ultrasonic cleaning for 10 minutes. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator. Each thin film was stacked on the prepared ITO transparent electrode with a vacuum degree of 5.0 占10-4 Pa by vacuum evaporation. First, hexaazatriphenylene (HAT) was thermally vacuum deposited to a thickness of 500Å on ITO to form a hole injection layer.

A hole transport layer was formed by vacuum deposition of the following compound 4-4'-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (NPB) (300Å), which is a material that transports holes on the hole injection layer. I did.

Compound N-([1,1'-bisphenyl]-4-yl)-N-(4-(11-([1,1'-biphenyl]-4-yl) with a film thickness of 100Å on the hole transport layer )-11H-benzo[a]carbazole-5-yl)phenyl)-[1,1'-biphenyl]-4-amine (EB1) (100Å) was vacuum deposited to form an electron blocking layer.

Subsequently, m-CBP and 4CzIPN were vacuum-deposited on the electron blocking layer at a weight ratio of 70:30 with a thickness of 300Å as shown below to form a light emitting layer.

A hole blocking layer was formed by vacuum depositing compound HB1 on the emission layer with a thickness of 100 Å.

Compound ET1 and compound LiQ (Lithium Quinolate) were vacuum-deposited at a weight ratio of 1:1 on the hole blocking layer to form an electron injection and transport layer with a thickness of 300Å. Lithium fluoride (LiF) in a thickness of 12 Å and aluminum in a thickness of 2,000 Å were sequentially deposited on the electron injection and transport layer to form a negative electrode.

Was maintained at the deposition rate was 0.4 ~ 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was 0.3Å / sec, aluminum is deposited at a rate of 2Å / sec, the degree of vacuum upon deposition ⅹ10 2 ^-7 The organic light emitting device was manufactured by maintaining ~ 5 x10 ^-6 torr.

Experimental example 1-1 to 1-7

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that the compound of Table 1 was used instead of the compound 4CzIPN in Experimental Example 1.

Comparative example 1-1 to 1-2

An organic light-emitting device was manufactured in the same manner as in Experimental Example 1, except that compounds of the following T1 to T2 were used instead of the compound 4CzIPN in Experimental Example 1.

When a current was applied to the organic light-emitting devices manufactured according to Experimental Examples 1-1 to 1-7 and Comparative Examples 1-1 to 1-2, the results shown in Table 1 were obtained.

division compound
(Luminescent layer) Voltage
(V@10mA/cm ² ) efficiency
(cd/A@10mA/cm ² ) Color coordinates
(x,y) Experimental Example 1 4CzIPN 4.8 21 (0.34, 0.62) Experimental Example 1-1 Compound 1 3.9 29 (0.33, 0.63) Experimental Example 1-2 Compound 2 4.1 29 (0.34, 0.63) Experimental Example 1-3 Compound 3 4.1 30 (0.33, 0.64) Experimental Example 1-4 Compound 9 4.0 29 (0.33, 0.65) Experimental Example 1-5 Compound 10 4.1 28 (0.34, 0.61) Experimental Example 1-6 Compound 13 4.0 30 (0.32, 0.62) Experimental Example 1-7 Compound 20 3.9 32 (0.33, 0.64) Comparative Example 1-1 T1 5.3 15 (0.35, 0.65) Comparative Example 1-2 T2 5.2 14 (0.39, 0.58)

As shown in Table 1, the devices of Experimental Examples 1-1 to 1-7 using the compound having the structure of Formula 1 as the core had lower voltage and increased efficiency than the device using the compound 4CzIPN in Experimental Example 1. I got the result.

In addition, when comparing the devices of Comparative Examples 1-1 to 1-2, it can be seen that the biscarbazole structure of Formula 1 has improved characteristics in terms of voltage and efficiency than the case of carbazole substituted or unsubstituted in the core.

As shown in the results of Table 1, it was confirmed that the compound according to the present invention has excellent light-emitting ability and high color purity, so that it can be applied to a delayed fluorescent organic light-emitting device.

Although the preferred experimental examples of the present invention have been described above, the present invention is not limited thereto, and it is possible to perform various modifications within the scope of the claims and the detailed description of the invention, and this also belongs to the scope of the invention. .

1: substrate
2: anode
3: light emitting layer
4: cathode
5: hole injection layer
6: hole transport layer
7: electron transport layer

Claims (7)

Compound represented by the following formula 3:
[Formula 3]

In Formula 3,
L is a phenylene group substituted with a cyano group,
X5 to X8 are each independently CR',
R is a substituted or unsubstituted aryl group,
R'is hydrogen. delete delete The method according to claim 1,
The compound represented by Formula 3 is a compound selected from the following structure:

. An organic light-emitting device comprising a first electrode, a second electrode, and one or more organic material layers disposed between the first electrode and the second electrode, wherein at least one of the organic material layers is defined in any one of claims 1 and 4 Organic light emitting device comprising the compound according to. The method of claim 5,
The organic material layer includes an emission layer,
The emission layer includes a host and a dopant,
The dopant is an organic light-emitting device, characterized in that the compound according to any one of claims 1 and 4. The method of claim 5,
The organic material layer includes an emission layer,
The emission layer includes a host, a sensitizer, and a fluorescent emitter,
The sensitizer is a compound according to any one of claims 1 and 4,
The organic light-emitting device, characterized in that the sensitizer has a delayed fluorescence characteristic of less than ΔE _st 0.2eV.

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