KR20200068393A - Compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention provides a compound of chemical formula 1 and an organic light emitting element comprising the same. In the chemical formula 1: Cz is a substituted or unsubstituted carbazolyl group; any two of X_1 to X_5 are N, and the rest thereof are CR; at least one of R is a cyano group; and the remaining substituents are the same as or different from each other, and are independently a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group.

Description

COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME

The present invention relates to a compound, more specifically a heterocyclic compound and an organic light emitting device including the same.

Organic light emitting diode (Organic Light Emitting Device, OLED) is a self-emission type device with wide viewing angle and excellent contrast, fast response time, excellent brightness, driving voltage and response speed characteristics, and multicolorization. have. A typical organic light-emitting diode may include an anode and a cathode and an organic layer interposed between the anode and the cathode. The organic layer may include a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, an electron transport layer and an electron injection layer. When a voltage is applied between the anode and the cathode, holes injected from the anode move to the light emitting layer via the hole transport layer, and electrons injected from the cathode move to the light emitting layer via the electron transport layer. Carriers, such as holes and electrons, recombine in the light emitting layer region to generate an exiton, and light is generated as the exciton changes to the ground state. In general, excitons generated when driving an organic light-emitting diode are randomly generated in a singlet state of 25% and triplet state of 75%, and in the case of a fluorescent light-emitting material, only 25% of singlet state light emission is generated by excitons. The internal quantum efficiency will remain at the maximum level of 25%. In order to improve these properties, iridium or platinum complexes that can use triplet energy are used, and it is known to possess excellent quantum efficiency properties. However, these materials are expensive, and their application is limited due to the instability of the blue light emitting material.

Patent Publication No. 10-2010-0082986

The problem to be solved by the present invention is a thermally activated delayed fluorescence (TADF) material capable of improving the actual quantum efficiency as it is possible to more efficiently transfer energy from the triplet state to the singlet state and the same. In providing an organic light emitting device.

An exemplary embodiment of the present invention provides a compound represented by Formula 1 below:

[Formula 1]

In Chemical Formula 1,

Cz is a substituted or unsubstituted carbazolyl group,

2 of X ₁ to X ₅ are N, the rest are CR,

At least one of R is a cyano group, the remaining substituents are the same or different, and each independently substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In addition, another exemplary embodiment of the present invention includes a first electrode, a second electrode, and one or more organic material layers provided between the first electrode and the second electrode, and at least one of the organic material layers is represented by Chemical Formula 1 It provides an organic light emitting device comprising a compound.

The compound according to the exemplary embodiments of the present invention relates to an organic light emitting device, and relates to a compound represented by Chemical Formula 1 and an organic light emitting device including the same. By including the compound represented by Chemical Formula 1 in one or more organic layers, preferably a light emitting layer and an electron transporting material, characteristics such as light emission efficiency, driving voltage, and lifetime of the device can be improved.

Such a compound may be used as a hole injection, hole transport material, host material, or electron injection, transport material for an organic electroluminescent device. The organic light emitting device using the same has excellent electrochemical and thermal stability, and thus has excellent life characteristics and high luminous efficiency even at a low driving voltage.

In addition, the present invention has a high photoluminescence quantum efficiency (Photoluminescence Quantum Yield, PLQY), and controls the overlap of HOMO and LUMO, singlet energy (Singlet energy, S1) and triplet energy (Triplet energy, T1) small Compounds exhibiting an energy gap (Δ EST ) can be provided.

1 is a view schematically showing a stacked structure of an organic light emitting device according to an exemplary embodiment of the present invention.

Hereinafter, the present invention will be described in detail.

In the present specification, "substituted or unsubstituted"deuterium;-CN; C ₁ to C ₆₀ alkyl group; C _{2 To} C ₆₀ Alkenyl group; C _{2 To} C ₆₀ Alkynyl group; C ₃ to C ₆₀ cycloalkyl group; C ₂ to C ₆₀ heterocycloalkyl group; C ₆ to C ₆₀ aryl group; And C ₂ to C ₆₀ substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl groups, or substituted or unsubstituted with two or more of the substituents attached thereto, or a substituent linked with two or more substituents selected from the substituents. It means substituted or unsubstituted with. For example, "substituent to which two or more substituents are connected" may be a 9-phenylcarbazolyl group. That is, the 9-phenylcarbazolyl group may be a heteroaryl group or may be interpreted as a substituent to which a phenyl group and a carbazolyl group are connected. The substituent may be further substituted.

According to an exemplary embodiment of the present application, the "substituted or unsubstituted" is deuterium, -CN, C ₁ to C ₂₀ straight or branched chain alkyl group, C ₆ to C ₆₀ aryl group, and C ₂ to C ₆₀ It is substituted or unsubstituted with one or more substituents selected from the group consisting of heteroaryl groups.

According to an exemplary embodiment of the present application, the "substituted or unsubstituted" is deuterium, C ₁ to C ₁₀ straight or branched alkyl group, C ₆ to C ₃₀ aryl group, and C ₂ to C ₃₀ heteroaryl It is substituted or unsubstituted with one or more substituents selected from the group consisting of groups.

According to an exemplary embodiment of the present application, the "substituted or unsubstituted" is deuterium, C ₁ to C ₆ straight or branched alkyl group, C ₆ to C ₁₈ aryl group, and C ₂ to C ₁₅ heteroaryl It is substituted or unsubstituted with one or more substituents selected from the group consisting of groups.

According to an exemplary embodiment of the present application, the "substituted or unsubstituted" is deuterium, phenyl group, biphenyl group, naphthyl group, terphenyl group, anthracenyl group, phenanthrenyl group, fluorenyl group, pyridine group, pyrimidine group, tria It is substituted or unsubstituted with one or more substituents selected from the group consisting of true groups and carbazolyl groups.

The term "substitution" 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 to a position where the hydrogen atom is substituted, that is, a position where the substituent can be substituted, and when two or more are substituted , 2 or more substituents may be the same or different from each other.

In the present specification, the alkyl group includes a straight chain or branched chain having 1 to 60 carbon atoms, and may be further substituted by other substituents. Carbon number of the alkyl group may be 1 to 60, specifically 1 to 40, more specifically, 1 to 20. Specific examples are methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methylbutyl group, 1-ethyl Butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 3,3-dimethylbutyl Group, 2-ethylbutyl group, heptyl group, n-heptyl group, 1-methylhexyl group, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2 -Ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethylpropyl group, 1,1-dimethylpropyl group, isohexyl group, 2-methylpentyl group, 4- Methylhexyl group, 5-methylhexyl group, and the like, but is not limited thereto.

In the present specification, the alkenyl group includes a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. The alkenyl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 2 to 20 carbon atoms. Specific examples include vinyl group, 1-propenyl group, isopropenyl group, 1-butenyl group, 2-butenyl group, 3-butenyl group, 1-pentenyl group, 2-pentenyl group, 3-pentenyl group, 3-methyl-1 -Butenyl group, 1,3-butadienyl group, allyl group, 1-phenylvinyl-1-yl group, 2-phenylvinyl-1-yl group, 2,2-diphenylvinyl-1-yl group, 2-phenyl-2 -(Naphthyl-1-yl)vinyl-1-yl group, 2,2-bis(diphenyl-1-yl)vinyl-1-yl group, stilbenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the alkynyl group includes a straight or branched chain having 2 to 60 carbon atoms, and may be further substituted by other substituents. Carbon number of the alkynyl group may be 2 to 60, specifically 2 to 40, more specifically, 2 to 20.

In the present specification, the cycloalkyl group includes a monocyclic or polycyclic group having 3 to 60 carbon atoms, and may be further substituted by other substituents. Here, polycyclic means a group in which a cycloalkyl group is directly connected to or condensed with another ring group. Here, the other cyclic group may be a cycloalkyl group, but may be another kind of cyclic group, such as a heterocycloalkyl group, an aryl group, a heteroaryl group, and the like. The cycloalkyl group may have 3 to 60 carbon atoms, specifically 3 to 40 carbon atoms, and more specifically 5 to 20 carbon atoms. Specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, 3-methylcyclopentyl group, 2,3-dimethylcyclopentyl group, cyclohexyl group, 3-methylcyclohexyl group, 4-methylcyclohexyl group, 2 ,3-dimethylcyclohexyl group, 3,4,5-trimethylcyclohexyl group, 4-tert-butylcyclohexyl group, cycloheptyl group, cyclooctyl group, and the like, but is not limited thereto.

In the present specification, the heterocycloalkyl group includes O, S, Se, N or Si as a hetero atom, monocyclic or polycyclic having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, polycyclic means a group in which a heterocycloalkyl group is directly connected to or condensed with another ring group. Here, the other cyclic group may be a heterocycloalkyl group, but may be another kind of cyclic group, for example, a cycloalkyl group, an aryl group, a heteroaryl group. The heterocycloalkyl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 3 to 20 carbon atoms.

In the present specification, the aryl group includes 6 to 60 carbon atoms or a monocyclic ring, and may be further substituted by other substituents. Here, polycyclic means a group in which an aryl group is directly connected or condensed with another ring group. Here, the other ring group may be an aryl group, but may be another kind of ring group, such as a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group, and the like. The number of carbon atoms of the aryl group may be 6 to 60, specifically 6 to 40, and more specifically 6 to 25. Specific examples of the aryl group include a phenyl group, biphenyl group, triphenyl group, naphthyl group, anthracenyl group, chrysenyl group, phenanthrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, phenenyl group, pyre Neil group, tetrasenyl group, pentasenyl group, fluorenyl group, indenyl group, acenaphthylenyl group, benzofluorenyl group, spirobifluorenyl group, 2,3-dihydro-1H-indenyl group, and condensed ring groups thereof And the like, but are not limited thereto.

In the present specification, the heteroaryl group includes at least one hetero atom selected from the group consisting of S, O, Se, N and Si, and includes a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and is added by another substituent. It can be substituted with. Here, the polycyclic group refers to a group in which a heteroaryl group is directly connected or condensed with another ring group. Here, the other ring group may be a heteroaryl group, but may be another type of ring group, for example, a cycloalkyl group, a heterocycloalkyl group, an aryl group, or the like. The heteroaryl group may have 2 to 60 carbon atoms, specifically 2 to 40 carbon atoms, and more specifically 3 to 25 carbon atoms. Specific examples of the heteroaryl group include pyridyl group, pyrrolyl group, pyrimidyl group, pyridazinyl group, furanyl group, thiophene group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, thiazolyl Group, isothiazolyl group, triazolyl group, furazanyl group, oxadiazolyl group, thiadiazolyl group, dithiazolyl group, tetrazolyl group, pyranyl group, thiopyranyl group, diazinyl group, oxazinyl group , Thiazinyl group, deoxynyl group, triazinyl group, tetrazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, isoquinazolinyl group, quinozolinyl group, naphthyridyl group, acridinyl group, phenanthridy Niyl group, imidazopyridinyl group, diazanaphthalenyl group, triazinden group, indolyl group, indolizinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiophene group, benzofuran group , Dibenzothiophene group, dibenzofuran group, carbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, phenazinyl group, dibenzosilol group, spirobi (dibenzosilol), dihydrophenazinyl group, Phenoxazinyl group, phenanthridyl group, imidazopyridinyl group, thienyl group, indolo[2,3-a]carbazolyl group, indolo[2,3-b]carbazolyl group, indolinyl group, 10, 11-dihydro-dibenzo[b,f]azepine group, 9,10-dihydroacridinyl group, phenanthrazinyl group, phenothiathiazinyl group, phthalazinyl group, naphthilidinyl group, phenanthrolinyl group, Benzo[c][1,2,5]thiadiazolyl group, 5,10-dihydrodibenzo[b,e][1,4]azasilinyl, pyrazolo[1,5-c]quinazolinyl group , Pyrido[1,2-b]indazolyl group, pyrido[1,2-a]imidazo[1,2-e]indolinyl group, 5,11-dihydroindeno[1,2-b ]Carbazolyl group, and the like, but is not limited thereto.

The compound according to an exemplary embodiment of the present invention may be represented by Chemical Formula 1.

More specifically, a compound having a structure in which a cyano group is directly substituted on a heterocycle containing 2 N and a carbazolyl group is substituted may exhibit excellent effects.

The compound represented by Chemical Formula 1 is a thermally active delayed fluorescence organic material, which compensates for the instability problem of the conventional luminescent material. In the thermally active delayed fluorescent organic material, the difference between the singlet state and the triplet state of the exciton is 0.3 eV or less, and in this case, the triplet state is transferred to the singlet state by heat corresponding to room temperature or device driving temperature. %.

In one embodiment of the present invention, Cz is deuterium, a straight or branched alkyl group having 1 to 6 carbon atoms, an aryl group having 6 to 20 carbon atoms, and at least one substituent selected from the group consisting of a heteroaryl group having 2 to 20 carbon atoms. It is a carbazolyl group unsubstituted or substituted with.

In one embodiment of the present invention, Cz is deuterium, a straight or branched alkyl group having 1 to 3 carbon atoms, an aryl group having 6 to 18 carbon atoms, and one or more substituents selected from the group consisting of a heteroaryl group having 2 to 18 carbon atoms. It is a carbazolyl group unsubstituted or substituted with.

In one embodiment of the present invention, Cz is a carbazolyl group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, an aryl group having 6 to 12 carbon atoms, and a heteroaryl group having 2 to 18 carbon atoms.

In one embodiment of the present invention, Cz is deuterium; Phenyl group; Biphenyl group; Triphenyl group; Naphthyl group; Anthracenyl group; Phenanthrenyl group; Triphenylenyl group; Fluorenyl group; Pyridine group; Pyrrol group; Pyrimidine group; Pyridazine group; Imidazole; Pyrazole group; Triazole group; Triazine group; Carbazolyl group; Tetrazole group; Diazine group; Isoquinoline group; Quinoline group; Quinol group; Quinazoline groups; Quinoxaline group; Acridine group; Phenanthridine group; Diazanaphthalene group; Indolescence; Benzimidazole; Benzocarbazole group; And a carbazolyl group unsubstituted or substituted with one or more substituents selected from the group consisting of phenazine groups.

In one embodiment of the present invention, Cz is deuterium; Phenyl group; Biphenyl group; Triphenyl group; Naphthyl group; Pyridine group; Pyrimidine group; Pyridazine group; Triazine group; Carbazolyl group; And it is a carbazolyl group unsubstituted or substituted with one or more substituents selected from the group consisting of diazinic groups.

In one embodiment of the present invention, Cz is a carbazolyl group unsubstituted or substituted with deuterium or phenyl groups.

In one embodiment of the present invention, Cz is represented by any one of the following Chemical Formulas 2-1 to 2-5.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

In Chemical Formulas 2-1 to 2-5,

A1 to A3 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 heteroaryl group,

n is an integer from 1 to 8, and when n is 2 or more, A1 is the same or different from each other,

m is an integer from 1 to 7, and when m is 2 or more, A2 is the same or different from each other,

는 카바졸릴기가 화학식 1에 연결되는 부위를 의미한다.

Means a site where the carbazolyl group is connected to Formula 1.

In one embodiment of the present invention, A1 to A3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

In one embodiment of the present invention, A1 to A3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 18 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 15 carbon atoms.

In one embodiment of the present invention, A1 to A3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted aryl group having 6 to 12 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 15 carbon atoms.

In one embodiment of the present invention, A1 to A3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Phenyl group; Biphenyl group; Naphthyl group; Pyridine group; Pimimidyl group; Or a carbazolyl group.

In one embodiment of the present invention, A1 to A3 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a phenyl group.

In one embodiment of the present invention, A1 is hydrogen or deuterium.

In one embodiment of the present invention, A2 is a phenyl group.

In one embodiment of the present invention, A3 is hydrogen or deuterium.

In one embodiment of the present invention, n is 1.

In one embodiment of the present invention, n is 8.

In one embodiment of the present invention, m is 1.

In one embodiment of the present invention, m is 7.

In one embodiment of the present invention, 2 of X ₁ to X ₅ are N, the rest are CR, at least one of R is a cyano group, and the remaining substituents are the same or different, and each independently substituted or Unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

는 하기 화학식 3-1 내지 화학식 3-5 중 어느 하나로 표시된다.In one embodiment of the present invention, the formula (1)

Is represented by any one of the following formulas 3-1 to 3-5.

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

In Formula 3-1, X ₃ to X ₅ are CR, at least one of R is a cyano group, and the remaining substituents are the same or different, and each independently substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

In Formula 3-2, X ₂ , X ₄ and X ₅ are CR, at least one of R is a cyano group, and the remaining substituents are the same or different, and each independently substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

In Formula 3-3, X ₂ , X ₃ and X ₅ are CR, at least one of R is a cyano group, and the remaining substituents are the same or different, and each independently substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

In Formula 3-4, X ₂ to X ₄ are CR, at least one of R is a cyano group, and the remaining substituents are the same or different, and each independently substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

In Formula 3-5, X ₁ , X ₄ and X ₅ are CR, at least one of R is a cyano group, and the remaining substituents are the same or different, and each independently substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

In one embodiment of the present invention, at least one of the R is a cyano group (-CN).

In one embodiment of the present invention, two of R are cyano groups.

In one embodiment of the present invention, the substituents other than the cyano group in R are the same or different, and each independently substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In one embodiment of the present invention, the substituents other than the cyano group in R are the same or different, and each independently substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

In one embodiment of the present invention, the substituents other than the cyano group among R are the same or different, and each independently substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

In one embodiment of the present invention, the substituents other than the cyano group in R are the same or different, and each independently substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 15 carbon atoms.

In one embodiment of the present invention, the substituents other than the cyano group in R are the same or different, and each independently substituted or unsubstituted aryl group having 6 to 13 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 15 carbon atoms.

In one embodiment of the present invention, the substituents other than the cyano group in R are the same or different, and each independently substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted triphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted anthracenyl group; A substituted or unsubstituted phenanthrenyl group; A substituted or unsubstituted triphenylenyl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted pyridine group; A substituted or unsubstituted pyrrole group; A substituted or unsubstituted pyrimidine group; A substituted or unsubstituted pyridazine group; A substituted or unsubstituted imidazole group; A substituted or unsubstituted pyrazole group; A substituted or unsubstituted triazole group; A substituted or unsubstituted triazine group; A substituted or unsubstituted carbazolyl group; A substituted or unsubstituted tetrazole group; A substituted or unsubstituted diazine group; A substituted or unsubstituted isoquinoline group; A substituted or unsubstituted quinoline group; A substituted or unsubstituted quinol group; A substituted or unsubstituted quinazoline group; A substituted or unsubstituted quinoxaline group; A substituted or unsubstituted acridine group; A substituted or unsubstituted phenanthridine group; A substituted or unsubstituted diazanaphthalene group; A substituted or unsubstituted indole group; A substituted or unsubstituted benzimidazole group; A substituted or unsubstituted benzocarbazole group; A substituted or unsubstituted phenazine group; A substituted or unsubstituted dibenzothiophene group; It is a substituted or unsubstituted dibenzofuranyl group.

In one embodiment of the present invention, the substituents other than the cyano group in R are the same or different, and each independently substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted triphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted fluorenyl group; A substituted or unsubstituted pyridine group; A substituted or unsubstituted pyrimidine group; A substituted or unsubstituted pyridazine group; A substituted or unsubstituted triazine group; A substituted or unsubstituted carbazolyl group; A substituted or unsubstituted diazine group; A substituted or unsubstituted dibenzothiophene group; It is a substituted or unsubstituted dibenzofuranyl group.

In one embodiment of the present invention, the substituents other than the cyano group in R are the same or different, and each independently substituted or unsubstituted phenyl group with an aryl group; A naphthyl group unsubstituted or substituted with an aryl group; A fluorenyl group unsubstituted or substituted with an aryl group; A pyridine group unsubstituted or substituted with an aryl group; A pyrimidine group unsubstituted or substituted with an aryl group; A pyridazine group unsubstituted or substituted with an aryl group; A carbazolyl group unsubstituted or substituted with an aryl group; Diazine group unsubstituted or substituted with an aryl group; A dibenzothiophene group unsubstituted or substituted with an aryl group; It is a dibenzofuranyl group unsubstituted or substituted with an aryl group.

In one embodiment of the present invention, the substituents other than the cyano group in R are the same or different, and each independently substituted or unsubstituted phenyl group with an aryl group; A carbazolyl group unsubstituted or substituted with an aryl group; Or a dibenzofuranyl group unsubstituted or substituted with an aryl group; Or a dibenzothiophene group unsubstituted or substituted with an aryl group.

In one embodiment of the present invention, the substituents other than the cyano group in R are the same or different, and each independently a phenyl group; A carbazolyl group unsubstituted or substituted with a phenyl group; Dibenzofuranyl group; Or dibenzothiophene group.

The compound according to the present invention was completed by confirming that the carbazolyl group can exhibit excellent luminescence properties by containing a cyano group together in a substituted N-containing hetero ring.

According to an exemplary embodiment of the present invention, the compound according to the present invention may be represented by at least one of the following compounds, but is not limited thereto.

In addition, by introducing various substituents to the structure of Formula 1, it is possible to synthesize a compound having intrinsic properties of the introduced substituents. For example, a hole injection layer material used in manufacturing an organic light emitting device, a hole transporting material, a light emitting layer material, a hole blocking layer material, an electron transporting layer material, or a substituent mainly used for an electron injection layer material may be introduced into the core structure, thereby in each organic material layer. Materials can be synthesized that meet the required conditions.

In addition, by introducing various substituents to the structure of Chemical Formula 1, it is possible to finely adjust the energy band gap, on the other hand, to improve the properties at the interface between organic substances, and to use various materials.

On the other hand, the compound represented by Formula 1 has a high glass transition temperature (Tg) and excellent thermal stability. This increase in thermal stability is an important factor providing driving stability to the device.

The compound according to the exemplary embodiment of the present invention can be prepared by a multi-step chemical reaction. Some intermediate compounds are prepared first, and compounds of Formula 1 can be prepared from those intermediate compounds. More specifically, a method for preparing a compound according to an exemplary embodiment of the present invention may be prepared as in the Examples described later.

Another exemplary embodiment of the present invention provides an organic light emitting device including the compound represented by Chemical Formula 1.

The organic light emitting device including the compound according to the present invention has an effect of excellent light emission efficiency even at a low driving voltage.

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

Specifically, the organic light emitting device according to an exemplary embodiment of the present invention includes a first electrode, a second electrode, and one or more organic material layers provided between the first electrode and the second electrode, and one layer of the organic material layer The above includes the compound represented by Formula 1 above.

1 illustrates a stacking order of an electrode and an organic material layer of an organic light emitting device according to an exemplary embodiment of the present invention. However, the scope of the present application is not intended to be limited by the above-described drawings, and the structure of the organic light emitting device known in the art may be applied to the present application.

Referring to FIG. 1, an organic light emitting device in which a first electrode, a hole injection layer, a light emitting layer, and a second electrode are sequentially stacked on a substrate is illustrated. However, it is not limited to such a structure. Specifically, the compound of Formula 1 may be included in the light emitting layer in the structure of FIG. 1.

Specifically, the organic light emitting device includes: a substrate/first electrode/light emitting layer/second electrode; A substrate/first electrode/hole injection layer/light emitting layer/second electrode; A substrate/first electrode/hole transport layer/light emitting layer/second electrode; A substrate/first electrode/hole injection layer/hole transport layer/light emitting layer/second electrode; A substrate/first electrode/light emitting layer/electron transport layer/second electrode; A substrate/first electrode/light emitting layer/electron injection layer/second electrode; A substrate/first electrode/light emitting layer/hole blocking layer/second electrode; A substrate/first electrode/light emitting layer/electron transport layer/electron injection layer/second electrode; A substrate/first electrode/light emitting layer/hole blocking layer/electron transport layer/second electrode; It may have a structure of a substrate/first electrode/light emitting layer/hole blocking layer/electron transport layer/electron injection layer/second electrode, etc., wherein at least one layer of organic material between the first electrode and the second electrode, such as a hole injection layer, The hole transport layer, the light emitting layer, the hole blocking layer, the electron transport layer, or the electron injection layer may include the compound of Formula 1 above. More specifically, the compound of Formula 1 may be used as a material of a light emitting layer, a hole blocking layer, an electron transport layer, or an electron injection layer in a device having the above structure.

In another exemplary embodiment, the organic light emitting device may include a charge generating layer. For example, the organic light emitting device may include two or more light emitting units including a light emitting layer, and a charge generating layer may be provided between two adjacent light emitting units. As another example, the organic light emitting device includes one or more light emitting units, and a charge generating layer may be provided between the light emitting unit and the first electrode, or between the light emitting unit and the second electrode.

The light emitting unit may be formed of only a light emitting layer, and if necessary, may further include one or more organic material layers such as a hole injection layer, a hole transport layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

For example, the organic light emitting device includes: a substrate/first electrode/light emitting unit/charge generating layer (n type)/charge generating layer (p type)/light emitting unit/second electrode; A substrate/first electrode/charge generating layer (n type)/charge generating layer (p type)/light emitting unit/second electrode; It may have a structure such as a substrate/first electrode/light emitting unit/charge generating layer (n type)/charge generating layer (p type)/second electrode, where the number of light emitting units is 2 or 3 or more as required Can be included. The light emitting unit includes a light emitting layer, and further includes one or more layers of a hole injection layer, a hole transport layer, a hole blocking layer, an electron transport layer, and an electron injection layer, if necessary.

The organic light emitting device according to an exemplary embodiment of the present application includes at least one layer of a hole blocking layer, an electron injection layer, and an electron transport layer as the organic material layer, and at least one layer of the hole blocking layer, the electron injection layer, and the electron transport layer is the Compounds.

The organic light emitting device according to the exemplary embodiment of the present application includes a light emitting layer as the organic material layer, and the light emitting layer contains the compound.

According to an exemplary embodiment of the present application, the light emitting layer including the compound is characterized in that the blue light emitting layer.

When the compound of Formula 1 is used as a light emitting layer material, the compound of Formula 1 may serve as a light emitting host, in which case the light emitting layer further includes a dopant. As an example, the compound of Formula 1 may be used as a p-type or n-type phosphorescent host.

According to an exemplary embodiment of the present invention, the organic light emitting device including the compound of Formula 1 may exhibit characteristics of HF (hyper fluorescence), wherein the compound of Formula 1 is a host and/or a dopant material. It can be used, but is not limited thereto.

Further, according to an exemplary embodiment of the present invention, the compound of Formula 1 may be used as a light emitting dopant in the light emitting layer of the organic light emitting device. When the compound according to the present invention is used as a light-emitting dopant, it is possible to exhibit an effect of improving quantum efficiency excellently as the transition from the triplet excited state to the singlet excited state is possible more efficiently. In addition, it can exhibit an effect of implementing various emission colors such as red, green, and blue. At this time, a known material can be used as the luminescent host material, for example, mCP(N,N-dicarbazolyl-3,5-benzene), Alq3, CBP(4,4'-N,N'-dicarbazol-biphenyl) , 9,10-di(naphthalene-2-yl)anthracene, TPBI(1,3,5-tris(N-phenylbenzimidazole-2-yl)benzene), TBADN(3-tert-butyl-9,10-di( naphthele-2-yl)anthracene), mCBP(3,3'-bis(carbazol-9-yl)biphenyl), and the like, but is not limited thereto.

In one embodiment, the organic light emitting device including the compound of Formula 1 may exhibit the properties of TADF, wherein the compound of Formula 1 is used as a dopant, and mCBP can be used as a host material, but is not limited thereto. no.

The organic light emitting device according to the present specification may be manufactured by materials and methods known in the art, except that the compound represented by Chemical Formula 1 is included in at least one layer of the organic material layer.

Materials that may be included in the organic thin film layer in addition to the compound represented by Chemical Formula 1 include, for example, a fluorescent dopant material, and if the fluorescent dopant material can be applied to an organic light emitting device, it is not particularly limited. For example, TBPe(2,5,8,11-tetra-tert-butylperylene), TTPA(9,10-Bis [N,N-di-(p-tolyl)-amino]anthracene), TBRb(2,8-di -tert-butyl5,11-bis(4-tert-butylphenyl)-6,12-diphenyltetracene) and DBP (tetraphenyl-dibenzoperiflanthene).

The compound represented by Chemical Formula 1 may independently constitute one or more layers of the organic material layer of the organic light emitting device. However, if necessary, an organic material layer may be formed by mixing with other materials.

In the organic light emitting device according to an exemplary embodiment of the present application, materials other than the compound of Formula 1 are illustrated below, but these are for illustration only and are not intended to limit the scope of the present application, and are known in the art Materials can be replaced.

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

As the anode material, materials having a relatively large work function may be used, and a transparent conductive oxide, metal, or conductive polymer may be used. Specific examples of the anode material 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); A combination of metal and oxide such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

As the cathode material, materials having a relatively low work function may be used, and a metal, metal oxide, or conductive polymer may be used. Specific examples of the cathode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; There is a multilayer structure material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

As the hole injection material, a known hole injection material may be used, for example, a phthalocyanine compound such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or Advanced Material, 6, p.677 (1994). Starburst amine derivatives, such as tris(4-carbazoyl-9-ylphenyl)amine (TCTA), 4,4',4"-tri[phenyl(m-tolyl)amino]triphenylamine (m- MTDATA), 1,3,5-tris[4-(3-methylphenylphenylamino)phenyl]benzene (m-MTDAPB), polyaniline/dodecylbenzenesulfonic acid (Polyaniline/Dodecylbenzenesulfonic acid) or poly( 3,4-ethylenedioxythiophene)/poly(4-ethylenedioxythiophene)/Poly(4-styrenesulfonate)), polyaniline/Camphor sulfonic acid or polyaniline/ Polyaniline/Poly(4-styrene-sulfonate) can be used.

As the hole transport material, a pyrazoline derivative, an arylamine-based derivative, a stilbene derivative, a triphenyldiamine derivative, etc. may be used, and a low molecular weight or high molecular weight material may also be used.

Electron transport materials include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, fluorenone Derivatives, diphenyldicyanoethylene and derivatives thereof, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and derivatives thereof, and the like may be used, as well as low molecular weight materials and high molecular weight materials.

As the electron injection material, for example, LiF is typically used in the art, but the present application is not limited thereto.

As the light emitting material other than the compound of Formula 1, red, green, or blue light emitting materials may be used, and if necessary, two or more light emitting materials may be mixed and used. Further, a fluorescent material may be used as the light emitting material, but it may also be used as a phosphorescent material. As the light emitting material, a material that combines holes and electrons injected from the anode and the cathode to emit light may be used alone, but materials in which the host material and the dopant material are involved in light emission may also be used.

The organic light emitting device according to an exemplary embodiment of the present application may be a front emission type, a back emission type, or a double-sided emission type, depending on the material used.

In one embodiment, in manufacturing an organic device having an anode as an ITO substrate and a cathode as a Li layer, a hole injection layer, a hole transport layer, an electron blocking layer, an organic emission layer, an electron transport layer, and an electron injection layer are sequentially formed on the ITO substrate. An organic device may be manufactured by vacuum deposition. At this time, the hole injection layer (Hloe Injecting Layer, HIL) can be deposited to a thickness of, for example, 10 nm, by adding an impurity (Dopant) about 5 to 20% so that the hole injection can be performed excellently . The hole transport layer (HTL) may be formed to a thickness of 70 to 100 nm, and the electron blocking layer may be formed to a thickness of 10 to 20 nm. Subsequently, the organic emission layer (OEL) may be formed to a thickness of 35 nm by using a host such as CBP, CP, mCBP and a dopant such as an organic compound according to the present invention in a weight ratio of 60:40. In addition, after depositing an electron transport layer at 35 nm, LiF can be formed as 1 nm as an electron injection layer, but the material, thickness, and weight ratio of each layer can be adjusted and used as needed, and is not limited thereto.

The heterocycle compound according to an exemplary embodiment of the present application may function on a principle similar to that applied to an organic light emitting device in organic electronic devices including organic solar cells, organic photoreceptors, and organic transistors.

According to an exemplary embodiment of the present application, an electronic device including the organic light emitting device according to the present invention can be provided. The electronic device may be a display including an organic light emitting device, but is not limited thereto.

Hereinafter, the present specification will be described in more detail through examples, but these are only for illustrating the present application and are not intended to limit the scope of the present application.

<Example>

Example 1. Synthesis of Compound 1

5 g (29.9 mmol) of carbazole was suspended in 150 ml of tetrahydrofuran, and 0.9 g (35.88 mmol) of sodium hydride was added thereto, followed by stirring at room temperature for 1 hour. Then, 4.9 g (29.9 mmol) of 5,6-difluoropyrazine-2,3-dicarbonitrile was added and stirred at 50°C for 12 hours. After the reaction is over, water is added and stirred for 30 minutes. Thereafter, the mixture was extracted with dichloromethane and distilled water, and the organic layer was distilled under reduced pressure and then filtered with silica gel. The organic solution was removed and recrystallized to obtain compound 1, 9.6 g (yield: 70%).

Example 2. Synthesis of Compound 2

Preparation of compound 2-1

1-bromo-9-phenyl-9H-carbazole 20g (62.07 mmol), bis(pinacolato)diboron 24.9g (93.1 mmol), Pd(dppf)Cl ₂ 2.3g (3.1 mmol), potassium acetate 12.2 g (124.1 mmmol) was suspended in 300 ml of 1,4-dioxane and stirred at reflux for 12 hours. After completion of the reaction, the mixed solution is filtered through celite. The filtrate was distilled under reduced pressure and then subjected to silica gel column to obtain compound 2-1, 13.7 g (yield: 60%).

Preparation of compound 2

5,6-dichloropyrazine-2,3-dicarbonitrile 5 g (25.1 mmol), compound 2-1 20.4 g (55.3 mmol), Pd(PPh ₃ ) ₄ 1.5 g (1.2 mmol), potassium carbonate 6.9 g (50.2 mmmol) was suspended in 125 ml of toluene, 25 ml of ethyl alcohol, and 25 ml of distilled water, followed by stirring at reflux for 12 hours. After the reaction is completed, the mixture is extracted with dichloromethane and distilled water, and the organic layer is distilled under reduced pressure and then filtered with silica gel. The organic solution was removed and recrystallized to obtain compound 2, 10 g (yield: 65%).

Example 3. Synthesis of Compound 3

5 g (29.9 mmol) of carbazole was suspended in 150 ml of tetrahydrofuran, and 0.9 g (35.88 mmol) of sodium hydride was added thereto, followed by stirring at room temperature for 1 hour. Then, 4.9 g (29.9 mmol) of 3,6-difluoropyrazine-2,5-dicarbonitrile was added and stirred at 50° C. for 12 hours. After the reaction is over, water is added and stirred for 30 minutes. Thereafter, the mixture was extracted with dichloromethane and distilled water, and the organic layer was distilled under reduced pressure and then filtered with silica gel. The organic solution was removed and recrystallized to obtain compound 3, 8.3g (yield: 60%).

<Comparative Example 1. Synthesis of Comparative Compound 1>

Synthesis of Comparative Compound 1

2,5-difluoropyrazine 3g (25.9 mmol), carbazole 8.6 g (51.7 mmol), cesium carbonate 33.7 g (103.4 mmol) were suspended in 150 ml of dimethylformamide and stirred at 190°C for 16 hours. . After the reaction was completed, the mixture was extracted with dichloromethane and distilled water, and the organic layer was distilled under reduced pressure, followed by silica gel column to obtain Comparative Compound 1, 7.4 g (yield: 70%).

<Experimental Example 1. Evaluation of luminescence properties of Example 1 and Comparative Example 1>

The ITO (Indium Tin Oxide) glass used as the positive electrode was ultrasonically washed for 30 minutes using IPA and distilled water, dried in an oven at 100° C. for 30 minutes, and then transferred to a vacuum deposition apparatus chamber.

Next, a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), an organic emitting layer (OEL), and electrons in turn on the ITO substrate A transport layer (Electron Transport Layer, ETL) and an electron injection layer (EIL) were deposited (0.5 to 1.0 Å/sec, 1 to 4 x 10 ^-7 torr), and an Al layer was deposited as a negative electrode. The organic light emitting layer was prepared to include dopants (Compounds 1 to 3 or Comparative Compound 1) on a host (CBP or mCBP) in a weight ratio of 60:40, respectively.

After vacuum deposition, the substrate was transferred to a glove box to undergo encapsulation. The sealing member may be provided with a glass cap equipped with a moisture absorbent using BaO therein, and applied to an epoxy sealant for sealing to prevent UV and moisture penetration into the deposition surface by UV irradiation. .

layer material Thickness (nm) Cathode Al 100 EIL LiF One ETL LGC201 35 OEL Host: CBP or mCBP
Dopant: Compounds 1-3 or Comparative Compound 1
Host: dopant=60:40 weight ratio 35 EBL TCTA 15 HTL NPB 75 HIL NPB: HATCN
NPB:HATCN 90:10 weight ratio 10 Anode ITO 150

The luminance, current efficiency, and emission peak of the organic light-emitting devices prepared in Examples 1 to 3 and Comparative Example 1 were measured using a current-voltmeter (Keithley 2635B) and a luminance meter (Spectra scan PR655) and the results are shown in Table 2. Shown. Luminance, efficiency, and emission peak data are the results measured at a current density standard of 10 mA/cm ² .

Sample No. Host Dopant Luminance
[cd/m ² ] efficiency
[cd/A] Luminous peak
[nm] Example 1 CBP Compound 1 5715 57.2 516 Example 2 CBP Compound 2 5214 52.1 520 Example 3 CBP Compound 3 5374 53.7 520 Comparative Example 1 mCBP Comparative Compound 1 4132 41.3 516

As can be seen from Table 1 above, Examples 1 to 3 and Comparative Example 1 have the same or similar emission region bands, but Examples 1 to 3 exhibited much better characteristics in terms of luminous efficiency and luminance.

Claims (10)

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

In Chemical Formula 1,
Cz is a substituted or unsubstituted carbazolyl group,
Any two of X ₁ to X ₅ are N, the rest are CR,
At least one of R is a cyano group, the remaining substituents are the same or different, and each independently substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group. The method according to claim 1,
The Cz is a compound represented by any one of the following formulas 2-1 to 2-5:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

In Chemical Formulas 2-1 to 2-5,
A1 to A3 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 heteroaryl group,
n is an integer from 1 to 8, and when n is 2 or more, A1 is the same or different from each other,
m is an integer from 1 to 7, and when m is 2 or more, A2 is the same or different from each other,

Means a position where the carbazolyl group is substituted. The method according to claim 1,
Formula 1

Is a compound represented by at least one of the following formulas 3-1 to 3-5:
[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

In Formula 3-1, X ₃ to X ₅ are CR, at least one of R is a cyano group, and the remaining substituents are the same or different, and each independently substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
In Formula 3-2, X ₂ , X ₄ and X ₅ are CR, at least one of R is a cyano group, and the remaining substituents are the same or different, and each independently substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
In Formula 3-3, X ₂ , X ₃ and X ₅ are CR, at least one of R is a cyano group, and the remaining substituents are the same or different, and each independently substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
In Formula 3-4, X ₂ to X ₄ are CR, at least one of R is a cyano group, and the remaining substituents are the same or different, and each independently substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
In Formula 3-5, X ₁ , X ₄ and X ₅ are CR, at least one of R is a cyano group, and the remaining substituents are the same or different, and each independently substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group. The method according to claim 1,
2 of R are cyano groups: The method according to claim 1,
Compounds represented by at least one of the following compounds:

An organic light emitting device including a first electrode, a second electrode, and an organic material layer provided between the first electrode and the second electrode, wherein the organic material layer includes a compound according to any one of claims 1 to 5. The method according to claim 6,
The organic material layer comprises at least one of a hole injection layer, a hole transport layer, a light emitting layer, a hole blocking layer, an electron injection layer and an electron transport layer. The method according to claim 6,
The organic material layer includes an emission layer, and the emission layer comprises the compound. The method according to claim 8,
The light emitting layer containing the compound is an organic light emitting device that is a blue light emitting layer. An electronic device comprising the organic light emitting device according to claim 6.

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