KR102187980B1 - Compound and organic light emitting device comprising the same - Google Patents

Abstract

The present specification provides a compound represented by Chemical Formula 1 and an organic light-emitting device including the same.

Description

Compound and organic light-emitting device comprising the same TECHNICAL FIELD

The present invention claims the benefit of the filing date of Korean Patent Application No. 10-2018-0036143 filed with the Korean Intellectual Property Office on March 28, 2018, the entire contents of which are incorporated herein.

The present specification relates to a 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. 10-2015-0005583

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

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

[Formula 1]

In Formula 1,

X is a direct bond; O; Or S,

Y is NR; O; Or S,

R1 is a substituted or unsubstituted C2 to C60 alkyl group; Or a substituted or unsubstituted C 3 to C 60 cycloalkyl group,

R and R2 to R4 are each independently hydrogen; heavy hydrogen; Halogen group; A substituted or unsubstituted silyl group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylamine group; A substituted or unsubstituted alkylamine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

a is 1 or 2,

b is 0 or 1,

c and e are each independently an integer of 0 to 4,

d is an integer from 0 to 2,

When a and c to e are 2 or more, the substituents in parentheses are the same as or different from each other.

In addition, an exemplary embodiment of the present specification is an organic light emitting device including 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 is It provides an organic light-emitting device comprising the compound according to an exemplary embodiment of the 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 improve lifetime characteristics in an organic light emitting device. In particular, the compounds described herein can be used as a material for a light emitting layer.

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 composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, 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.

According to an exemplary embodiment of the present specification, the compound represented by Formula 1 is a delayed fluorescent compound.

In general organic light emitting devices, the number of excitons generated in singlet and triplet is generated at a ratio of 25:75 (singlet: triplet), and fluorescence, phosphorescence, and thermally activated delayed fluorescence according to the luminescence type according to exciton movement It can be divided into light emission. In the case of phosphorescent emission, excitons in a triplet excited state move to a ground state to emit light, and in the case of the fluorescence emission, excitons in a singlet excited state are in the ground state ( ground state) to emit light, and in the thermally activated delayed fluorescence emission, an inverse interphase transition is induced from a triplet excited state to a singlet excited state, and the singlet excited state It means that excitons move to the ground state and cause fluorescence emission.

The thermally activated delayed fluorescence emission is distinguished from fluorescence emission in that the peak position of the emission spectrum is the same as that of fluorescence, but the decay time is long.Although the attenuation time is long, the peak position of the emission spectrum is the phosphorescence spectrum and S ₁ -T _It differs from phosphorescence in that it differs by the difference of ₁ energy. At this time, S ₁ is a singlet energy level, and T ₁ is a triplet energy level.

According to an exemplary embodiment of the present specification, the difference (ΔE _ST ) between the singlet energy level and the triplet energy level of the compound represented by Chemical Formula 1 is 0 eV or more and 0.3 eV or less, preferably Is 0 eV or more and 0.2 eV or less. When the difference between the singlet energy level and the triplet energy level of the compound represented by Chemical Formula 1 satisfies the above range, the exciton generated in the triplet is converted to a singlet by inverse interphase transfer (RISC). As the moving rate and speed increase, the time for the excitons to stay in the triplet decreases, thereby increasing the efficiency and lifespan of the organic light-emitting device.

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 at an ortho position in a benzene ring and two substituents substituted at 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 , wherein R _a and R _b are each hydrogen; A substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. Specifically, the boron group includes a dimethyl boron group, a diethyl boron group, a t-butylmethyl boron group, a diphenyl 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 a straight chain or a 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 methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 9-methyl-anthracenylamine Group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, and the like, 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, the 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 carbons 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 the heterocyclic group 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 2 to 25. In another exemplary 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, R1 is a substituted or unsubstituted alkyl group having 2 to 60 carbon atoms; Or a substituted or unsubstituted C3 to C60 cycloalkyl group.

According to an exemplary embodiment of the present specification, R1 is a substituted or unsubstituted alkyl group having 2 to 30 carbon atoms; Or a substituted or unsubstituted C 3 to C 30 cycloalkyl group.

According to an exemplary embodiment of the present specification, R1 is a substituted or unsubstituted alkyl group having 2 to 15 carbon atoms; Or a substituted or unsubstituted C 3 to C 15 cycloalkyl group.

According to an exemplary embodiment of the present specification, R1 is a substituted or unsubstituted alkyl group having 2 to 15 carbon atoms.

According to an exemplary embodiment of the present specification, R1 is a substituted or unsubstituted alkyl group having 3 to 15 carbon atoms.

According to an exemplary embodiment of the present specification, R1 is a methyl group unsubstituted or substituted with a halogen group; Or it is an ethyl group unsubstituted or substituted with a halogen group.

According to an exemplary embodiment of the present specification, R1 is a substituted or unsubstituted branched alkyl group having 3 to 15 carbon atoms.

According to an exemplary embodiment of the present specification, R1 is a substituted or unsubstituted isopropyl group; Or a substituted or unsubstituted t-butyl group.

According to an exemplary embodiment of the present specification, R1 is an isopropyl group unsubstituted or substituted with a carbazole group; Or a t-butyl group unsubstituted or substituted with a carbazole group.

According to an exemplary embodiment of the present specification, R1 is a substituted or unsubstituted cycloalkyl group having 3 to 15 carbon atoms.

According to an exemplary embodiment of the present specification, R1 is a substituted or unsubstituted cycloalkyl group having 6 to 15 carbon atoms.

According to an exemplary embodiment of the present specification, R1 is a substituted or unsubstituted cyclohexane group.

According to an exemplary embodiment of the present specification, R and R2 to R4 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

According to an exemplary embodiment of the present specification, R and R2 to R4 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C1-C60 alkyl group; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted C2 to C60 heterocyclic group.

According to an exemplary embodiment of the present specification, R and R2 to R4 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C1-C30 alkyl group; 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, R and R2 to R4 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C1 to C15 alkyl group; A substituted or unsubstituted aryl group having 6 to 15 carbon atoms; Or a substituted or unsubstituted C 2 to C 15 heterocyclic group.

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

According to an exemplary embodiment of the present specification, R2 to R4 are each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted C1-C15 alkyl group.

According to an exemplary embodiment of the present specification, R2 to R4 are each independently hydrogen; heavy hydrogen; A methyl group unsubstituted or substituted with a halogen group; A substituted or unsubstituted isopropyl group; Or a substituted or unsubstituted t-butyl group.

According to an exemplary embodiment of the present specification, Formula 1 is represented by the following Formula 2.

[Formula 2]

In Formula 2,

The definitions of X, R1 to R3, a, c and d are as described above.

According to an exemplary embodiment of the present specification, Formula 1 is represented by the following Formula 3 or 4.

[Formula 3]

[Formula 4]

In Formulas 3 and 4,

The definitions of X, Y, R1 to R4, a and c to e are as described above.

According to an exemplary embodiment of the present specification, Formula 1 is represented by the following Formula 5 or 6.

[Formula 5]

[Formula 6]

In Formulas 5 and 6,

The definitions of X, Y, R1 to R4, a and c to e are as described above.

According to an exemplary embodiment of the present specification, Chemical Formula 1 is represented by the following Chemical Formula 7 or 8.

[Formula 7]

[Formula 8]

In Formulas 7 and 8,

The definitions of X, Y, R1 to R4, a and c to e are as described 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.

Therefore, the inventors of the present invention believe that the compound of Formula 1 having such characteristics is applied to a material for an organic light emitting device, that is, a light emitting layer, a hole injection layer, a hole transport layer, an electron blocking layer or a charge generation layer, particularly when applied to a light emitting layer, It has been found that it is possible to achieve a lower voltage or longer life. In addition, compared to a material having a small molecular weight and high sublimation property, such as F4TCNQ, deposition is easier, and a stable interface with an electrode or an adjacent organic material layer can be formed compared to HAT-CN.

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.

According to an exemplary embodiment of the present specification, the organic material layer includes an emission layer, the emission layer includes a dopant, and the dopant includes the compound according to the exemplary embodiment of the present specification.

According to an exemplary embodiment of the present specification, the light emitting material of the light emitting layer is a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, wherein the light emitting layer is the aforementioned delayed fluorescent material. As a dopant of the light-emitting layer, wherein at least one of the excitation singlet energy and the excitation triplet energy has a higher value than the light emitting material of the above-described delayed fluorescent material, has a hole transporting ability, an electron transporting ability, and a long wavelength of light emission An organic compound having a high glass transition temperature and a high glass transition temperature may be included as a host.

According to an exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes a host.

According to the exemplary embodiment of the present specification, the triplet energy level of the host may be 2.5 eV or more, and preferably 2.7 eV or more and 3.1 eV or less. When the triplet energy level of the host satisfies the above range, the host exciton energy is efficiently transferred to the dopant, and the triplet/singlet excitons of the host or dopant and the surrounding hole (or electron)-polaron Exciton quenching by the interaction of is minimized. Accordingly, it is possible to prevent the lifespan of the light-emitting diode device from being reduced by electro-oxidation and photo-oxidation, and thus, a light-emitting device having a long life can be implemented.

Further, according to an exemplary embodiment of the present specification, the organic material layer includes a host, and the host is at least one of the following structures, but is not limited thereto.

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 have a structure further including at least one of a hole injection layer, a hole buffer layer, a hole transport layer, an electron blocking layer, a hole blocking 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 inverted type organic light emitting device 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, 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.

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 blocking layer/light emitting layer/electron transport layer/cathode

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

(12) Anode/hole injection layer/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode

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

(14) Anode/Hole transport layer/Light-emitting layer/Hole blocking layer/Electron transport layer/Anode

(15) Anode/Hole transport layer/Light emitting layer/Hole blocking layer/Electron transport layer/Electron injection layer/Anode

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

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

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 hole transport layer 6, 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 composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light-emitting layer 7, an electron transport layer 8, 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 7. 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. As the 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 the material for the hole transport layer, 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.

An electron blocking 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 blocking 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 8 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 8 may be 1 to 50 nm. Here, if the thickness of the electron transport layer 8 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 8 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 serve to facilitate injection of 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.

The light-emitting layers 3 and 7 according to the exemplary embodiment of the present specification may include the compound of Formula 1 above. In this case, the light emitting layers 3 and 7 may be formed of only the compound of Formula 1, but the compound of Formula 1 may exist in a mixed or doped state with other light emitting layer materials known in the art. The compound of Formula 1 may be doped with 0.1 to 50% by weight of the emission layer.

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 blocking layer, hole blocking layer, electron transport layer, and electron injection layer are further formed between the emission layer and the anode or the cathode, and between the emission layer and the charge generation layer. Can be included.

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 compound according to the present invention can act 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.

<Production Example>

The compound represented by Formula 1 can be prepared by introducing a nitrogen-containing compound into fluorobenzene substituted with a cyano group through SnAr reaction as follows. The compounds of the specific examples were synthesized through the following procedure.

Preparation Example 1-1: Synthesis of Compound 1

2,5-di-tert-butyl-4,6-difluoroisophthalonitrile 15 g (54.3 mmol), 9H-carbazole 109 mmol and dimethylformamide (DMF) 150 mL were mixed and heated to 60°C. I did. Potassium carbonate (271.5 mmol) was added and stirred for 3 hours in a reflux state. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with chloroform and hexane to obtain Compound 1 (24.8 g) (yield 80%).

MS[M+H] ⁺ = 571

Preparation Example 1-2: Synthesis of Compound 2

2,5-dicyclohexyl-4,6-difluoroisophthalonitrile 17.8 g (54.3 mmol), 9H-carbazole 109 mmol, and DMF 150 mL were mixed and heated to 60°C. Potassium carbonate (271.5 mmol) was added and stirred for 3 hours in a reflux state. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with chloroform and hexane to obtain compound 2 (27.7 g) (yield 82%).

MS[M+H] ⁺ = 623

Preparation Example 1-3: Synthesis of Compound 3

2-cyclohexyl-4,6-difluoroisophthalonitrile 13.4 g (54.3 mmol), 9H-carbazole 109 mmol, and DMF 150 mL were mixed and heated to 60°C. Potassium carbonate (271.5 mmol) was added and stirred for 3 hours in a reflux state. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with chloroform and hexane to obtain compound 3 (23.8 g) (yield 81%).

MS[M+H] ⁺ = 541

Preparation Example 1-4: Synthesis of Compound 4

2,5-dicyclohexyl-4,6-difluoroisophthalonitrile 17.8 g (54.3 mmol), 3,6-di-tert-butyl-9H-carbazole 109 mmol, and DMF 150 mL were mixed. Heated to 60°C. Potassium carbonate (271.5 mmol) was added and stirred for 3 hours in a reflux state. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with chloroform and hexane to obtain compound 4 (35.9 g) (yield 78%).

MS[M+H] ⁺ = 847

Preparation Example 1-5: Synthesis of Compound 5

4,6-difluoro-2,5-diisopropylisophthalonitrile 13.5 g (54.3 mmol), 3,6-di-tert-butyl-9H-carbazole 109 mmol, and DMF 150 mL were mixed. Heated to 60°C. Potassium carbonate (271.5 mmol) was added and stirred for 3 hours in a reflux state. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with chloroform and hexane to obtain compound 5 (33.3 g) (yield 80%).

MS[M+H] ⁺ = 767

Preparation Example 1-6: Synthesis of Compound 6

13.5 g (54.3 mmol) of 4,6-difluoro-2,5-diisopropylisophthalonitrile, 109 mmol of 5H-benzofuro[3,2-c]carbazole, and 150 mL of DMF were mixed. Heated to 60°C. Potassium carbonate (271.5 mmol) was added and stirred for 3 hours in a reflux state. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with chloroform and hexane to obtain compound 6 (30.2 g) (yield 77%).

MS[M+H] ⁺ = 723

Preparation Example 1-7: Synthesis of Compound 7

4,6-difluoro-2,5-diisopropylisophthalonitrile 13.5 g (54.3 mmol), 5-phenyl-5,12-dihydroindolo[3,2-a]carbazole 109 mmol And 150 mL of DMF were mixed and heated to 60°C. Potassium carbonate (271.5 mmol) was added and stirred for 3 hours in a reflux state. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with chloroform and hexane to obtain compound 7 (35.5 g) (yield 75%).

MS[M+H] ⁺ = 873

Preparation Example 1-8: Synthesis of Compound 8

15 g (54.3 mmol) of 2,5-di-tert-butyl-4,6-difluoroisophthalonitrile, 109 mmol of 10H-phenocyazine, and 150 mL of DMF were mixed and heated to 60°C. Potassium carbonate (271.5 mmol) was added and stirred for 3 hours in a reflux state. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with chloroform and hexane to obtain compound 8 (26.5 g) (yield 77%).

MS[M+H] ⁺ = 635

Preparation Example 1-9: Synthesis of Compound 9

2,5-difluoro-4,6-diisopropylisophthalonitrile 13.5 g (54.3 mmol), 9H-carbazole 109 mmol, and DMF 150 mL were mixed and heated to 60°C. Potassium carbonate (271.5 mmol) was added and stirred for 3 hours in a reflux state. After the reaction, the reaction solution returned to room temperature was reverse-precipitated in water to obtain a solid, and then recrystallized twice with chloroform and hexane to obtain compound 9 (24.2 g) (yield 82%).

MS[M+H] ⁺ = 543

In addition to the compounds 1 to 9, other compounds represented by Chemical Formula 1 may be synthesized by introducing various types of substituents using the same reaction as in Preparation Example.

<Comparative Example 1>

In the present embodiment, an organic light emitting device was manufactured by including the compound represented by Formula 1 according to an exemplary embodiment of the present specification together with a host material (m-CBP) having a triplet energy value of 2.9 eV in the emission layer, and characteristics Was evaluated.

A glass substrate coated with a thin film of ITO (indium tin oxide) to 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 cleaning 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 thus prepared ITO transparent electrode by vacuum evaporation at a vacuum degree of 5Х10 ^-4 Pa. First, the following compound HAT-CN was thermally vacuum deposited on ITO to a thickness of 500 Å 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 compound 4CzIPN were vacuum-deposited on the electron blocking layer at a weight ratio of 70:30 with a thickness of 300 Å as follows 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.

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

In the above process, the deposition rate of organic material was maintained at 0.4 Å/sec to 0.7 Å/sec, lithium fluoride at the cathode was maintained at 0.3 Å/sec, and the deposition rate for aluminum was 2 Å/sec. An organic light emitting device was manufactured by maintaining ×10 ^-7 torr to 5 × 10 ^-6 torr.

<Experimental Examples 1 to 9>

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

<Comparative Examples 2 to 7>

An organic light-emitting device was manufactured in the same manner as in Comparative Example 1, except that compounds of the following T1 to T6 were used instead of the compound 4CzIPN in Comparative Example 1.

When a current was applied to the organic light-emitting devices manufactured according to Experimental Examples 1 to 9 and Comparative Examples 1 to 7, the results of Table 1 were obtained.

division compound
(Luminescent layer) Voltage
(V@10mA/cm ² ) efficiency
(cd/A@10mA/cm ² ) Color coordinates
(x,y) Comparative Example 1 4CzIPN 4.5 13 (0.32, 0.62) Experimental Example 1 One 4.1 19 (0.22, 0.63) Experimental Example 2 2 4.0 19 (0.23, 0.62) Experimental Example 3 3 4.1 20 (0.23, 0.62) Experimental Example 4 4 4.1 21 (0.22, 0.66) Experimental Example 5 5 4.0 20 (0.23, 0.67) Experimental Example 6 6 4.0 19 (0.22, 0.68) Experimental Example 7 7 3.9 20 (0.23, 0.67) Experimental Example 8 8 4.0 21 (0.24, 0.68) Experimental Example 9 9 3.9 19 (0.22, 0.66) Comparative Example 2 T1 4.2 12 (0.31, 0.63) Comparative Example 3 T2 4.4 4 (0.15, 0.38) Comparative Example 4 T3 4.5 3 (0.17, 0.39) Comparative Example 5 T4 4.3 11 (0.25, 0.60) Comparative Example 6 T5 4.3 12 (0.27, 0.61) Comparative Example 7 T6 4.2 11 (0.28, 0.60)

As shown in Table 1, the devices of Experimental Examples 1 to 9 using the compound having the structure of Formula 1 as a core had a lower voltage and increased efficiency than those using 4CzIPN.

In addition, when comparing the devices of Comparative Examples 2 to 7 with the experimental examples of the present application, it can be seen that the structures of the experimental examples of the present application have both improved characteristics in terms of voltage and efficiency.

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.

<Example 2>

The HOMO and LUMO energy levels were confirmed by dissolving the measured compound in dimethylformamide (DMF) at a concentration of 5 mM and the electrolyte at 0.1 M, and comparing the oxidation and reduction potentials through CV instrument measurement and comparing the ferrocene compound as a reference. .

Measurement of HOMO energy level

The HOMO energy level of the compound and the LUMO energy level are the circulating voltage comparing the oxidation and reduction potentials of a dimethylformamide (DMF) solution in which the measured compound is dissolved at a concentration of 5 mM and the electrolyte is dissolved at a concentration of 0.1 M based on a ferrocene compound. It was measured by cyclic voltammetry (CV). Specific measurement conditions are as follows.

CV device: Iviumstat from Ivium Tech

Measurement solution: A dimethylformamide (DMF) solution in which the measurement compound is dissolved in a concentration of 5 mM and an electrolyte (KNO ₃ , Aldrich) is dissolved in a concentration of 0.1 M.

Working Electrode: Carbon electrode

Reference Electorde: Al/AgCl electrode

Counter Electrode: Platinum electrode

Measurement temperature: 25℃

Scan rate: 50mV/S

The HOMO energy level (E(HOMO)) and the LUMO energy level (E(LUMO)) were calculated through the following equation.

E(HOMO)=[V _solvent -(E _{onset ox} -E _1/2 (solvent)) eV

E(LUMO)=[V _solvent -(E _{onset red} -E _1/2 (solvent))eV

In the above formula, V _solvent is the energy level of the solvent, E _1/2 (solvent) is the half-wave level of the solvent, E _{onset ex} is the starting point of oxidation, and E _{onset red} is the starting point of reduction.

Measurement of triplet energy

Triplet energy (T ₁ ) was measured in a cryogenic state using the characteristics of triplet excitons with a long life. Specifically, after dissolving the compound in a toluene solvent to prepare a sample having a concentration of 10 ^-5 M, the sample was put in a quartz kit and cooled to 77 K, and a 300 nm light source was irradiated to the sample for phosphorescence measurement, and phosphorescence while changing the wavelength. Measure the spectrum. For the measurement of the spectrum, a spectrophotometer (FP-8600 spectrophotometer, JASCO) was used.

The vertical axis of the phosphorescence spectrum was made into phosphorescence intensity, and the horizontal axis was made into wavelength. A tangent line was drawn with respect to the rise of the short wavelength side of the phosphorescent spectrum, the wavelength value (λ _edge1 (nm)) of the intersection of the tangent line and the horizontal axis was calculated, and then this wavelength value was substituted into the following conversion equation 1 to calculate triplet energy. .

Conversion formula (F1): T ₁ (eV) = 1239.85/λ _edge1

The tangent to the rise on the short wavelength side of the phosphorescence spectrum is drawn as follows. First, the maximum value of the shortest wavelength side among the maximum values of the spectrum is checked. At this time, the maximum point having a peak intensity of 15% or less of the maximum peak intensity of the spectrum is not included in the maximum value of the shortest wavelength side described above. The tangent line at each point on the spectrum curve from the short wavelength side of the phosphorescence spectrum to the maximum value is considered. Among these tangents, the tangent with the largest inclination value (that is, the tangent to the inflection point) is taken as the tangent to the rise of the short wavelength side of the phosphorescent spectrum.

Measurement of singlet energy

Singlet energy (S ₁ ) was measured by the following method.

A 10 ^-5 M toluene solution of the compound to be measured was prepared and placed in a quartz cell, and the emission spectrum (vertical axis: luminescence intensity, horizontal axis: wavelength) of the 300 nm light source of the sample was measured at room temperature (300 K). A tangent line was drawn with respect to the rise on the short wavelength side of the emission spectrum, and the wavelength value (λ _edge2 (nm)) of the intersection of the tangent line and the horizontal axis was substituted into the following conversion equation 2 to calculate singlet energy. The emission spectrum was measured using a JASCO spectrophotometer (FP-8600 spectrophotometer).

Conversion formula 2: S ₁ (eV) = 1239.85/λ _edge2

The tangent to the rise on the short wavelength side of the emission spectrum is drawn as follows. First, the maximum value of the shortest wavelength side among the maximum values of the spectrum is checked. The tangent line at each point on the spectrum curve from the short wavelength side of the emission spectrum to the maximum value is considered. Among these tangents, the tangent with the largest inclination value (that is, the tangent to the inflection point) is taken as the tangent to the rise of the short wavelength side of the emission spectrum. The maximum point having a peak intensity of 15% or less of the maximum peak intensity of the spectrum is not included in the maximum value on the shortest wavelength side described above.

compound S ₁ (eV) T ₁ (eV) HOMO(eV) LUMO(eV) △E _ST (eV) One 2.44 2.38 5.71 3.03 0.06 2 2.43 2.37 5.77 3.05 0.06 3 2.43 2.38 5.78 3.01 0.05 4 2.42 2.40 5.73 3.00 0.02 5 2.42 2.39 5.76 3.08 0.03 6 2.43 2.38 5.71 3.01 0.05 7 2.43 2.40 5.72 3.06 0.03 8 2.44 2.41 5.76 3.09 0.03 9 2.43 2.39 5.75 3.07 0.04 T1 2.54 2.47 5.88 3.05 0.07 T2 2.73 2.40 6.07 2.94 0.33 T3 2.73 2.39 6.06 2.97 0.34 T4 2.54 2.41 5.89 3.09 0.13 T5 2.53 2.40 5.88 3.08 0.13 T6 2.54 2.41 5.87 3.11 0.13 4CzIPN 2.44 2.39 5.55 3.15 0.05

It can be seen that all of the compounds 1 to 9 used in the present examples have a ΔE _ST of 0.3 eV or less, which is suitable as a delayed fluorescent material.

In the case of compounds T2 and T3 used as comparative examples, it could be confirmed that they are not suitable as delayed fluorescent materials, and 4CzIPN, T1, T4 to T6 correspond to delayed fluorescent materials with ΔE _ST of 0.3 eV or less, but as shown in Table 1. As shown, it was found that the characteristics of Compounds 1 to 9 were all improved in terms of voltage and efficiency.

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: light emitting layer
8: electron transport layer

Claims (9)

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

In Formula 1,
X is a direct bond; O; Or S,
Y is NR; O; Or S,
R1 is an alkyl group having 2 to 15 carbon atoms unsubstituted or substituted with carbazole; Or a cycloalkyl group having 3 to 15 carbon atoms,
R is an aryl group,
R2 and R3 are each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted C 1 to C 15 alkyl group,
R4 is hydrogen,
a is 1 or 2,
b is 0 or 1,
c and e are each independently an integer of 0 to 4,
d is an integer from 0 to 2,
When a and c to e are 2 or more, the substituents in parentheses are the same as or different from each other. The method according to claim 1,
Formula 1 is a compound represented by the following Formula 2:
[Formula 2]

In Formula 2,
The definitions of X, R1 to R3, a, c and d are the same as in Formula 1. The method according to claim 1,
Formula 1 is a compound represented by the following formula 3 or 4:
[Formula 3]

[Formula 4]

In Formulas 3 and 4,
The definitions of X, Y, R1 to R4, a and c to e are the same as in Formula 1. The method according to claim 1,
Formula 1 is a compound represented by the following formula 5 or 6:
[Formula 5]

[Formula 6]

In Formulas 5 and 6,
The definitions of X, Y, R1 to R4, a and c to e are the same as in Formula 1. The method according to claim 1,
Formula 1 is a compound represented by the following formula 7 or 8:
[Formula 7]

[Formula 8]

In Formulas 7 and 8,
The definitions of X, Y, R1 to R4, a and c to e are the same as in Formula 1. The method according to claim 1,
The compound represented by Formula 1 is any one selected from the following structures:

. 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 to 6 Organic light-emitting device comprising the compound according to. The method of claim 7,
The organic material layer includes a light emitting layer having a dopant,
The dopant is an organic light-emitting device, characterized in that the compound. The method of claim 8,
The emission layer further comprises a host,
The organic light emitting device of the host is at least one of the following structures:

..

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