KR20190103060A - Novel compound and organic light emitting device comprising the same - Google Patents

Abstract

The present invention relates to a compound represented by chemical formula 1 and an organic light-emitting device comprising the same. According to the present invention, the compound represented by the chemical formula 1 may be used as a material for an organic material layer in the organic light-emitting device. The compound of the chemical formula 1 according to at least one embodiment may improve the efficiency, driving voltage, and/or lifetime characteristics of the organic light-emitting device.

Description

Novel compound and organic light-emitting device including the same {NOVEL COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME}

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

This application claims the benefit of the filing date of Korean Patent Application No. 10-2018-0023621 filed with the Korea Intellectual Property Office on February 27, 2018, the entire contents of which are incorporated herein.

In general, organic light emitting phenomenon refers to a phenomenon of converting electrical energy into light energy using an organic material. An organic light emitting device using an organic light emitting phenomenon usually has a structure including an anode, a cathode, and an organic material layer therebetween. In this case, the organic material layer is often made of a multilayer structure composed of different materials in order to increase the efficiency and stability of the organic light emitting device, for example, it may be made of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer. When the voltage is applied between the two electrodes in the structure of the organic light emitting device, holes are injected into the organic material layer at the anode and electrons are injected into the organic material layer, and excitons are formed when the injected holes and the electrons meet each other. When it falls back to the ground, it glows.

There is a continuing need for the development of new materials for such organic light emitting devices.

Korea Patent Publication No. 10-1317923

In the present specification, a compound represented by Chemical Formula 1 and an organic light emitting device including the same are described.

An exemplary embodiment of the present specification provides a compound represented by the following formula (1).

[Formula 1]

In Chemical Formula 1,

X is hydrogen; Or cyano group,

R is a heterocyclic group containing at least one substituted or unsubstituted N,

Ar is hydrogen; heavy hydrogen; Substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

a is an integer of 0 to 4,

When a is 2 or more, Ar is 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 one or more organic material layers disposed between the first electrode and the second electrode, wherein the organic material layer is represented by Formula 1 above. It provides an organic light emitting device comprising the compound represented.

The compound represented by Chemical Formula 1 may be used as a material of the organic material layer of the organic light emitting device, for example, hole injection, hole transport, hole injection and hole transport, electron blocking, light emission, hole blocking, electron transport or electron injection material. The compound of Formula 1 according to at least one exemplary embodiment may improve efficiency, driving voltage, and / or lifetime characteristics in the organic light emitting device.

Compound of Formula 1 according to an embodiment of the present invention has a high electron acceptability, excellent heat resistance can maintain a suitable deposition temperature when manufacturing an organic light emitting device. In addition, since the sublimation temperature is high, high purity can be achieved by the sublimation refining method, and it does not cause contamination to the deposition apparatus or the organic light emitting device for deposition in manufacturing the organic light emitting device.

In addition, the compound according to an exemplary embodiment of the present invention may have a TADF (delayed fluorescence) property of ΔE _ST (difference between singlet energy and triplet energy) of 0.3 eV or less.

FIG. 1 shows an example of an organic light emitting element composed of 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 element consisting of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7 and a cathode 4 It is.
3 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 8, a light emitting layer 3, a hole blocking layer 9, an electron injection and transport layer ( 10 shows an example of an organic light emitting element composed of a cathode 4.

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

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

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

는 연결 부위를 의미한다.In the present specification,

Means a linking site.

As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Nitrile group; Nitro group; Hydroxyl group; Amino group; Phosphine oxide groups; An alkoxy group; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy groups; Aryl sulfoxy group; Silyl groups; Boron group; An alkyl group; Cycloalkyl group; Alkenyl groups; Aryl group; Aralkyl group; Ar alkenyl group; Alkylaryl group; Alkylamine group; Aralkyl amine groups; Heteroarylamine group; Arylamine group; Aryl phosphine group; And it is substituted or unsubstituted with one or more groups selected from the group consisting of a heterocyclic group, or substituted or unsubstituted with a group to which two or more groups of the group is connected. For example, "group where two or more groups are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a group in which two phenyl groups are linked.

In the present specification, "adjacent" The group may mean a substituent substituted with an atom directly connected to an atom in which the corresponding substituent is substituted, a substituent positioned closest in structural conformation to the substituent, or another substituent substituted in an atom in which the substituent is substituted. For example, two substituents substituted at the ortho position in the benzene ring and two substituents substituted at the same carbon in the aliphatic ring may be interpreted as "adjacent" to each other. Alternatively, a substituent substituted for N in carbazole and a substituent of carbon 1 or carbon 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 silyl group may be represented by a chemical formula of -SiR _a R _b R _c , wherein R _a , R _b and R _c are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group. Specific examples of the silyl group include trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, and phenylsilyl group, but are not limited thereto. Do not.

In the present specification, the boron group may be represented by a chemical formula of -BR _d R _e , wherein R _d and R _e are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group. The boron group may include, but is not limited to, a dimethyl boron group, a diethyl boron group, a t-butyl methyl boron group, a diphenyl boron group, a phenyl boron group, and the like.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 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-methylbutyl, 1-ethylbutyl, pentyl, n-pentyl Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 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-ethylpropyl, 1 , 1-dimethylpropyl, isohexyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present specification, the alkoxy group may be linear, branched or cyclic. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C40. 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 and the like It may be, but is not limited thereto.

Substituents comprising alkyl groups, alkoxy groups and other alkyl group moieties described herein include both straight and pulverized forms.

In the present specification, the alkenyl group may be linear or branched, and the carbon number 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 one embodiment, the cycloalkyl group has 3 to 40 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. 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 is not limited thereto.

In the present specification, the alkylamine group is not particularly limited in carbon number, but is preferably 1 to 40. Specific examples of the alkylamine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine 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 or a substituted or unsubstituted diarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group, may be a polycyclic aryl group. The arylamine group including two or more aryl groups may simultaneously include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group.

Specific examples of the arylamine group include a phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 3-methylphenylamine group, 4-methylnaphthylamine group, 2-methylbiphenylamine group, 9- Methyl anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyl tolylamine group and the like, but is not limited thereto.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group or a substituted or unsubstituted diheteroarylamine group. The heteroaryl group in the heteroarylamine group may be a monocyclic heteroaryl group, may be a polycyclic heteroaryl group. The heteroarylamine group including two or more heteroaryl groups may simultaneously include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group.

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

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

In the present specification, the aryl group is not particularly limited, but preferably has 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 monocyclic aryl group may be a phenyl group, a biphenyl group, a terphenyl group, and the like, but is not limited thereto. The polycyclic aryl group may be naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, or 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-diphenyl fluorenyl group). However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a ring group containing one or more of N, O, P, S, Si, and Se as hetero atoms, and carbon number is not particularly limited, but is preferably 1 to 60 carbon atoms. According to an exemplary embodiment, the heterocyclic group has 1 to 30 carbon atoms. Examples of the heterocyclic group include pyridinyl group, pyrrolyl group, pyrimidinyl group, pyridazinyl group, furanyl group, thiophenyl group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, Isothiazolyl group, triazolyl group, oxadiazolyl group, thiadiazolyl group, dithiazolyl group, tetrazolyl group, pyranyl group, thiopyranyl group, pyrazinyl group, oxazinyl group, thiazinyl group, deoxyyl group , Triazinyl group, tetragenyl group, quinolinyl group, isoquinolinyl group, quinolyl group, quinazolinyl group, quinoxalinyl group, naphthyridinyl group, acridinyl group, xanthenyl group, phenanthridinyl group, diazanap Thalenyl group, triazaindenyl group, indolyl group, indolinyl group, indolinyl group, phthalazinyl group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, benzothiazolyl group, benzoxa Zolyl group, benzimidazolyl group, benzothiophenyl group, benzofuranyl group, Dibenzothiophenyl group, dibenzofuranyl group, carbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, indolocarbazolyl group, indenocarbazolyl group, phenazinyl group, imidazopyridinyl group, phenoxazinyl Group, phenantridinyl group, phenanthrolinyl group, phenothiazinyl group (phenothiazinyl) group, imidazopyridinyl group, imidazophenantridinyl group and the like, but is not limited thereto.

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

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

In the present specification, the aralkyl amine group refers to an amine group substituted with an aryl group and an alkyl group.

In the present specification, the aralkenyl group means an alkenyl group substituted with an aryl group.

In the present specification, the aralkyl group means an alkyl group substituted with an aryl group.

In the present specification, an alkylaryl group means an aryl group substituted with an alkyl group.

In the present specification, the aryl group in the aryloxy group, arylthioxy group, aryl sulfoxy group, aralkyl group, aralkenyl group, aralkylamine group, arylamine group, arylphosphine group and arylheteroarylamine group includes The description may apply.

In the present specification, the alkyl group in the alkylthioxy group, the alkyl sulfoxy group, the alkylaryl group, the alkylamine group and the aralkylamine group, the description of the alkyl group described above can be applied.

In the present specification, the heteroaryl group described above may be applied to the heteroaryl group in the heteroarylamine group and the arylheteroarylamine 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 about the heteroaryl group described above may be applied except that the heteroarylene group is a divalent group.

In the present specification, the meaning of combining with adjacent groups to form a ring means combining with adjacent groups with each other for a substituted or unsubstituted aliphatic hydrocarbon ring; Substituted or unsubstituted aromatic hydrocarbon ring; Substituted or unsubstituted aliphatic heterocycle; Substituted or unsubstituted aromatic heterocycle; Or to form a condensed ring thereof.

In the present specification, the aliphatic hydrocarbon ring means a ring composed only of carbon and hydrogen atoms as a ring which is not aromatic. Specifically, examples of the aliphatic hydrocarbon ring include cyclopropane, cyclobutane, cyclobutene, cyclopentane, cyclopentene, cyclohexane, cyclohexene, 1,4-cyclohexadiene, cycloheptane, cycloheptene, cyclooctane, cyclooctene, and the like. There is, but is not limited to these.

In the present specification, the aromatic hydrocarbon ring means an aromatic ring composed only of carbon and hydrogen atoms. Specifically, examples of the aromatic hydrocarbon ring include benzene, naphthalene, anthracene, phenanthrene, perylene, fluoranthene, triphenylene, penalene, pyrene, tetracene, chrysene, pentacene, fluorene, indene, acene Naphthylene, benzofluorene, spirofluorene and the like, but are not limited thereto.

In the present specification, the aliphatic heterocycle means an aliphatic ring including at least one of heteroatoms. Specifically, examples of aliphatic heterocycles include oxirane, tetrahydrofuran, 1,4-dioxane, pyrrolidine, piperidine, morpholine, oxepan, Azocaine, thiocaine and the like, but are not limited to these.

In the present specification, the aromatic heterocycle means an aromatic ring including at least one of heteroatoms. Specifically, examples of aromatic heterocycles 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, azine Cridine, phenanthridine, diazanaphthalene, triazaindene, 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.

In the present specification, the triplet energy T1 is a difference value between the energy level of the ground state and the energy level of the triplet excited state.

In the present specification, the singlet energy S1 is a difference value between the energy level of the ground state and the energy level of the singlet excited state.

In the present specification, triplet energy and singlet energy can be measured using a spectrometer capable of measuring fluorescence and phosphorescence.

The triplet energy is obtained by preparing a solution at a concentration of 10 ^-5 M using toluene or tetrahydrofuran (THF) in a cryogenic state using liquefied nitrogen, and irradiating a light source with an absorption wavelength band of a substance to the solution to emit light. Except for singlet emission, triplet emission spectra can be confirmed by analysis. When electrons are excited from the light source, the electron stays in the triplet energy level much longer than the singlet energy level, allowing separation of the two components in cryogenic conditions.

The singlet energy is measured using a fluorescent device, and unlike the aforementioned triplet energy level measuring method, the singlet energy may be measured by irradiating a light source at room temperature. The following examples describe more detailed methods of measuring triplet energy and singlet energy.

In this specification, "HOMO" is the highest occupied molecular orbital, and "LUMO" is the lowest unoccupied molecular orbital.

In this specification, "energy level" means the energy size. Therefore, even when the energy level is displayed in the negative (-) direction from the vacuum level, the energy level is interpreted to mean the absolute value of the corresponding energy value. For example, an energy level of "large" means that the absolute value increases in the negative direction from the vacuum level. In addition, in the present specification, the expression such as "deep" or "high" is the same as the expression that the energy level is large.

The HOMO energy level is measured using UV photoelectron spectroscopy (UPS), which irradiates UV on the surface of the thin film, and detects protruding electrons to measure ionization potential of the material. After dissolving in a solvent with an electrolyte solution can be measured by using a cyclic voltammetry (CV) to measure the oxidation potential (voltage oxidation) through a voltage sweep (voltage sweep).

The LUMO energy level can be obtained by measuring inverse photoelectron spectroscopy (IPES) or electrochemical reduction potential. In addition to the above method, the LUMO energy level can be calculated using the HOMO energy level and the singlet energy level.

In an exemplary embodiment of the present specification, the HOMO energy level and the LUMO energy level are ferrocene as the oxidation and reduction potential of the dimethylformamide (DMF) solution in which the measurement compound is dissolved at a concentration of 5 mM and an electrolyte at a concentration of 0.1M. It may be a value measured by cyclic voltammetry (CV), which is confirmed based on the compound. Specifically, the HOMO energy level and LUMO energy level of the present specification were measured by the energy level measuring method of Examples described later.

In one embodiment of the present specification, Ar is hydrogen.

In one embodiment of the present specification, a is 0.

In one embodiment of the present specification, R is represented by the following formula (2).

[Formula 2]

In Chemical Formula 2,

R1 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or groups adjacent to each other combine to form a substituted or unsubstituted ring.

In one embodiment of the present specification, R1 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, R1 and R2 combine with each other to form a substituted or unsubstituted ring, or R2 and R3 combine with each other to form a substituted or unsubstituted ring, or R3 and R4 represent each other Combine to form a substituted or unsubstituted ring, R5 and R6 combine with each other to form a substituted or unsubstituted ring, or R6 and R7 combine with each other to form a substituted or unsubstituted ring, or R7 and R8 form Combine with each other to form a substituted or unsubstituted ring.

In one embodiment of the present specification, R1 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C _1-10 alkyl group; A substituted or unsubstituted C _6-30 aryl group; Or a substituted or unsubstituted C _2-30 heterocyclic group, or groups adjacent to each other combine to form a substituted or unsubstituted C _6-30 ring.

In one embodiment of the present specification, R1 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C _1-6 alkyl group; A substituted or unsubstituted C _6-20 aryl group; Or a substituted or unsubstituted C _2-20 heterocyclic group, or groups adjacent to each other combine to form a substituted or unsubstituted C _6-24 ring.

In one embodiment of the present specification, R1 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C _1-6 alkyl group; A substituted or unsubstituted C _6-12 aryl group; Or a substituted or unsubstituted C _2-16 heterocyclic group, or groups adjacent to each other combine to form a substituted or unsubstituted C _6-20 ring.

In one embodiment of the present specification, the substituted or unsubstituted ring formed by bonding groups adjacent to each other in the R1 to R8 is substituted or unsubstituted benzene; Or substituted or unsubstituted benzofuran; Substituted or unsubstituted benzothiophene; Or substituted or unsubstituted indene.

In one embodiment of the present specification, the substituted or unsubstituted ring formed by bonding groups adjacent to each other in the R1 to R8 is benzene; Benzofuran; Benzothiophene; Or indene substituted with a methyl group.

In one embodiment of the present specification, R1 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; An alkyl group; Aryl group; Or a heterocyclic group unsubstituted or substituted with R 61, or groups adjacent to each other combine to form an aromatic hydrocarbon ring or a heterocycle.

In one embodiment of the present specification, R61 is a substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroring group.

In one embodiment of the present specification, R61 is a substituted or unsubstituted C _1-10 alkyl group; A substituted or unsubstituted C _6-20 aryl group; Or a substituted or unsubstituted C _2-20 heterocyclic group.

In one embodiment of the present specification, R61 is a substituted or unsubstituted C _1-6 alkyl group; A substituted or unsubstituted C _6-16 aryl group; Or a substituted or unsubstituted C _2-16 heterocyclic group.

In one embodiment of the present specification, R61 is an aryl group unsubstituted or substituted with an alkyl group, an aryl group, or a cyano group; Or a heterocyclic group.

In one embodiment of the present specification, the heterocyclic group of R61 is a heterocyclic group including one or more elements selected from the group consisting of O and S.

In one embodiment of the present specification, the heterocyclic group of R61 is a heteroaryl group.

In one embodiment of the present specification, the heterocyclic group of R61 is a heteroaryl group including one or more elements selected from the group consisting of O and S.

In one embodiment of the present specification, Chemical Formula 2 is represented by any one of the following Chemical Formulas 2-1 to 2-3.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In Chemical Formulas 2-1 to 2-3,

X 1 is O; S; C (R31) (R32); Or N (R33),

X2 is O; S; C (R34) (R35); Or N (R36),

Y is O; S; C (R37) (R38); Or N (R39),

R31 and R32 are the same as or different from each other, and each independently hydrogen; An alkyl group; Or an aryl group, R31 and R32 are each a phenyl group, combine with each other to form a fluorene ring,

R34 and R35 are the same as or different from each other, and each independently hydrogen; An alkyl group; Or an aryl group, R34 and R35 are each a phenyl group, combine with each other to form a fluorene ring,

R37 and R38 are the same as or different from each other, and each independently hydrogen; An alkyl group; Or an aryl group, R37 and R38 are each a phenyl group, combine with each other to form a fluorene ring,

R33, R36 and R39 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

R40 and R41 are the same as or different from each other, and each independently an alkyl group,

a1 is 0 or 1, a2 is 0 or 1, a40 is 0 or 1, a41 is 0 or 1, and a1 + a2 + a40 + a41 is 1 or more.

In one embodiment of the present specification, Chemical Formula 2-1 is represented by the following Chemical Formula 4-1 or 4-2.

[Formula 4-1]

[Formula 4-2]

In Chemical Formulas 4-1 and 4-2,

Definitions of X1, X2, R40 and R41 are the same as defined in the formula 2-1,

a1 is 0 or 1, a2 is 0 or 1, a1 + a2 is 1 or 2,

a40 is 0 or 1, a41 is 0 or 1, and a40 + a41 is 1 or 2.

In one embodiment of the present specification, Chemical Formula 2-1 is represented by the following Chemical Formula 4-3.

[Formula 4-3]

In Chemical Formula 4-3,

Definitions of X1 and X2 are as defined in Formula 2-1,

a1 is 0 or 1, a2 is 0 or 1, and a1 + a2 is 1 or 2.

In one embodiment of the present specification, Chemical Formula 2-1 is represented by any one of the following Chemical Formulas 5-1 to 5-4.

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

In Chemical Formulas 5-1 to 5-4, the definitions of X1, X2, R40, and R41 are the same as defined in Chemical Formula 2-1.

In one embodiment of the present specification, Chemical Formula 2-3 is represented by any one of the following Chemical Formulas 3-2 to 3-7.

[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

[Formula 3-7]

In Chemical Formulas 3-2 to 3-7,

The definition of Y is as defined in formula 2-3.

In one embodiment of the present specification, R31 and R32 are the same as or different from each other, and each independently hydrogen; An alkyl group of C _1-10 ; Or a C _6-20 aryl group, or R 31 and R 32 are each a phenyl group and combine with each other to form a fluorene ring.

In one embodiment of the present specification, R31 and R32 are the same as or different from each other, and each independently hydrogen; An alkyl group of C _1-6 ; Or a C _6-12 aryl group, or R 31 and R 32 are each a phenyl group and combine with each other to form a fluorene ring.

In one embodiment of the present specification, R31 and R32 are the same as or different from each other, and each independently hydrogen; Methyl group; Or a phenyl group, or R31 and R32 are each a phenyl group and combine with each other to form a fluorene ring.

In one embodiment of the present specification, R34 and R35 are the same as or different from each other, and each independently hydrogen; An alkyl group of C _1-10 ; Or a C _6-20 aryl group, or R 34 and R 35 are each a phenyl group, and combine with each other to form a fluorene ring.

In one embodiment of the present specification, R34 and R35 are the same as or different from each other, and each independently hydrogen; An alkyl group of C _1-6 ; Or a C _6-12 aryl group, or R 34 and R 35 are each a phenyl group, and combine with each other to form a fluorene ring.

In one embodiment of the present specification, R34 and R35 are the same as or different from each other, and each independently hydrogen; Methyl group; Or a phenyl group, or R34 and R35 are each a phenyl group and combine with each other to form a fluorene ring.

In one embodiment of the present specification, R37 and R38 are the same as or different from each other, and each independently hydrogen; An alkyl group of C _1-10 ; Or a C _6-20 aryl group, or R 37 and R 38 are each a phenyl group and combine with each other to form a fluorene ring.

In one embodiment of the present specification, R37 and R38 are the same as or different from each other, and each independently hydrogen; An alkyl group of C _1-6 ; Or a C _6-12 aryl group, or R 37 and R 38 are each a phenyl group and combine with each other to form a fluorene ring.

In one embodiment of the present specification, R37 and R38 are the same as or different from each other, and each independently hydrogen; Methyl group; Or a phenyl group, or R37 and R38 are each a phenyl group and combine with each other to form a fluorene ring.

In one embodiment of the present specification, R33, R36 and R39 are the same as or different from each other, and are each independently a substituted or unsubstituted C _1-10 alkyl group; A substituted or unsubstituted C _6-20 aryl group; Or a substituted or unsubstituted C _2-20 heterocyclic group.

In one embodiment of the present specification, R33, R36 and R39 are the same as or different from each other, and each independently a substituted or unsubstituted C _1-6 alkyl group; A substituted or unsubstituted C _6-16 aryl group; Or a substituted or unsubstituted C _2-16 heterocyclic group.

In one embodiment of the present specification, R33, R36 and R39 are the same as or different from each other, and each independently an aryl group unsubstituted or substituted with an alkyl group, an aryl group, or a cyano group; Or a heterocyclic group.

In one embodiment of the present specification, the heterocyclic groups R33, R36 and R39 are heterocyclic groups including one or more elements selected from the group consisting of O and S.

In one embodiment of the present specification, the heterocyclic group of R 33, R 36 and R 39 is a heteroaryl group.

In one embodiment of the present specification, the heterocyclic groups R33, R36 and R39 are heteroaryl groups including one or more elements selected from the group consisting of O and S.

In one embodiment of the present specification, R33, R36 and R39 are the same as or different from each other, and each independently a phenyl group; Methylphenyl group; Cyanophenyl group; Biphenyl group; Dimethyl fluorenyl group; Dibenzofuranyl group; Or a dibenzothiophenyl group.

In one embodiment of the present specification, R33, R36 and R39 are the same as or different from each other, and each independently a phenyl group; 4-methylphenyl group; 4-cyanophenyl group; (1,1'-biphenyl) -4-yl group; 9,9'-dimethyl-9H-fluoren-2-yl group; Dibenzofuran-3-yl group; Or a dibenzothiophen-3-yl group.

In one embodiment of the present specification, X1 and X2 are the same.

In one embodiment of the present specification, X1 and X2 are different.

In one embodiment of the present specification, R40 and R41 are the same as or different from each other, and are each independently a C _1-10 alkyl group.

In one embodiment of the present specification, R40 and R41 are the same as or different from each other, and are each independently a C _1-6 alkyl group.

In one embodiment of the present specification, R40 and R41 are the same as or different from each other, and each independently a methyl group; Or t-butyl group.

In one embodiment of the present specification, R40 and R41 are the same as each other.

In one embodiment of the present specification, R41 and R41 are different from each other.

In one embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Chemical Formulas 7-1 to 7-3.

[Formula 7-1]

[Formula 7-2]

[Formula 7-3]

In Chemical Formulas 7-1 to 7-3, the definitions of X, R, Ar, and a are the same as defined in Chemical Formula 1.

In one embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Chemical Formulas 8-1 to 8-3.

[Formula 8-1]

[Formula 8-2]

[Formula 8-3]

In Chemical Formulas 8-1 to 8-3, definitions of X, R, Ar, and a are the same as defined in Chemical Formula 1.

In one embodiment of the present specification, Chemical Formula 1 is represented by the following Chemical Formula 9.

[Formula 9]

In Chemical Formula 9,

Any one of G1 to G5 is X, any one of G1 to G5 is R, a group other than X or R in G1 to G5 is hydrogen,

The definitions of X and R are as defined in formula (1).

In one embodiment of the present invention, the compound of Formula 1 is any one selected from the following compounds.

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

The present invention adjusts the HOMO and LUMO energy levels of the compound by introducing a variety of substituents in the core structure of Formula 1, to provide a compound having a variety of energy bandgap.

In one embodiment, the compound represented by Formula 1 is a delayed fluorescent material. The delayed fluorescent material is a material that converts triplet excitons into singlet excitons and converts them into light, unlike the phosphors that convert singlet excitons into triplet excitons and converts them into light, and because of this process, it exhibits delayed fluorescent characteristics. Delayed fluorescent materials can theoretically convert both singlet excitons and triplet excitons to light, enabling 100% internal quantum efficiency, overcoming the limitations of lifetime and efficiency of phosphors.

Delayed fluorescence (also referred to as thermally activated delayed fluorescence: abbreviated as "TADF") is a singlet of 75% triplet excitons generated by electric field excitation at room temperature or in the light emitting layer temperature in a light emitting device. Reverse Intersystem Crossing (hereinafter, abbreviated as 'RISC') occurs with excitons. The singlet excitons generated by the inverse crossover are fluorescently luminescent as in the case of the 25% singlet excitons generated by the direct excitation, thereby enabling 100% internal quantum efficiency.

In order to express the TADF phenomenon, it is effective to reduce the difference (ΔE _ST ) between the triplet energy and the singlet energy of the organic compound. In order to reduce ΔE _ST , it is important to localize (clearly separate) the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) in the molecule.

According to an exemplary embodiment of the present specification, the difference (ΔE _{ST_D} ) between the singlet energy (S1 _D ) and the triplet energy (T1 _D ) of the compound represented by Formula 1 is 0 eV or more and 0.3 eV or less.

In one embodiment, the difference between the singlet energy (S1 _D ) and the triplet energy (T1 _D ) of the compound represented by Formula 1 (ΔE _{ST_D} ) is 0 eV or more and 0.2 eV or less. When the difference between the singlet energy (S1 _D ) and the triplet energy (T1 _D ) of the compound represented by Formula 1 satisfies the above range, the excitons of the triplet energy level are singlet energy due to inverse crossover (RISC). Since the excitons stay in the triplet energy level is reduced by increasing the rate and speed of moving to the level, there is an advantage that the efficiency and lifespan of the organic light emitting device is increased.

In one embodiment, the triplet energy (T1 _D ) of the compound represented by Formula 1 is 2.1eV to 2.8eV.

In addition, the organic light emitting device according to the present invention is an organic light emitting device including a first electrode, a second electrode, and at least one organic layer disposed between the first electrode and the second electrode, the organic layer is represented by the formula It includes a compound represented.

In one embodiment, the compound represented by Formula 1 is included in the light emitting layer.

In one embodiment, the organic material layer includes a light emitting layer, the light emitting layer comprises a dopant, the dopant is a compound represented by the formula (1).

In one embodiment, the light emitting layer including the compound represented by Formula 1 further includes a host. In this case, the compound represented by Formula 1 may act as a dopant. At this time, the content of the compound of Formula 1 is 1 part by weight to 50 parts by weight with respect to 100 parts by weight of the host.

In one embodiment, the triplet energy T1 _H of the host is 2.4 eV to 3.2 eV.

In one embodiment, the singlet energy S1 _H of the host is 2.6eV to 3.6eV.

In one embodiment, the host material may be appropriately selected and used as long as the triplet energy (T1 _H ) of the host is greater than the triplet energy (T1 _D ) of the compound represented by Formula 1.

In one embodiment, the host may be any one selected from the following compounds, but is not limited thereto.

The organic material layer of the organic light emitting device of the present specification may be formed of a single layer structure, but may be formed of a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting diode of the present specification may include 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 light emitting layer as the organic layer.

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

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

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

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

In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing an organic material layer and an anode material on a substrate from a cathode material. However, the manufacturing method is not limited thereto.

In one 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.

For example, the organic light emitting diode may have a laminated structure as described below, but is not limited thereto.

(1) anode / hole transport layer / light emitting layer / cathode

(2) anode / hole injection layer / hole transport layer / light emitting layer / cathode

(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 / cathode

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

(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 / cathode

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

(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 the organic light emitting device according to the exemplary embodiment of the present specification is illustrated in FIGS. 1 to 3.

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

FIG. 2 shows an example of an organic light emitting element composed of a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7 and a cathode 4 It is. In such a structure, the compound of Formula 1 may be included in the hole injection layer or the hole transport layer, but is preferably included in the light emitting layer.

3 shows a substrate 1, an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 8, a light emitting layer 3, a hole blocking layer 9, an electron injection and transport layer ( 10 shows an example of an organic light emitting element composed of a cathode 4. In such a structure, the compound of Formula 1 is a hole injection layer (5), a hole transport layer (6), an electron blocking layer (8), a light emitting layer (3), a hole blocking layer (9) or an electron injection and transport layer (10) ), But is preferably included in the light emitting layer.

As the anode material, a material having a large work function is usually preferred to facilitate hole injection into the organic material layer. Specific examples of the positive electrode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc and gold or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide (IZO); Combinations of metals and oxides 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, and the like, but are not limited thereto.

The hole injection layer is a layer for injecting holes received from the electrode into the light emitting layer or an adjacent layer provided toward the light emitting layer. The hole injection material has the ability to transport holes, has an effect of hole injection at the anode, an excellent hole injection effect on the light emitting layer or the light emitting material, and transfers excitons generated from the light emitting layer to the electron injection layer or the electron injection material. It is preferable to use the compound which prevents and is excellent in thin film formation ability. The highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrin, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene Organic, anthraquinone, and polyaniline and polythiophene-based conductive polymers, but are not limited thereto.

The hole transport layer is a layer that receives holes from the hole injection layer and transports holes to the light emitting layer or an adjacent layer provided toward the light emitting layer. As the hole transporting material, a material capable of transporting holes from the anode or the hole injection layer to be transferred to the light emitting layer is suitable. Specific examples of the hole transport material include 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), triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyaryls Alkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino substituted chalcone derivatives, oxazole derivatives, styryl anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, Silasein derivatives, polysilane-based, aniline-based copolymers, conductive polymer oligomers (particularly thiophene oligomers) and the like, but are not limited thereto.

A hole buffer layer may be further provided between the hole injection layer and the hole transport layer. As the hole buffer layer, a hole injection or transport material known in the art may be used.

An electron blocking layer may be provided between the hole transport layer and the light emitting layer, and a material known in the art may be used. The electron blocking layer is a layer for preventing the flow of the electrons to the anode to the light emitting layer and to control the flow of holes flowing into the light emitting layer to control the performance of the entire device. The electron blocking material is preferably a compound having the ability to prevent the inflow of electrons from the light emitting layer to the anode and to control the flow of holes injected into the light emitting layer or the light emitting material. In one embodiment, an arylamine-based organic material may be used as the electron blocking layer, but is not limited thereto.

A hole blocking layer may be provided between the electron transport layer and the light emitting layer, and a material known in the art may be used. The hole blocking layer is a layer that blocks the flow of holes from the light emitting layer to the cathode and controls the performance of the entire device by controlling the electrons flowing into the light emitting layer. As the hole blocking material, a compound having the ability to prevent the inflow of holes from the light emitting layer to the cathode and to control the electrons injected into the light emitting layer or the light emitting material is preferable. As the hole blocking material, an appropriate material may be used according to the configuration of the organic material layer used in the device. The hole blocking layer is positioned between the light emitting layer and the cathode, and is preferably provided in contact with the light emitting layer.

The electron transport layer may play a role of smoothing the transport of electrons. Materials known in the art such as Alq ₃ (tris (8-hydroxyquinolino) aluminum), PBD, TAZ, spiro-PBD, BAlq, SAlq can be used. The electron transport layer may have a thickness of about 1 nm to about 50 nm. Here, when the thickness of the electron transporting layer is 1 nm or more, there is an advantage in that the electron transporting property is prevented from being lowered. When the thickness of the electron transporting layer is 50 nm or less, the thickness of the electron transporting layer is so thick that the driving voltage is increased to improve the movement of electrons. There is an advantage that can be prevented.

The electron injection layer serves to facilitate the injection of electrons. Alq ₃ (tris (8-hydroxyquinolino) aluminum), PBD, TAZ, spiro-PBD, BAlq or SAlq can be made of organic compounds, complexes or metal compounds known in the art. Organic materials that can be used in the electron injection layer include fluorenone, anthraquinomimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, benzoimidazole, perylenetetracarboxylic acid, and preorenil Den methane, anthrone and the like, derivatives thereof, metal complex compounds and nitrogen-containing 5-membered ring derivatives, and the like, but are not limited thereto. With the metal compound is a metal halide, and cargo may be used, such as LiQ, LiF, may be is used NaF, KF, RbF, CsF, FrF, BeF _2, MgF _2, CaF _2, SrF _2, BaF ₂ and RaF ₂ etc. . The electron injection layer may have a thickness of about 1 nm to about 50 nm. Here, when the thickness of the electron injection layer is 1 nm or more, there is an advantage that the electron injection characteristics may be prevented from being lowered. When the thickness of the electron injection layer is 50 nm or less, the thickness of the electron injection layer is too thick, so that the driving voltage is increased to improve the movement of electrons. There is an advantage that can be prevented from being raised. In one embodiment, the electron injection layer may be formed by mixing the organic material and the metal compound.

It is preferable that the cathode material is a material having a small work function to facilitate electron injection into the organic material layer. Specific examples of the negative electrode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead or alloys thereof; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto. The cathode may be formed to a thickness thin enough to transmit light when the organic light emitting device is a front or double-sided light emitting structure, and may be formed thick enough to reflect light when the organic light emitting device is a bottom emitting structure. Can be.

One or more organic material layers such as the hole injection layer, the hole buffer layer, the hole transport layer, the electron blocking layer, the hole blocking layer, the electron transport layer, and the electron injection layer are further disposed between the light emitting layer and the anode or the cathode, and the light emitting layer and the charge generating layer. May be included.

The light emitting material is a material capable of emitting light in the 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 with respect to fluorescence or phosphorescence is preferable. Specific examples thereof include 8-hydroxyquinoline aluminum complex (Alq ₃ ); Carbazole series compounds; Dimerized styryl compounds; BAlq; 10-hydroxybenzoquinoline-metal compound; Benzoxazole, benzothiazole and benzimidazole series compounds; Poly (p-phenylenevinylene) (PPV) -based polymers; Spiro compounds; Polyfluorene, rubrene and the like, but are not limited thereto.

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

The dopant material of the light emitting layer includes an aromatic amine derivative, a styrylamine compound, an aromatic hydrocarbon compound substituted with a carbazole group, a boron complex, a fluoranthene compound, a metal complex, and the like. As the aromatic amine derivative, pyrene, anthracene, chrysene, periplanthene and the like having an arylamine group may be used as a condensed aromatic ring derivative having a substituted or unsubstituted arylamine group. As the styrylamine compound, a compound in which at least one arylvinyl group is substituted with a substituted or unsubstituted arylamine may be used. Examples of the styrylamine compound include, but are not limited to, styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like. The metal complex may be an iridium complex, a platinum complex, or the like, but is 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.

<Production example>

The compound represented by the formula (1) is introduced into the halide-substituted benzene or cyanobenzene various kinds of carbazoles through the Buchwald reaction (Buchwald) reaction, and finally isoindolin-1,3-dione It can be prepared by introducing.

Preparation Example 1-1 Synthesis of Compound 1

Synthesis of Compound 1-A

30 g (229.8 mmol) of 1-chloro-4-fluorobenzene, 275.8 mmol of sodium tertoxide, 229.8 mmol of 5-phenyl-5,12-dihydroindolo [3,2-a] carbazole and 300 mL of toluene The mixture was mixed, refluxed, heated for 30 minutes, and 4.6 mmol of tetrakistriphenylphosphinepalladium was added thereto, followed by stirring for 3 hours in a reflux state. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 87.5 g of Compound 1-A (yield 86%).

MS [M + H] ⁺ = 443

Synthesis of Compound 1

20 g (45.1 mmol) of compound 1-A, 54.2 mmol of sodium tert-butoxide, 45.1 mmol of isoindolin-1,3-dione, and 200 mL of toluene were mixed, refluxed, heated for 30 minutes, and tetrakistriphenylphosphine 0.9 mmol of palladium was added and the mixture was stirred for 2 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 18 g of compound 1 (yield 72%).

MS [M + H] ⁺ = 554

Preparation Example 1-2 Synthesis of Compound 2

Synthesis of Compound 1-B

30 g (229.8 mmol) of 1-chloro-4-fluorobenzene, 275.8 mmol of sodium tertoxide, 229.8 mmol of 5-phenyl-5,8-dihydroindolo [2,3-c] carbazole and 300 mL of toluene The mixture was mixed, refluxed, heated for 30 minutes, and 4.6 mmol of tetrakistriphenylphosphinepalladium was added thereto, followed by stirring for 3 hours in a reflux state. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 84.5 g of compound 1-B (yield 83%).

MS [M + H] ⁺ = 443

Synthesis of Compound 2

20 g (45.1 mmol) of compound 1-B, 54.2 mmol of sodium tertoxide, 45.1 mmol of isoindolin-1,3-dione, and 200 mL of toluene were mixed, refluxed, heated for 30 minutes, and tetrakistriphenylphosphine 0.9 mmol of palladium was added and the mixture was stirred for 2 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 18.5 g of compound 2 (yield 74%).

MS [M + H] ⁺ = 554

Preparation Example 1-3 Synthesis of Compound 3

Synthesis of Compound 1-C

30 g (229.8 mmol) of 1-chloro-4-fluorobenzene, 275.8 mmol of sodium tertoxide, 229.8 mmol of 9-phenyl-9H, 9'H-3,3'-bicarbazole and 300 mL of toluene were mixed and rippled After luxing and heating for 30 minutes, 4.6 mmol of tetrakistriphenylphosphinepalladium was added and the mixture was stirred for 3 hours in a reflux state. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 95.4 g of Compound 1-C (yield 80%).

MS [M + H] ⁺ = 519

Synthesis of Compound 3

23.4 g (45.1 mmol) of compound 1-C, 54.2 mmol of sodium tertoxide, 45.1 mmol of isoindolin-1,3-dione, and 200 mL of toluene were mixed, refluxed, heated for 30 minutes, and tetrakistriphenylphosphine 0.9 mmol of palladium was added and the mixture was stirred for 2 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 19.9 g of compound 3 (yield 70%).

MS [M + H] ⁺ = 630

Preparation Example 1-4: Synthesis of Compound 4

Synthesis of Compound 1-D

30 g (192.8 mmol) of 5-chloro-2-fluorobenzonitrile, 231.4 mmol of sodium tertoxide, 192.8 mmol of 5-phenyl-5,12-dihydroindolo [3,2-a] carbazole and toluene 200 mL was mixed, refluxed, heated for 30 minutes, and 3.8 mmol of tetrakistriphenylphosphinepalladium was added, followed by stirring for 3 hours in a reflux state. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 59 g of compound 1-D (yield 81%).

MS [M + H] ⁺ = 468

Synthesis of Compound 4

21.1 g (45.1 mmol) of compound 1-D, 54.2 mmol of sodium tertoxide, 45.1 mmol of isoindolin-1,3-dione, and 200 mL of toluene were mixed, refluxed, heated for 30 minutes, and tetrakistriphenylphosphine 0.9 mmol of palladium was added and the mixture was stirred for 2 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 19 g of compound 4 (yield 73%).

MS [M + H] ⁺ = 579

Preparation Example 1-5: Synthesis of Compound 5

Synthesis of Compound 1-E

30 g (192.8 mmol) of 5-chloro-2-fluorobenzonitrile, 231.4 mmol of sodium tertoxide, 192.8 mmol of 5-phenyl-5,8-dihydroindolo [2,3-c] carbazole and toluene 200 mL was mixed, refluxed, heated for 30 minutes, and 3.8 mmol of tetrakistriphenylphosphinepalladium was added, followed by stirring for 3 hours in a reflux state. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 75.8 g of Compound 1-E (yield 84%).

MS [M + H] ⁺ = 468

Synthesis of Compound 5

21.1 g (45.1 mmol) of compound 1-E, 54.2 mmol of sodium tertoxide, 45.1 mmol of isoindolin-1,3-dione, and 200 mL of toluene were mixed, refluxed, heated for 30 minutes, and tetrakistriphenylphosphine. 0.9 mmol of palladium was added and the mixture was stirred for 2 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 19.6 g of compound 5 (yield 75%).

MS [M + H] ⁺ = 579

Preparation Example 1-6: Synthesis of Compound 6

Synthesis of Compound 1-F

30 g (192.8 mmol) of 5-chloro-2-fluorobenzonitrile, 231.4 mmol of sodium tertbutoxide, 192.8 mmol of 9-phenyl-9H, 9'H-3,3'-bicarbazole and 200 mL of toluene The mixture was refluxed, heated for 30 minutes, and 3.8 mmol of tetrakistriphenylphosphinepalladium was added thereto, followed by stirring for 3 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice with chloroform / hexane to give 82.9 g of Compound 1-F (yield 79%).

MS [M + H] ⁺ = 544

Synthesis of Compound 6

24.5 g (45.1 mmol) of compound 1-F, 54.2 mmol of sodium tertoxide, 45.1 mmol of isoindolin-1,3-dione, and 200 mL of toluene were mixed, refluxed, heated for 30 minutes, and tetrakistriphenylphosphine 0.9 mmol of palladium was added and the mixture was stirred for 2 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 21.3 g of compound 6 (yield 72%).

MS [M + H] ⁺ = 655

Preparation Example 1-7: Synthesis of Compound 7

Synthesis of Compound 1-G

30 g (192.8 mmol) of 2-chloro-6-fluorobenzonitrile, 231.4 mmol of sodium tertoxide, 192.8 mmol of 5-phenyl-5,12-dihydroindolo [3,2-a] carbazole and toluene 200 mL was mixed, refluxed, heated for 30 minutes, and 3.8 mmol of tetrakistriphenylphosphinepalladium was added, followed by stirring for 3 hours in a reflux state. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice with chloroform / hexane to give 69.5 g of Compound 1-G (yield 77%).

MS [M + H] ⁺ = 468

Synthesis of Compound 7

21.1 g (45.1 mmol) of compound 1-G, 54.2 mmol of sodium tertoxide, 45.1 mmol of isoindolin-1,3-dione, and 200 mL of toluene were mixed, refluxed, heated for 30 minutes, and tetrakistriphenylphosphine 0.9 mmol of palladium was added and the mixture was stirred for 2 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 17.7 g of compound 7 (yield 68%).

MS [M + H] ⁺ = 579

Preparation Example 1-8: Synthesis of Compound 8

Synthesis of Compound 1-H

30 g (192.8 mmol) of 2-chloro-6-fluorobenzonitrile, 231.4 mmol of sodium tertoxide, 192.8 mmol of 5-phenyl-5,8-dihydroindolo [2,3-c] carbazole and toluene 200 mL was mixed, refluxed, heated for 30 minutes, and 3.8 mmol of tetrakistriphenylphosphinepalladium was added, followed by stirring for 3 hours in a reflux state. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 70.4 g of Compound 1-H (yield 78%).

MS [M + H] ⁺ = 468

Synthesis of Compound 8

21.1 g (45.1 mmol) of compound 1-H, 54.2 mmol of sodium tert-butoxide, 45.1 mmol of isoindolin-1,3-dione, and 200 mL of toluene were mixed, refluxed, heated for 30 minutes, and tetrakistriphenylphosphine 0.9 mmol of palladium was added and the mixture was stirred for 2 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 18 g of compound 8 (yield 69%).

MS [M + H] ⁺ = 579

Preparation Example 1-9 Synthesis of Compound 9

Synthesis of Compound 1-I

30 g (192.8 mmol) of 2-chloro-6-fluorobenzonitrile, 231.4 mmol of sodium tertbutoxide, 192.8 mmol of 9-phenyl-9H, 9'H-3,3'-bicarbazole and 200 mL of toluene The mixture was refluxed, heated for 30 minutes, and 3.8 mmol of tetrakistriphenylphosphinepalladium was added thereto, followed by stirring for 3 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 78.7 g of compound 1-I (yield 75%).

MS [M + H] ⁺ = 544

Synthesis of Compound 9

24.5 g (45.1 mmol) of compound 1-I, 54.2 mmol of sodium tertoxide, 45.1 mmol of isoindolin-1,3-dione, and 200 mL of toluene were mixed, refluxed, heated for 30 minutes, and tetrakistriphenylphosphine 0.9 mmol of palladium was added and the mixture was stirred for 2 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 18.9 g of compound 9 (yield 64%).

MS [M + H] ⁺ = 655

Preparation Example 1-10 Synthesis of Compound 10

Synthesis of Compound 1-J

30 g (192.8 mmol) of 4-chloro-2-fluorobenzonitrile, 231.4 mmol of sodium tertoxide, 5- (dibenzo [b, d] furan-2-yl) -5,7-dihydroindolo 192.8 mmol of [2,3-b] carbazole and 200 mL of toluene were mixed, refluxed and heated for 30 minutes, and 3.8 mmol of tetrakistriphenylphosphinepalladium was added thereto, followed by stirring for 3 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 76.4 g of Compound 1-J (yield 71%).

MS [M + H] ⁺ = 558

Synthesis of Compound 10

25.1 g (45.1 mmol) of compound 1-J, 54.2 mmol of sodium tertoxide, 45.1 mmol of isoindolin-1,3-dione, and 200 mL of toluene were mixed, refluxed, heated for 30 minutes, and tetrakistriphenylphosphine 0.9 mmol of palladium was added and the mixture was stirred for 2 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 18.4 g of compound 10 (yield 61%).

MS [M + H] ⁺ = 669

Preparation Example 1-11 Synthesis of Compound 11

Synthesis of Compound 1-K

3-chloro-4-fluorobenzonitrile 30 g (192.8 mmol), sodium tert-butoxide 231.4 mmol, 3,6-bis (dibenzo [b, d] furan-2-yl) -9H-carbazole 192.8 mmol and 200 mL of toluene were mixed, refluxed and heated for 30 minutes, and 3.8 mmol of tetrakistriphenylphosphinepalladium was added thereto, followed by stirring for 3 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice with chloroform / hexane to give 83.3 g of compound 1-K (yield 68%).

MS [M + H] ⁺ = 635

Synthesis of Compound 11

28.6 g (45.1 mmol) of compound 1-K, 54.2 mmol of sodium tertoxide, 45.1 mmol of isoindolin-1,3-dione, and 200 mL of toluene were mixed, refluxed, heated for 30 minutes, and tetrakistriphenylphosphine 0.9 mmol of palladium was added and the mixture was stirred for 2 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 20.2 g of compound 11 (yield 60%).

MS [M + H] ⁺ = 746

Preparation Example 1-12 Synthesis of Compound 12

Synthesis of Compound 1-L

30 g (192.8 mmol) of 3-chloro-4-fluorobenzonitrile, 231.4 mmol of sodium tertoxide, 9,9 ''-di ([1,1'-biphenyl] -4-yl) -9H, 192.8 mmol of 9'H, 9''H-3,3 ': 6', 3 ''-tercarbazole and 200 mL of toluene were mixed, refluxed and heated for 30 minutes, and 3.8 mmol of tetrakistriphenylphosphinepalladium was added. The mixture was added and stirred for 3 hours in a reflux state. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice with chloroform / hexane to give 117.5 g of compound 1-L (yield 65%).

MS [M + H] ⁺ = 937

Synthesis of Compound 12

42.3 g (45.1 mmol) of compound 1-L, 54.2 mmol of sodium tertoxide, 45.1 mmol of isoindolin-1,3-dione, and 200 mL of toluene were mixed, refluxed, heated for 30 minutes, and tetrakistriphenylphosphine 0.9 mmol of palladium was added and the mixture was stirred for 2 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 27.4 g of compound 12 (yield 58%).

MS [M + H] ⁺ = 1048

Preparation Example 1-13: Synthesis of Compound 13

Synthesis of Compound 1-M

30 g (192.8 mmol) of 5-chloro-2-fluorobenzonitrile, 231.4 mmol of sodium tertoxide, 192.8 mmol of 8H-benzofuro [2,3-c] carbazole and 200 mL of toluene are mixed and refluxed The mixture was heated for 30 minutes, and 3.8 mmol of tetrakistriphenylphosphinepalladium was added thereto, followed by stirring for 3 hours in a reflux state. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 53 g of compound 1-M (yield 70%).

MS [M + H] ⁺ = 393

Synthesis of Compound 13

17.7 g (45.1 mmol) of compound 1-M, 54.2 mmol of sodium tertoxide, 45.1 mmol of isoindolin-1,3-dione, and 200 mL of toluene were mixed, refluxed, heated for 30 minutes, and tetrakistriphenylphosphine 0.9 mmol of palladium was added and the mixture was stirred for 2 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 14.5 g of compound 13 (yield 64%).

MS [M + H] ⁺ = 504

Preparation Example 1-14: Synthesis of Compound 14

Synthesis of Compound 1-N

30 g (192.8 mmol) of 5-chloro-2-fluorobenzonitrile, 231.4 mmol of sodium tertbutoxide, 192.8 mmol of 8H-benzo [4,5] cyeno [2,3-c] carbazole and toluene 200 The mL was mixed, refluxed and heated for 30 minutes, and 3.8 mmol of tetrakistriphenylphosphinepalladium was added thereto, followed by stirring for 3 hours in a reflux state. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice with chloroform / hexane to give 52.8 g of Compound 1-N (yield 67%).

MS [M + H] ⁺ = 409

Synthesis of Compound 14

18.4 g (45.1 mmol) of compound 1-N, 54.2 mmol of sodium tertoxide, 45.1 mmol of isoindolin-1,3-dione, and 200 mL of toluene were mixed, refluxed, heated for 30 minutes, and tetrakistriphenylphosphine 0.9 mmol of palladium was added and the mixture was stirred for 2 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 14.5 g of compound 14 (yield 62%).

MS [M + H] ⁺ = 520

Preparation Example 1-15 Synthesis of Compound 15

Synthesis of Compound 1-O

25.2 g (192.8 mmol) of 1-chloro-4-fluorobenzene, 231.4 mmol of sodium tertoxide, 192.8 mmol of 8,8-dimethyl-5,8-dihydroindeno [2,1-c] carbazole, and 200 mL of toluene was mixed, refluxed, heated for 30 minutes, and 3.8 mmol of tetrakistriphenylphosphinepalladium was added and stirred for 3 hours in a reflux state. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 52.4 g of compound 1-O (yield 69%).

MS [M + H] ⁺ = 394

Synthesis of Compound 15

17.8 g (45.1 mmol) of compound 1-O, 54.2 mmol of sodium tertoxide, 45.1 mmol of isoindolin-1,3-dione, and 200 mL of toluene were mixed, refluxed, heated for 30 minutes, and tetrakistriphenylphosphine 0.9 mmol of palladium was added and the mixture was stirred for 2 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 14.8 g of compound 15 (yield 65%).

MS [M + H] ⁺ = 505

Preparation Example 1-16 Synthesis of Compound 16

Synthesis of Compound 1-P

30 g (192.8 mmol) of 3-chloro-4-fluorobenzonitrile, 231.4 mmol of sodium tertbutoxide, 192.8 mmol of 11H-benzo [a] carbazole and 200 mL of toluene were mixed, refluxed and heated for 30 minutes 3.8 mmol of tristriphenylphosphinepalladium was added and the mixture was stirred for 3 hours in a reflux state. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 48.3 g of Compound 1-P (yield 71%).

MS [M + H] ⁺ = 353

Synthesis of Compound 16

15.9 g (45.1 mmol) of compound 1-P, 54.2 mmol of sodium tertoxide, 45.1 mmol of isoindolin-1,3-dione, and 200 mL of toluene were mixed, refluxed, heated for 30 minutes, and tetrakistriphenylphosphine 0.9 mmol of palladium was added and the mixture was stirred for 2 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 14 g of compound 16 (yield 67%).

MS [M + H] ⁺ = 464

Preparation Example 1-17: Synthesis of Compound 17

Synthesis of Compound 1-Q

30 g (192.8 mmol) of 3-chloro-4-fluorobenzonitrile, 231.4 mmol of sodium tertbutoxide, 192.8 mmol of 7H-benzo [c] carbazole, and 200 mL of toluene were mixed, refluxed and heated for 30 minutes 3.8 mmol of tristriphenylphosphinepalladium was added and the mixture was stirred for 3 hours in a reflux state. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 49.6 g of Compound 1-Q (yield 73%).

MS [M + H] ⁺ = 353

Synthesis of Compound 17

15.9 g (45.1 mmol) of compound 1-Q, 54.2 mmol of sodium tert-butoxide, 45.1 mmol of isoindolin-1,3-dione, and 200 mL of toluene were mixed, refluxed, heated for 30 minutes, and tetrakistriphenylphosphine 0.9 mmol of palladium was added and the mixture was stirred for 2 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 13.2 g of compound 17 (yield 63%).

MS [M + H] ⁺ = 464

Preparation Example 1-18 Synthesis of Compound 18

Synthesis of Compound 1-R

30 g (192.8 mmol) of 3-chloro-4-fluorobenzonitrile, 231.4 mmol of sodium tertbutoxide, 192.8 mmol of 7H-benzo [b] carbazole, and 200 mL of toluene were mixed, refluxed and heated for 30 minutes 3.8 mmol of tristriphenylphosphinepalladium was added and the mixture was stirred for 3 hours in a reflux state. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice with chloroform / hexane to give 51.7 g of compound 1-R (yield 76%).

MS [M + H] ⁺ = 353

Synthesis of Compound 18

15.9 g (45.1 mmol) of compound 1-R, 54.2 mmol of sodium tertoxide, 45.1 mmol of isoindolin-1,3-dione, and 200 mL of toluene were mixed, refluxed, heated for 30 minutes, and tetrakistriphenylphosphine 0.9 mmol of palladium was added and the mixture was stirred for 2 hours under reflux. After the reaction, the reaction solution was returned to room temperature, extracted with water, and the organic layer was recrystallized twice from chloroform / hexane to give 13.8 g of compound 18 (yield 66%).

MS [M + H] ⁺ = 464

In addition to the compounds 1 to 18, the compound represented by the formula (1) can be synthesized by introducing a variety of substituents using the same reaction as the preparation example.

Comparative Example 1

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and ultrasonically cleaned. At this time, Fischer Co. product was used as a detergent, and distilled water filtered secondly as a filter of Millipore Co. product was used as distilled water. After ITO was washed for 30 minutes, ultrasonic washing was performed twice with distilled water for 10 minutes. After washing the distilled water, ultrasonic washing with a solvent of isopropyl alcohol, acetone, methanol, dried and transported to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator. Each thin film was deposited on the ITO transparent electrode thus prepared at a vacuum degree of 5 10 10 ⁻⁴ Pa by vacuum deposition. First, the following compound HAT-CN was thermally vacuum deposited to a thickness of 500 kPa on ITO to form a hole injection layer.

Compound 4-4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (NPB) (300 Pa), which is a substance for transporting holes on the hole injection layer, was vacuum deposited to form a hole transport layer. It was.

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

Subsequently, m-CBP (triple energy = 2.9 eV) and compound 4CzIPN were deposited under vacuum at a weight ratio of 70:30 to form a light emitting layer on the electron blocking layer with a film thickness of 300 kPa.

Compound HB1 was vacuum deposited on the light emitting layer at a film thickness of 100 μs to form a hole blocking layer.

The following compound ET1 and compound LiQ (Lithium Quinolate) were vacuum deposited on the hole blocking layer in a weight ratio of 1: 1 to form an electron injection and transport layer at a thickness of 300 μs. On the electron injection and transport layer, lithium fluoride (LiF) and aluminum were deposited sequentially to have a thickness of 12 kW to form a cathode.

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

Experimental Examples 1 to 18

An organic light emitting diode was manufactured according to the same method as Comparative Example 1 except for using the compound of Table 1 instead of the compound 4CzIPN in Comparative Example 1.

Comparative Example 2

An organic light emitting diode was manufactured according to the same method as Comparative Example 1 except for using the compound of T1 shown below instead of compound 4CzIPN in Comparative Example 1.

When the current was applied to the organic light emitting diodes produced by Experimental Examples 1 to 18 and Comparative Examples 1 to 2, the results of the following [Table 1] were obtained.

division compound
(Light emitting layer) Voltage
(V @ 10mA / cm ² ) efficiency
(cd / A @ 10mA / cm ² ) CIE color coordinates
(x, y) Comparative Example 1 4CzIPN 4.5 14 (0.32, 0.62) Experimental Example 1 One 4.1 19 (0.23, 0.63) Experimental Example 2 2 4.1 20 (0.22, 0.62) Experimental Example 3 3 4.0 20 (0.23, 0.62) Experimental Example 4 4 4.0 22 (0.24, 0.66) Experimental Example 5 5 4.0 21 (0.23, 0.67) Experimental Example 6 6 3.9 22 (0.23, 0.68) Experimental Example 7 7 3.9 22 (0.24, 0.67) Experimental Example 8 8 4.0 21 (0.24, 0.68) Experimental Example 9 9 3.9 20 (0.24, 0.66) Example 10 10 4.1 19 (0.23, 0.63) Example 11 11 4.1 19 (0.24, 0.63) Example 12 12 4.0 20 (0.24, 0.65) Example 13 13 3.9 21 (0.23, 0.64) Example 14 14 4.0 20 (0.24, 0.65) Example 15 15 4.1 20 (0.24, 0.66) Example 16 16 4.0 19 (0.23, 0.65) Example 17 17 4.0 21 (0.23, 0.66) Example 18 18 3.9 20 (0.24, 0.63) Comparative Example 2 T1 4.7 4 (0.20, 0.51)

As shown in Table 1, the devices of Experimental Examples 1 to 18 using the compound having the structure of Formula 1 as a core have a lower voltage and higher efficiency than the device using 4CzIPN.

In addition, when comparing the device of Example 2 with the device of Comparative Example 2, it can be seen that the structure of the embodiments of the present invention is improved in both voltage and efficiency than the structure in which the ring is further condensed to isoindolin-1,3-dione. there was.

As shown in Table 1, it was confirmed that the compound according to the present invention is excellent in light emitting ability and high in color purity and applicable to delayed fluorescent organic light emitting devices.

<Example 2>

Measurement of triplet energy

Triplet energy (T1) was measured at cryogenic conditions using the properties of triplet excitons, which have long lifespan. Specifically, after dissolving the compound in toluene solvent to prepare a sample having a concentration of 10 ^-5 M, the sample is put in a quartz kit and cooled to 77K, and the 300 nm light source is irradiated to the sample for measuring phosphorescence while changing the wavelength Measure the spectrum. The spectrophotometer (FP-8600 spectrophotometer, JASCO Corporation) was used for the measurement of the spectrum.

The vertical axis of the phosphorescence spectrum was phosphorescence intensity, and the horizontal axis was wavelength. A tangent line was drawn for the rise of the short wavelength side of the phosphorescence spectrum, and the wavelength value (λ _edge1 (nm)) of the intersection point of the tangent line and the horizontal axis was obtained, and the wavelength value was substituted into the following equation 1 to calculate the triplet energy. .

Conversion formula 1: T1 (eV) = 1239.85 / λ _edge1

The tangent to the rise of the short wavelength side of the phosphorescence spectrum is drawn as follows. First, the maximum value of the shortest wavelength side of the maximum value of a spectrum is confirmed. At this time, the maximum point which has the peak intensity of 15% or less of the maximum peak intensity of a spectrum is not included in the maximum value of the shortest wavelength side mentioned above. The tangent line at each point on the spectral curve from the short wavelength side of the phosphorescence spectrum to the maximum value is considered. Of these tangent lines, the tangent line having the largest slope value (that is, the tangent line at the inflection point) is a tangent line to the rise of the short wavelength side of the phosphorescence spectrum.

Measurement of singlet energy

Singlet energy (S1) was measured by the following method.

A 10 ^-5 M toluene solution of the compound to be measured was prepared, placed in a quartz cell, and the emission spectrum (vertical axis: light emission intensity, horizontal axis: wavelength) of the 300 nm light source of the sample was measured at room temperature (300 K). The tangent line was drawn about the rise of the short wavelength side of this emission spectrum, and the singlet energy was computed by substituting the wavelength value ((lambda _edge2 (nm)) of the intersection of this tangent line and a horizontal axis in following conversion formula 2). The emission spectrum was measured by using a spectrophotometer (FP-8600 spectrophotometer) of JASCO.

Conversion formula 2: S1 (eV) = 1239.85 / λ _edge2

The tangent to the rise of the short wavelength side of the emission spectrum is drawn as follows. First, the maximum value of the shortest wavelength side of the maximum value of a spectrum is confirmed. The tangent line at each point on the spectral curve from the short wavelength side of the emission spectrum to the maximum value is considered. Of these tangent lines, the tangent line having the largest slope value (that is, the tangent line at the inflection point) is a tangent line to the rise of the short wavelength side of the emission spectrum. The maximum point which has the peak intensity of 15% or less of the maximum peak intensity of a spectrum is not included in the maximum value of the shortest wavelength side mentioned above.

compound S1 (eV) T1 (eV) △ E _ST (eV) One 2.54 2.39 0.15 2 2.55 2.39 0.16 3 2.54 2.39 0.15 4 2.43 2.40 0.03 5 2.42 2.38 0.04 6 2.42 2.37 0.05 7 2.43 2.41 0.02 8 2.44 2.42 0.02 9 2.43 2.40 0.03 10 2.44 2.41 0.03 11 2.43 2.40 0.03 12 2.43 2.39 0.04 13 2.44 2.39 0.05 14 2.43 2.38 0.05 15 2.44 2.39 0.05 16 2.42 2.38 0.04 17 2.43 2.38 0.05 18 2.44 2.40 0.04 T1 2.74 2.38 0.36 4CzIPN 2.44 2.39 0.05

Compounds 1 to 18 used in the Examples herein all were suitable as delayed fluorescent materials with an ΔE _ST of 0.3 eV or less.

Compound T1 used as a comparative example was confirmed to be not suitable as a delayed fluorescent material.

Compound 4CzIPN used as a comparative example corresponds to a delayed fluorescent material with ΔE _ST of 0.3 eV or less, but as seen in Table 1, it was found that Compounds 1 to 18 had improved characteristics 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 various modifications can be made within the scope of the claims and the detailed description of the invention, which also belong to the scope of the invention. .

1: substrate
2: anode
3: light emitting layer
4: cathode
5: hole injection layer
6: hole transport layer
7: electron transport layer
8: electron blocking layer
9: hole blocking layer
10: electron injection and transport layer

Claims (9)

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

In Chemical Formula 1,
X is hydrogen; Or cyano group,
R is a heterocyclic group containing at least one substituted or unsubstituted N,
Ar is hydrogen; heavy hydrogen; Substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,
a is an integer of 0 to 4,
When a is 2 or more, Ar is the same as or different from each other. The method according to claim 1,
R is a compound represented by Formula 2 below:
[Formula 2]

In Chemical Formula 2,
R1 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or groups adjacent to each other combine to form a substituted or unsubstituted ring. The compound of claim 2, wherein Formula 2 is represented by one of Formulas 2-1 to 2-3:
[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In Chemical Formulas 2-1 to 2-3,
X 1 is O; S; C (R31) (R32); Or N (R33),
X2 is O; S; C (R34) (R35); Or N (R36),
Y is O; S; C (R37) (R38); Or N (R39),
R31 and R32 are the same as or different from each other, and each independently hydrogen; An alkyl group; Or an aryl group, R31 and R32 are each a phenyl group, combine with each other to form a fluorene ring,
R34 and R35 are the same as or different from each other, and each independently hydrogen; An alkyl group; Or an aryl group, R34 and R35 are each a phenyl group, combine with each other to form a fluorene ring,
R37 and R38 are the same as or different from each other, and each independently hydrogen; An alkyl group; Or an aryl group, R37 and R38 are each a phenyl group, combine with each other to form a fluorene ring,
R33, R36 and R39 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
R40 and R41 are the same as or different from each other, and each independently an alkyl group,
a1 is 0 or 1, a2 is 0 or 1, a40 is 0 or 1, a41 is 0 or 1, and a1 + a2 + a40 + a41 is 1 or more. The compound of claim 3, wherein Formula 2-3 is represented by any one of the following Formulas 3-2 to 3-7:
[Formula 3-2]

[Formula 3-3]

[Formula 3-4]

[Formula 3-5]

[Formula 3-6]

[Formula 3-7]

In Chemical Formulas 3-2 to 3-7,
The definition of Y is as defined in formula 2-3. The compound according to claim 3, wherein Formula 2-1 is represented by any one of Formulas 5-1 to 5-4:
[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

In Chemical Formulas 5-1 to 5-4,
Definitions of X1, X2, R40 and R41 are the same as defined in Chemical Formula 2-1. The compound of claim 1, wherein the compound represented by Chemical Formula 1 is any one selected from the following structures:

. The compound of claim 1, wherein the difference (ΔE _{ST_D} ) between the singlet energy (S1 _D ) and the triplet energy (T1 _D ) of the compound represented by Chemical Formula 1 is 0 eV or more and 0.3 eV or less. 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 the organic material layer comprises a compound according to any one of claims 1 to 7. It is an organic light emitting device. The method according to claim 8,
The organic material layer includes a light emitting layer,
The light emitting layer includes a dopant,
The dopant is an organic light emitting device that is a compound represented by the formula (1).

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