KR102402732B1 - Compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

Compound and organic light emitting device including same {COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME}

The present invention claims the benefit of the filing date of Korean Patent No. 10-2019-0087711 filed with the Korean Intellectual Property Office on July 19, 2019, the entire contents of which are incorporated herein by reference.

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

A phenomenon using a phenomenon in which reverse intersystem crossing (hereinafter, appropriately abbreviated as “RISC”) from triplet excitons to singlet excitons occurs (thermal-activated delayed fluorescence (also called “thermal-excited delayed fluorescence”): The fluorescence emitting material using Thermally Activated Delayed Fluorescence (hereinafter, appropriately abbreviated as "TADF") and the possibility of use in organic EL devices are reported.Utilizing delayed fluorescence by this TADF mechanism, fluorescence by electric field excitation is used. Also in light emission, an internal quantum efficiency of 100% equivalent to phosphorescence is theoretically possible.

In order to develop the TADF phenomenon, at room temperature or the temperature of the light emitting layer in the light emitting device, 75% of triplet excitons generated by electric field excitation and inverse interterminal crossover from singlet excitons need to occur. In addition, 100% internal quantum efficiency is theoretically possible because singlet excitons generated by inverse intersystem crossover emit fluorescence similarly to 25% singlet excitons generated by direct excitation. In order for this inverse intersystem crossing to occur, the absolute value (ΔE _ST ) of the difference between the lowest singlet excitation energy level (S ₁ ) and the lowest triplet excitation energy level (T ₁ ) is required to be small.

E_ST를 작게 하는 것이 유효하고,

E_ST를 작게 하기 위해서는, 분자 내의 최고 피점 분자 궤도(HOMO)와 최저 공분자 궤도(LUMO)를 혼재시키지 않고 국재화시키는 것(명확하게 분리하는 것)이 유효하다.For example, in order to express the TADF phenomenon,

It is effective to make E _ST small,

In order to make E _ST small, it is effective to localize (clearly separate) the highest occluded molecular orbital (HOMO) and lowest co-molecule orbital (LUMO) in a molecule|numerator without mixing.

However, when localizing the highest occluded molecular orbital (HOMO) and lowest co-molecular orbital (LUMO) in a molecule without coexisting, the π-conjugated system in the molecule is reduced or cut, making it difficult to achieve stability and, as a result, light emission. This will shorten the life of the device. Therefore, a new method of increasing the efficiency and lifespan of the TADF element is demanded.

US Patent Application Publication No. 2004-0251816

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

The present invention provides a compound represented by the following formula (1).

[Formula 1]

In Formula 1,

R ₁ To R ₆ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted alkyl group, a halogen group, a nitrile group, a substituted or unsubstituted silyl group, a substituted or unsubstituted phosphine oxide group, A substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group,

L is a direct bond, a substituted or unsubstituted arylene group, or a substituted or unsubstituted heteroarylene group,

A is a substituted or unsubstituted trivalent aryl group, or a substituted or unsubstituted trivalent heteroaryl group,

B ₁ and B ₂ are the same as or different from each other, and are each independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heteroaryl group, a substituted or unsubstituted a substituted or unsubstituted aryloxy group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted alkynyl group,

a to e are integers from 0 to 4,

When a is plural, R ₁ are the same as or different from each other,

When b is plural, R ₂ are the same as or different from each other,

When c is plural, R ₃ are the same as or different from each other,

When d is plural, R ₄ are the same as or different from each other,

When e is plural, R ₅ is the same as or different from each other.

In addition, the present invention is a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the compound.

The compound according to an exemplary embodiment of the present specification may be used as a material for an organic material layer of an organic light emitting device, and by using the compound, it is possible to improve efficiency, low driving voltage, and/or lifespan characteristics in an organic light emitting device.

1 and 2 show an organic light emitting device according to an exemplary embodiment of the present specification.

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

The present specification provides a compound represented by Formula 1 above.

The compound of Formula 1 according to an exemplary embodiment of the present invention is a spiro[diindolo[3,2-b:3',2',1'-de]acridine-10,9'- having electron donor properties fluorene]. When a substituent having an electron accepting property is introduced into the core structure into -AB ₁ B ₂ , the overall conjugation of the material is interrupted, so that the orbital separation of HOMO and LUMO occurs appropriately. That is, the CT characteristics in the material are increased, which can lead to an increase in efficiency. The greater the separation between the HOMO orbital and the LUMO orbital, the smaller the energy difference between the singlet and the triplet. In other words, if there is a lot of overlap between HOMO orbitals and LUMO orbitals, the singlet energy increases. Since the triplet energy of a substance increases as the conjugation is broken, if a substituent with electron accepting properties is introduced into AB ₁ B ₂ , as described above, the overlap between the HOMO orbital and the LUMO orbital decreases, and the singlet (singlet) is lowered and triplet energy is increased, so that the singlet and triplet gap is reduced, so that the reverse transfer rate is increased and quenching between triplets is reduced. This can lead to an increase in overall efficiency.

For example, AB ₁ B ₂ may be introduced as a substituent having an electron accepting property, and as a substituent having an electron accepting property, triazine, pyrimidine, pyridine, an N-containing heteroaryl group, an aryl group substituted with a nitrile group, or nitrile A heteroaryl group substituted with a group may be used. When the compound of Formula 1 in which indolospyrocarbazole is introduced as an electron donor is used as a TADF material, the emission color, efficiency, and lifespan of the organic light-emitting device can be improved.

In the present specification, compounds having various energy band gaps can be synthesized by introducing various substituents into the core structure of the compound represented by Formula 1 above. In addition, in the present specification, the HOMO and LUMO energy levels of the compound can be controlled by introducing various substituents into the core structure of the structure as described above.

Through singlet energy control, a material can emit blue, green, and red light, and it can be designed to have a narrow energy gap by controlling the triplet energy level.

In addition, it is possible to realize a high-efficiency, long-life organic light-emitting device with delayed fluorescence characteristics due to the effect of increasing the orientation of the material.

The difference (ΔEST) between the singlet energy level (S1) and the triplet energy level (T1) of the compound represented by Formula 1 is 0 eV or more and 0.3 eV or less.

In the present specification, the difference (ΔEST) between the singlet energy level (S1) and the triplet energy level (T1) of the compound represented by Formula 1 means the absolute value of T1-S1.

In the present specification, triplet energy can be measured using a spectroscopic instrument capable of measuring fluorescence and phosphorescence, and in the case of measurement conditions, toluene or TEF as a solvent in a cryogenic state using liquid nitrogen at a concentration of 10 ^-6 M A solution is prepared, singlet emission is excluded from the spectrum emitted by irradiating the solution with a light source in the absorption wavelength band of the material, and the spectrum emitted from triplet is analyzed and confirmed. When the electrons are reversed from the light source, the time the electrons stay in the triplet is much longer than the time the electrons stay in the singlet, so the separation of the two components is possible at cryogenic temperatures.

In the present specification, singlet energy is measured using a fluorescent device, and unlike the triplet energy measurement method described above, a light source is irradiated at room temperature.

When the difference between the singlet energy level (S1) and the triplet energy (T1) level of the compound represented by Formula 1 satisfies the above range, the exciton generated from the triplet is converted to a singlet by reverse intersystem transition (RISC). As the moving rate and speed increase, the time the excitons stay in the triplet is reduced, so that the efficiency and lifespan of the organic light emitting diode are increased.

The conjugation length of a compound and the energy bandgap are closely related. Specifically, the longer the conjugation length of the compound, the smaller the energy bandgap. In the present invention, the HOMO and LUMO energy levels of the compound can also be controlled by introducing the core structure having the above structure.

In addition, by introducing various substituents into the core structure of the structure as described above, a compound having the intrinsic properties of the introduced substituent can be synthesized. For example, by introducing a substituent mainly used for a hole injection layer material, a hole transport material, a light emitting layer material, and an electron transport layer material used in manufacturing an organic light emitting device into the core structure, a material satisfying the conditions required for each organic material layer can be synthesized. can

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

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

As used herein, the term "substituted or unsubstituted" refers to deuterium; nitrile group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted arylamine group; a substituted or unsubstituted aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group, is substituted with a substituent to which two or more of the above exemplified substituents are connected, or does not have any substituents. For example, the "substituent to which two or more substituents are connected" may be an aryl group substituted with an aryl group, an aryl group substituted with a heteroaryl group, a heterocyclic group substituted with an aryl group, an aryl group substituted with an alkyl group, and the like.

In the present specification, the halogen group may be F, Cl, Br, I, or the like.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specifically, it is preferably 1 to 20 carbon atoms. More specifically, it is preferable that it has 1-10 carbon atoms. Specific examples include a methyl group; ethyl group; Profile group; n-propyl group; isopropyl group; butyl group; n-butyl group; isobutyl group; tert-butyl group; sec-butyl group; 1-methylbutyl group; 1-ethylbutyl group; pentyl group; n-pentyl group; isopentyl group; neopentyl group; tert-pentyl group; hexyl group; n-hexyl group; 1-methylpentyl group; 2-methylpentyl group; 4-methyl-2-pentyl group; 3,3-dimethylbutyl group; 2-ethylbutyl group; heptyl group; n-heptyl group; 1-methylhexyl group; cyclopentylmethyl group; cyclohexylmethyl group; octyl group; n-octyl group; tert-octyl group; 1-methylheptyl group; 2-ethylhexyl group; 2-propylpentyl group; n-nonyl group; 2,2-dimethylheptyl group; 1-ethylpropyl group; 1,1-dimethylpropyl group; isohexyl group; 2-methylpentyl group; 4-methylhexyl group; 5-methylhexyl group, and the like, but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, more preferably 3 to 20 carbon atoms. Specifically, a cyclopropyl group; cyclobutyl group; cyclopentyl group; 3-methylcyclopentyl group; 2,3-dimethylcyclopentyl group; cyclohexyl group; 3-methylcyclohexyl group; 4-methylcyclohexyl group; 2,3-dimethylcyclohexyl group; 3,4,5-trimethylcyclohexyl group; 4-tert-butylcyclohexyl group; cycloheptyl group; There is a cyclooctyl group, and the like, but is not limited thereto.

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C30. Specifically, it is preferably 1 to 20 carbon atoms. More specifically, it is preferable that it has 1 to 10 carbon atoms. Specifically, a methoxy group; ethoxy group; n-propoxy group; isopropoxy group; i-propyloxy group; n-butoxy group; isobutoxy group; tert-butoxy group; sec-butoxy group; n-pentyloxy group; neopentyloxy group; isopentyloxy group; n-hexyloxy group; 3,3-dimethylbutyloxy group; 2-ethylbutyloxy group; n-octyloxy group; n-nonyloxy group; n-decyloxy group; benzyloxy group; It may be a p-methylbenzyloxy group, but is not limited thereto.

In the present specification, the amine group is -NH ₂ ; an alkylamine group; N-alkylarylamine group; arylamine group; N-aryl heteroarylamine group; It may be selected from the group consisting of an N-alkylheteroarylamine group and a heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group include a methylamine group; dimethylamine group; ethylamine group; diethylamine group; phenylamine group; naphthylamine group; biphenylamine group; anthracenylamine group; 9-methylanthracenylamine group; diphenylamine group; N-phenylnaphthylamine group; ditolylamine group; N-phenyltolylamine group; triphenylamine group; N-phenylbiphenylamine group; N-phenylnaphthylamine group; N-biphenylnaphthylamine group; N-naphthylfluorenylamine group; N-phenylphenanthrenylamine group; N-biphenylphenanthrenylamine group; N-phenylfluorenylamine group; N-phenylterphenylamine group; N-phenanthrenylfluorenylamine group; N-biphenylfluorenylamine group and the like, but is not limited thereto.

In the present specification, the silyl group may be represented by the formula of -SiRaRbRc, wherein Ra, Rb and Rc are the same as or different from each other, and each independently hydrogen; a substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. The silyl group is specifically a trimethylsilyl group; triethylsilyl group; t-butyldimethylsilyl group; vinyl dimethyl silyl group; propyldimethylsilyl group; triphenylsilyl group; diphenylsilyl group; There is a phenylsilyl group, but is not limited thereto.

In the present specification, the phosphine oxide group is specifically a diphenylphosphine oxide group; Dinaphthyl phosphine oxide group, and the like, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms. The aryl group may be monocyclic or polycyclic. When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but preferably 6 to 30 carbon atoms. More specifically, it is preferable that it has 6 to 20 carbon atoms. Specifically, the monocyclic aryl group includes a phenyl group; biphenyl group; It may be a terphenyl group, and the like, but is not limited thereto. When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it has 10 to 30 carbon atoms, and more specifically, it is preferable that it has 10 to 20 carbon atoms. Specifically, the polycyclic aryl group includes a naphthyl group; anthracenyl group; phenanthryl group; triphenyl group; pyrenyl group; phenalenyl group; perylenyl group; chrysenyl group; It may be a fluorenyl group, but is not limited thereto.

As used herein, the "adjacent" group means a substituent substituted on an atom directly connected to the atom in which the substituent is substituted, a substituent sterically closest to the substituent, or another substituent substituted on the atom in which the substituent is substituted. can For example, two substituents substituted at an ortho position in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as "adjacent" groups.

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

In the present specification, the heteroaryl group includes one or more atoms other than carbon, that is, heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se and S. The number of carbon atoms is not particularly limited, but preferably has 2 to 30 carbon atoms, more preferably 2 to 20 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heteroaryl group include a thiophene group; furanyl group; pyrrole group; imidazolyl group; thiazolyl group; oxazolyl group; oxadiazolyl group; pyridyl group; bipyridyl group; pyrimidyl group; triazinyl group; triazolyl group; acrydyl group; pyridazinyl group; pyrazinyl group; quinolinyl group; quinazolinyl group; quinoxalinyl group; phthalazinyl group; pyrido pyrimidyl group; pyrido pyrazinyl group; pyrazino pyrazinyl group; isoquinolinyl group; indolyl group; carbazolyl group; benzoxazolyl group; benzimidazolyl group; benzothiazolyl group; benzocarbazolyl group; benzothiophene group; dibenzothiophene group; benzofuranyl group; phenanthroline; isoxazolyl group; thiadiazolyl group; There is a phenothiazinyl group and a dibenzofuranyl group, but is not limited thereto.

In the present specification, the arylene group means that the aryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the aryl group described above may be applied.

In the present specification, the heteroarylene group means that the heteroaryl group has two bonding positions, that is, a divalent group. Except that each of these is a divalent group, the description of the heteroaryl group described above may be applied.

In an exemplary embodiment of the present specification, the R ₁ to R ₆ are the same as or different from each other, and each independently hydrogen, deuterium, a substituted or unsubstituted C 1 to C 10 alkyl group, a halogen group, a nitrile group, or an alkyl group Or an unsubstituted silyl group, a phosphine oxide group unsubstituted or substituted with an aryl group, a substituted or unsubstituted C6-C30 aryl group, or a substituted or unsubstituted 3-30 heteroaryl group.

In an exemplary embodiment of the present specification, the R ₁ to R ₆ are the same as or different from each other, and each independently hydrogen, deuterium, a nitrile group, F, Br, Cl, I, a silyl group substituted with a methyl group, or a phenyl group phosphine oxide group, methyl group, ethyl group, propyl group, isopropyl group, butyl group, terbutyl group, phenyl group, biphenyl group, naphthyl group, terphenyl group, anthracene group, carbazole group, dibenzofuran group, or dibenzothi It's Oppengi.

In an exemplary embodiment of the present specification, R ₁ to R ₆ are hydrogen.

In an exemplary embodiment of the present specification, L is a direct bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroarylene group having 3 to 30 carbon atoms.

In an exemplary embodiment of the present specification, L is a direct bond, a substituted or unsubstituted arylene group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroarylene group including N, O or S having 3 to 30 carbon atoms. to be.

In one embodiment of the present specification, L is a direct bond; an arylene group having 6 to 30 carbon atoms that is unsubstituted or substituted with a nitrile group or an alkyl group; or a heteroarylene group containing 3 to 30 carbon atoms, N, O, or S substituted or unsubstituted with a nitrile group or an alkyl group.

In one embodiment of the present specification, L is a direct bond; phenylene group; divalent biphenyl group; a divalent terphenyl group; a divalent anthracene group; a divalent phenanthrene group; a divalent triphenylene group; a divalent carbazole group; a divalent dibenzofuran group; a divalent dibenzothiophene group; a divalent triazine group; a divalent pyrimidine group; or a divalent pyridine group,

the phenylene group; divalent biphenyl group; a divalent terphenyl group; a divalent anthracene group; a divalent phenanthrene group; a divalent triphenylene group; a divalent carbazole group; a divalent dibenzofuran group; a divalent dibenzothiophene group; a divalent triazine group; a divalent pyrimidine group; Alternatively, the divalent pyridine group is unsubstituted or substituted with a nitrile group or an alkyl group.

In one embodiment of the present specification, L is a direct bond; a phenylene group unsubstituted or substituted with a nitrile group or an alkyl group; a divalent dibenzofuran group; or a divalent dibenzothiophene group.

In one embodiment of the present specification, L is a direct bond; a phenylene group unsubstituted or substituted with a nitrile group; a divalent dibenzofuran group; or a divalent dibenzothiophene group.

In an exemplary embodiment of the present specification, when L is a phenylene group substituted with a nitrile group, A is bonded to the core structure and the ortho position.

In an exemplary embodiment of the present specification, when L is a phenylene group substituted with a nitrile group, A is bonded to the core structure and the meta position.

In the exemplary embodiment of the present specification, when L is a phenylene group substituted with a nitrile group, A is bonded to the core structure and the para (para) position.

In an exemplary embodiment of the present specification, L is a phenylene group, a divalent dibenzofuran group; or when a divalent dibenzothiophene group, the phenylene group, a divalent dibenzofuran group; Alternatively, the divalent dibenzothiophene group is unsubstituted or substituted with 1 to 3 nitrile groups.

In an exemplary embodiment of the present specification, L is a phenylene group, a divalent dibenzofuran group; or when a divalent dibenzothiophene group, the phenylene group, a divalent dibenzofuran group; Alternatively, the divalent dibenzothiophene group is substituted with one nitrile group.

In an exemplary embodiment of the present specification, L is a phenylene group, a divalent dibenzofuran group; or when a divalent dibenzothiophene group, the phenylene group, a divalent dibenzofuran group; or a divalent dibenzothiophene group is substituted with two nitrile groups.

In an exemplary embodiment of the present specification, L is a phenylene group, a divalent dibenzofuran group; or when a divalent dibenzothiophene group, the phenylene group, a divalent dibenzofuran group; Alternatively, the divalent dibenzothiophene group is substituted with three nitrile groups.

In an exemplary embodiment of the present specification, A is a substituted or unsubstituted trivalent aryl group, or a substituted or unsubstituted trivalent heteroaryl group.

In an exemplary embodiment of the present specification, A is a substituted or unsubstituted trivalent aryl group, or a substituted or unsubstituted trivalent N-containing heteroaryl group.

In an exemplary embodiment of the present specification, A is a substituted or unsubstituted trivalent aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted trivalent N-containing heteroaryl group having 3 to 30 carbon atoms.

In an exemplary embodiment of the present specification, A is a trivalent aryl group having 6 to 30 carbon atoms substituted or unsubstituted with a nitrile group, or a trivalent N-containing heteroaryl group having 3 to 30 carbon atoms unsubstituted or substituted with a nitrile group .

In an exemplary embodiment of the present specification, A is a trivalent phenyl group, a trivalent triazine group, a trivalent pyrimidine group, or a trivalent pyridine group, and the trivalent phenyl group, a trivalent pyrimidine group, or a trivalent pyridine group Each is substituted or unsubstituted with a nitrile group.

In an exemplary embodiment of the present specification, A is a trivalent phenyl group, a trivalent triazine group, a trivalent pyrimidine group unsubstituted or substituted with a nitrile group, or a trivalent pyridine group unsubstituted or substituted with a nitrile group.

In an exemplary embodiment of the present specification, A is a trivalent triazine group.

In an exemplary embodiment of the present specification, A is a trivalent pyrimidine group unsubstituted or substituted with a nitrile group.

In an exemplary embodiment of the present specification, A is a trivalent pyridine group unsubstituted or substituted with a nitrile group.

In an exemplary embodiment of the present specification, A is a trivalent phenyl group unsubstituted or substituted with a nitrile group.

In an exemplary embodiment of the present specification, A is a trivalent pyrimidine group unsubstituted or substituted with one nitrile group.

In an exemplary embodiment of the present specification, A is a trivalent pyridine group unsubstituted or substituted with one nitrile group.

In an exemplary embodiment of the present specification, A is a trivalent phenyl group unsubstituted or substituted with one nitrile group.

In an exemplary embodiment of the present specification, A is a trivalent pyridine group unsubstituted or substituted with two nitrile groups.

In an exemplary embodiment of the present specification, A is a trivalent phenyl group unsubstituted or substituted with two nitrile groups.

In an exemplary embodiment of the present specification, A is a trivalent phenyl group unsubstituted or substituted with three nitrile groups.

In an exemplary embodiment of the present specification, A is any one selected from the following substituents.

The dotted line indicates L and a connection portion.

In an exemplary embodiment of the present specification, -L-A is substituted with 0 to 3 nitrile groups.

In an exemplary embodiment of the present specification, -L-A is substituted with 0 nitrile groups.

In an exemplary embodiment of the present specification, -L-A is substituted with one nitrile group.

In an exemplary embodiment of the present specification, -L-A is substituted with two nitrile groups.

In an exemplary embodiment of the present specification, -L-A is substituted with three nitrile groups.

In an exemplary embodiment of the present specification, the B ₁ and B ₂ are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 10 alkyl group, a substituted or unsubstituted C 3 to C 10 cycloalkyl group, A substituted or unsubstituted C 6 to C 30 aryl group, a substituted or unsubstituted C 3 to C 30 heteroaryl group, a substituted or unsubstituted C 1 to C 10 alkoxy group, a substituted or unsubstituted C 6 to C 30 an aryloxy group, a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms, a substituted or unsubstituted alkenyl group having 1 to 10 carbon atoms, or a substituted or unsubstituted alkynyl group having 1 to 10 carbon atoms.

In an exemplary embodiment of the present specification, the B ₁ and B ₂ are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 10 alkyl group, a substituted or unsubstituted C 3 to C 10 cycloalkyl group, a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

In an exemplary embodiment of the present specification, B ₁ and B ₂ are the same as or different from each other, and each independently a substituted or unsubstituted C3 to C10 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group , or a substituted or unsubstituted C 3 to C 30 heteroaryl group.

In an exemplary embodiment of the present specification, B ₁ and B ₂ are the same as or different from each other, and each independently a substituted or unsubstituted C 6 to C 30 aryl group, or a substituted or unsubstituted C 3 to C 30 hetero It is an aryl group.

In an exemplary embodiment of the present specification, the B ₁ and B ₂ are the same as or different from each other, and each independently an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with an alkyl group, or a substituted or unsubstituted carbon number 3 to 30 is a heteroaryl group of

In an exemplary embodiment of the present specification, the B ₁ and B ₂ are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; a biphenyl group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; a terphenyl group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; an anthracene group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; a phenanthrene group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; a triphenylene group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; a pyrene group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; a fluorene group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; a carbazole group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; a dibenzofluorene group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms; or a dibenzothiophene group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms.

In an exemplary embodiment of the present specification, B ₁ and B ₂ are the same as or different from each other, and each independently a phenyl group, a biphenyl group, a terphenyl group, an anthracene group, a phenant unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms. Rene group, triphenylene group, pyrene group, fluorene group, dibenzofuran group or dibenzothiophene group.

In an exemplary embodiment of the present specification, the B ₁ and B ₂ are a phenyl group unsubstituted or substituted with a terbutyl group; or a biphenyl group.

In an exemplary embodiment of the present specification, the B ₁ and B ₂ are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with a terbutyl group; biphenyl group; It is a dibenzofuran group or a dibenzothiophene group.

In the exemplary embodiment of the present specification, B ₁ is a phenyl group unsubstituted or substituted with a terbutyl group, and B ₂ is a dibenzofuran group or a dibenzothiophene group.

In an exemplary embodiment of the present specification, B ₁ is an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with an alkyl group, and B ₂ is a substituted or unsubstituted heteroaryl group having 3 to 30 carbon atoms.

In an exemplary embodiment of the present specification, B ₂ is an aryl group having 6 to 30 carbon atoms substituted or unsubstituted with an alkyl group, and B ₁ is a heteroaryl group having 3 to 30 carbon atoms substituted or unsubstituted.

In the exemplary embodiment of the present specification, B ₁ is a phenyl group, and B ₂ is a dibenzofuran group or a dibenzothiophene group.

In the exemplary embodiment of the present specification, B ₂ is a phenyl group unsubstituted or substituted with a terbutyl group, and B ₁ is a dibenzofuran group or a dibenzothiophene group.

In an exemplary embodiment of the present specification, B ₂ is a phenyl group, and B ₁ is a dibenzofuran group or a dibenzothiophene group.

In an exemplary embodiment of the present specification, the compound of Formula 1 is selected from the following structures.

In the present specification, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

In this specification, when a member is said to be located "on" another member, this includes not only a case in which a member is in contact with another member but also a case in which another member exists between the two members.

The organic light emitting device of the present invention includes a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein one or more of the organic material layers may include the aforementioned compound.

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

The organic material layer of the organic light emitting device of the present invention may have a single-layer structure, but may have a multi-layer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention may have a structure including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc. as an organic material layer. However, the structure of the organic light emitting device is not limited thereto and may include a smaller number of organic material layers.

For example, the structure of the organic light emitting device of the present invention may have a structure as shown in FIGS. 1 and 2 , but is not limited thereto.

1 illustrates a structure of an organic light emitting device in which an anode 2 , a light emitting layer 3 , and a cathode 4 are sequentially stacked on a substrate 1 .

2 shows an anode 2, a hole injection layer 5, a hole transport layer 6, an electron blocking layer 7, a light emitting layer 3, a hole blocking layer 8, an electron injection and transport layer on the substrate 1 The structure of the organic light emitting device in which (9) and the cathode (4) are sequentially stacked is exemplified. The compound of the present invention is preferably contained in the light emitting layer (3).

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

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

The organic light emitting device may have, for example, a stacked structure as follows, 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 transport layer/light emitting layer/electron transport layer/cathode

(4) anode / hole transport layer / light emitting layer / electron transport layer / electron injection layer / cathode

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

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

(7) anode/hole transport layer/electron blocking layer/light emitting layer/electron transport layer/cathode

(8) anode / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / electron injection layer / cathode

(9) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / cathode

(10) anode / hole injection layer / hole transport layer / electron blocking layer / light emitting layer / electron transport layer / electron injection layer / cathode

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

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

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

(14) anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode

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

In an exemplary embodiment of the present invention, the organic material layer includes an emission layer, and the emission layer includes the compound of Formula 1 above.

In an exemplary embodiment of the present invention, the light emitting layer includes the compound of Formula 1 as a dopant.

In an exemplary embodiment of the present invention, the light emitting layer includes the compound of Formula 1 as a thermally activated delayed fluorescence (TADF) dopant.

In an exemplary embodiment of the present invention, the light emitting layer includes a host and a dopant.

In an exemplary embodiment of the present invention, the light emitting layer includes a host and a thermally activated delayed fluorescence dopant.

In an exemplary embodiment of the present invention, the light emitting layer includes a fluorescent host or a phosphorescent host.

In an exemplary embodiment of the present invention, the light emitting layer includes a host and a dopant in a mass ratio of 99:1 to 50:50.

In an exemplary embodiment of the present invention, the light emitting layer includes a host and a dopant in a mass ratio of 90:10 to 60:40.

In an exemplary embodiment of the present invention, the light emitting layer includes a host and a dopant in a mass ratio of 80:20 to 60:40.

In an exemplary embodiment of the present invention, the light emitting layer includes a host and a thermally activated delayed fluorescence dopant in a mass ratio of 90:10 to 60:40.

In an exemplary embodiment of the present invention, the light emitting layer includes a host and a thermally activated delayed fluorescence dopant in a mass ratio of 80:20 to 60:40.

When the content of the host and the dopant satisfies the above range, it is possible to manufacture an organic light emitting device having high efficiency and long lifespan by inversely transferring triplet energy to singlet energy.

In the exemplary embodiment of the present specification, the organic material layer includes a light emitting layer, the light emitting layer includes the compound as a dopant of the light emitting layer, and may further include a host. In this case, the content of the dopant may be included in an amount of 1 part by weight to 60 parts by weight, preferably 30 parts by weight to 50 parts by weight, based on 100 parts by weight of the host.

According to an exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes at least one selected from a condensed aromatic ring derivative and a heterocyclic compound as a host of the emission layer.

According to an exemplary embodiment of the present specification, the condensed aromatic ring derivative includes an anthracene derivative, a pyrene derivative, a naphthalene derivative, a pentacene derivative, a phenanthrene compound, a fluoranthene compound, and the like, and the hetero ring-containing compound includes a carbazole derivative , a dibenzofuran derivative, a ladder-type furan compound, a pyrimidine derivative, and the like, but is not limited thereto.

According to an exemplary embodiment of the present specification, the light emitting layer includes the compound as a dopant, and may further include a compound represented by the following Chemical Formula F as a host, but is not limited thereto.

[Formula F]

In the formula F,

L13 is a substituted or unsubstituted (b+1) valent aryl group; Or a substituted or unsubstituted (b+1) valent heteroaryl group,

G11 and G12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; cyano group; Or a heteroaryl group containing O or S,

b13 is an integer of 1 to 3, and when b13 is 2 or more, L13 is the same as or different from each other,

는 서로 같거나 상이하다.b is 1 or 2, if b is 2

are the same or different from each other.

According to an exemplary embodiment of the present specification, the organic material layer includes an emission layer, and the emission layer includes a dopant including the compound described above and a host represented by Formula F in a weight ratio of 1:99 to 50:50.

In an exemplary embodiment of the present specification, in Formula F, L13 is a substituted or unsubstituted (b+1) aryl group having 6 to 16 carbon atoms; or a substituted or unsubstituted C2-C16 (b+1) heteroaryl group.

In the exemplary embodiment of the present specification, in Formula F, L13 is a substituted or unsubstituted (b+1) aryl group having 6 to 12 carbon atoms; or a substituted or unsubstituted C2-C12 (b+1) heteroaryl group.

In an exemplary embodiment of the present specification, in Formula F, L13 is a substituted or unsubstituted (b+1) valent phenyl group; a substituted or unsubstituted (b+1) biphenyl group; a substituted or unsubstituted (b+1) dibenzofuranyl group; or a substituted or unsubstituted (b+1) valent pyridinyl group.

In an exemplary embodiment of the present specification, in Formula F, when L13 is a substituted (b+1) valent aryl group, the substituent of the (b+1) valent aryl group is an aryl group substituted with a heteroaryl group.

In an exemplary embodiment of the present specification, in Formula F, G11 and G12 are the same as or different from each other, and each independently hydrogen; or a cyano group.

In an exemplary embodiment of the present specification, in Formula F, b13 is 1.

In an exemplary embodiment of the present specification, in Formula F, b13 is 2.

In an exemplary embodiment of the present specification, the compound represented by Formula F is any one selected from the following compounds.

In an exemplary embodiment of the present invention, the light emitting layer includes a host, a dopant, and a fluorescent light emitting material.

In an exemplary embodiment of the present invention, the light emitting layer includes a host, a thermally activated delayed fluorescent dopant, and a fluorescent light.

In an exemplary embodiment of the present invention, the light emitting layer may include the compound represented by Formula 1 as a dopant, a fluorescent host or a phosphorescent host, and further include a fluorescent light emitting material. The dopant content may be 1 to 50 parts by weight based on 100 parts by weight of the host, and the content of the fluorescent material may be 0 to 10 parts by weight based on 100 parts by weight of the host.

In an exemplary embodiment of the present invention, the content of the dopant is 10 to 50 parts by weight based on 100 parts by weight of the host, and the fluorescent material is 2 to 10 parts by weight based on 100 parts by weight of the host.

In addition, when a fluorescent material is further included in the light emitting layer, the compound represented by Formula 1 transfers exciton energy to the fluorescent material to cause light emission in the fluorescent material, so that high-brightness light emission is possible, An organic light emitting diode having a low driving voltage and a long lifespan can be manufactured.

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

According to an exemplary embodiment of the present specification, the organic material layer includes an emission layer, the emission layer includes the compound, and further includes a fluorescent light-emitting material. In this case, the content of the fluorescent material may be included in an amount of 0 parts by weight to 10 parts by weight based on 100 parts by weight of the compound. Since the fluorescent material receives excitons from the compound and finally emits light, the color purity of the device can be increased by using the fluorescent material having a narrow half maximum width, and exciton-polaron quenching of the compound can be performed. There is an advantage of increasing the life of the device by preventing it. The full width at half maximum means the thickness of the peak at a height that is half (1/2) of the maximum emission peak height on the emission spectrum.

Examples of the fluorescent material may include an anthracene-based compound, a pyrene-based compound, a floranthene-based compound, a perylene-based compound, a boron-based compound, or the following structures, but is not limited thereto.

In addition, the compound of Formula 1 may be used as a thermally activated delayed fluorescence dopant (TADF), and the compound of Formula 1 has a ΔE _st value of 0.3 eV or less of delayed fluorescence and an orientation factor characteristic of more than 0.7 When used as a green-based thermally activated delayed fluorescent dopant with

The thermally activated delayed fluorescence refers to a phenomenon in which a reverse intersystem transition is induced from a triplet excited state to a singlet excited state by thermal energy, and excitons in the singlet excited state move to the ground state to cause fluorescence. . In addition, the ΔE _st refers to a value of singlet energy - triplet energy.

In an exemplary embodiment of the present invention, the organic material layer includes a hole injection layer, a hole transport layer, or a hole injection and transport layer, and the hole injection layer, the hole transport layer, or the hole injection and transport layer may include the compound of Formula 1 can

In an exemplary embodiment of the present invention, the organic material layer includes an electron injection layer, an electron transport layer, or an electron injection and transport layer, and the electron injection layer, the electron transport layer, or the electron injection and transport layer may contain the compound of Formula 1 can

In an exemplary embodiment of the present invention, the organic material layer may include an electron blocking layer or a hole blocking layer, and the electron blocking layer or the hole blocking layer may include the compound of Formula 1 above.

The compound may be formed into an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method refers to spin coating, dip coating, inkjet printing, screen printing, spraying, roll coating, and the like, but is not limited thereto.

For example, the organic light emitting device according to the present invention uses a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, to form a metal or a conductive metal oxide or an alloy thereof on a substrate. to form an anode, an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an organic material layer including the compound of Formula 1 thereon, a material that can be used as a cathode is deposited thereon It can be manufactured by In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

As the anode material, a material having a large work function is generally preferred so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); ZnO:Al or SnO ₂ : a combination of a metal such as Sb and an oxide; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDT), polypyrrole, and polyaniline, but are not limited thereto.

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

The hole injection material is a material capable of well injecting holes from the anode at a low voltage, and it is preferable that the highest occupied molecular orbital (HOMO) of the hole injection material is between the work function of the anode material and the HOMO of the surrounding organic material layer. Specific examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. of organic substances, anthraquinones, polyaniline and polythiophene-based conductive polymers, and the like, but are not limited thereto.

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

The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ); carbazole-based compounds; dimerized styryl compounds; BAlq; 10-hydroxybenzo quinoline-metal compounds; compounds of the benzoxazole, benzthiazole and benzimidazole series; Poly(p-phenylenevinylene) (PPV)-based polymers; spiro compounds; polyfluorene, rubrene, and the like, but is not limited thereto.

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

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

The present specification also provides a method of manufacturing an organic light emitting device formed using the compound.

Examples of the dopant material include an aromatic compound, a strylamine compound, a boron complex, a fluoranthene compound, and a metal complex. Specifically, the aromatic compound is a condensed aromatic ring derivative having a substituted or unsubstituted arylamino group, and includes pyrene, anthracene, chrysene, periflanthene, and the like, having an arylamino group. As the styrylamine compound, a substituted or unsubstituted A compound in which at least one arylvinyl group is substituted with an arylamine, one or two or more substituents selected from the group consisting of an aryl group, a silyl group, an alkyl group, a cycloalkyl group, and an arylamino group are substituted or unsubstituted. Specifically, there are styrylamine, styryldiamine, styryltriamine, styryltetraamine, and the like, but is not limited thereto. In addition, examples of the metal complex include, but are not limited to, an iridium complex and a platinum complex.

The electron transport layer is a layer that receives electrons from the electron injection layer and transports them to the light emitting layer. do. Specific examples include Al complex of 8-hydroxyquinoline; complexes comprising Alq3; organic radical compounds; hydroxyflavone-metal complexes, and the like, but are not limited thereto. The electron transport layer may be used with any desired cathode material as used in accordance with the prior art. In particular, examples of suitable cathode materials are conventional materials having a low work function and followed by a layer of aluminum or silver. Specifically cesium, barium, calcium, ytterbium and samarium, followed in each case by an aluminum layer or a silver layer.

The electron injection layer is a layer that injects electrons from the electrode, has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect with respect to the light emitting layer or the light emitting material, and hole injection of excitons generated in the light emitting layer A compound which prevents movement to a layer and is excellent in the ability to form a thin film is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

The hole blocking layer is a layer that blocks the holes from reaching the cathode, and may be generally formed under the same conditions as the hole injection layer. Specifically, there are oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, aluminum complex, and the like, but is not limited thereto.

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

Synthesis example One.

of intermediate 1 synthesis

Dissolve 13 g of 6-bromo-5-phenyl-5,12-dihydroindolo [3,2-a] carbazole in 200 ml of THF, wait for 30 minutes at -78 ° C., and then 3.03 ml of n-BuLi (1.6 M) After the slow dropwise addition, a solution of 5.7 g of 9H-fluoren-9-one in THF was slowly added dropwise. After waiting at room temperature for 1 hour, water was added, followed by extraction using ethyl acetate, and all solvents were removed. Thereafter, the mixture was stirred with acetic acid and HCl (10:1) for 2 hours, and then filtered and recrystallized to obtain 11 g of Intermediate 1. (yield 70%).

MS[M+H]+ = 495

Synthesis of compound 1

In a nitrogen atmosphere, 7 g of Intermediate 1 and 4.5 g of 5-(4,6-diphenyl-1,3,5-triazin-2-yl)-2-fluorobenzonitrile were added to 80 ml of dimethylformamide and then cesium After 14 g of carbonate was added, stirred at 100° C. for 8 hours, and then poured into water to obtain a solid compound. Then, 9 g of compound 1 was obtained through recrystallization. (yield 77%).

MS[M+H]+ = 827

Synthesis of compound 2

In a nitrogen atmosphere, 7 g of Intermediate 1, 4.6 g of 2-(4-fluorophenyl) -4,6-diphenyl-1,3,5-triazine was put into 80 ml of dimethylformamide, 14 g of cesium carbonate was added, and then 100 After stirring at ℃ for 8 hours, it was poured into water to obtain a solid compound. Then, 8.4 g of compound 2 was obtained through recrystallization. (yield 74%).

MS[M+H]+ = 802

Synthesis of compound 3

In a nitrogen atmosphere, 7 g of Intermediate 1 and 5.0 g of 5-(4,6-diphenylpyrimidin-2-yl)-2-fluorobenzonitrile were added to 80 ml of dimethylformamide, 14 g of cesium carbonate was added, and then 100 ° C. After stirring for 8 hours, it was poured into water to obtain a solid compound. Then, 8.8 g of compound 3 was obtained through recrystallization. (yield 75%).

MS[M+H]+ = 826

Synthesis of compound 4

In a nitrogen atmosphere, 7 g of Intermediate 1, 5.3 g of 2-(3-cyano-4-fluorophenyl)-4,6-diphenylpyridine-5-carbonitrile was put into 80 ml of dimethylformamide, and 14 g of cesium carbonate was added. After stirring at 100° C. for 8 hours, it was poured into water to obtain a solid compound. Then, 9.1 g of compound 4 was obtained through recrystallization. (yield 76%).

MS[M+H]+ = 851

compound 5 synthesis

In a nitrogen atmosphere, 7 g of Intermediate 1, 5.3 g of 2-(2-fluorophenyl) -4,6-diphenylpyridine-3,5-dicarbonitrile were added to 80 ml of dimethylformamide, 14 g of cesium carbonate was added, and then 100 After stirring at ℃ for 8 hours, it was poured into water to obtain a solid compound. Thereafter, 9.2 g of compound 5 was obtained through recrystallization. (yield 76%).

MS[M+H]+ = 851

Synthesis of compound 6

In a nitrogen atmosphere, 7 g of Intermediate 1 and 3.6 g of 2-fluoro-4,6-diphenyl-1,3,5-triazine were put into 80 ml of dimethylformamide, 14 g of cesium carbonate was added, and then stirred at 100° C. for 8 hours. It was poured into water to obtain a solid compound. Then, 8.1 g of compound 6 was obtained through recrystallization. (yield 79%).

MS[M+H]+ = 726

Synthesis of compound 7

In a nitrogen atmosphere, 7 g of Intermediate 1 and 3.9 g of 4-fluoro-2,6-diphenylpyrimidine-5-carbonitrile were added to 80 ml of dimethylformamide, 14 g of cesium carbonate was added, and then stirred at 100° C. for 8 hours and then washed with water. poured to obtain a solid compound. Then, 7.7 g of compound 7 was obtained through recrystallization. (yield 73%).

MS[M+H]+ = 750

Synthesis of compound 8

7 g of Intermediate 1 in a nitrogen atmosphere, 5-(4-(dibenzo[b,d]furan-3-yl)-6-phenyl-1,3,5-triazin-2-yl)-2-fluorobenzo After putting 6.3 g of nitrile in 80 ml of dimethylformamide, 14 g of cesium carbonate was added, and after stirring at 100° C. for 8 hours, it was poured into water to obtain a solid compound. Then, 9.7 g of compound 8 was obtained through recrystallization. (yield 75%).

MS[M+H]+ = 918

Synthesis of compound 9

In a nitrogen atmosphere, 7 g of Intermediate 1 and 6.5 g of 4-(dibenzo[b,d]thiophen-2-yl)-2-(4-fluorophenyl)-6-phenylpyrimidine-5-carbonitrile were reacted with dimethyl After putting in 80ml of formamide, 14g of cesium carbonate was added, stirred at 100°C for 8 hours, and then poured into water to obtain a solid compound. Then, 9.4 g of compound 9 was obtained through recrystallization. (Yield 71%).

MS[M+H]+ = 933

Synthesis of compound 10

In a nitrogen atmosphere, 7 g of Intermediate 1, 2-(1-fluorodibenzo[b,d]furan-2-yl)-4,6-diphenyl-1,3,5-triazine 5.9g were mixed with dimethylformamide After putting in 80ml, 14g of cesium carbonate was added, stirred at 100°C for 8 hours, and then poured into water to obtain a solid compound. Thereafter, 9.2 g of compound 10 was obtained through recrystallization. (yield 73%).

MS[M+H]+ = 893

Synthesis of compound 11

In a nitrogen atmosphere, 7 g of Intermediate 1 and 6.2 g of 2-(1-fluorodibenzo[b,d]thiophen-2-yl)-4,6-diphenyl-1,3,5-triazine were mixed with dimethylform After putting in 80ml of amide, 14g of cesium carbonate was added, stirred at 100°C for 8 hours, and then poured into water to obtain a solid compound. Then, 9.6 g of compound 11 was obtained through recrystallization. (yield 75%).

MS[M+H]+ = 909

< comparative example 1-1>

A glass substrate coated with a thin film of ITO (Indium Tin Oxide) to a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone and methanol, dried, and transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator. Each thin film was laminated on the prepared ITO transparent electrode by vacuum deposition at a vacuum degree of 5.0×10 ⁻⁴ Pa. First, hexaazatriphenylene-hexanitrile (HAT-CN) was thermally vacuum deposited to a thickness of 500 Å on ITO to form a hole injection layer.

The following compound NPB was vacuum-deposited on the hole injection layer to form a hole transport layer (300 Å).

An electron blocking layer (100 Å) was formed by vacuum-depositing the following compound EB1 to a thickness of 100 Å on the hole transport layer.

Then, on the electron blocking layer, the following compounds m-CBP and A1 to a thickness of 300 Å were vacuum-deposited at a weight ratio of 70:30 to form a light emitting layer.

A hole blocking layer was formed by vacuum-depositing the following compound HB1 to a thickness of 100 Å on the light emitting layer.

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

In the above process, the deposition rate of the organic material was maintained at 0.4 Å/sec to 0.7 Å/sec, the deposition rate of lithium fluoride of the negative electrode was maintained at 0.3 Å/sec, and the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 2x10. ^- Maintaining ⁷ torr to 5x10 ^{- 6} torr, an organic light emitting device was manufactured.

< Experimental example 1-1 to 1-11>

An organic light emitting diode was manufactured in the same manner as in Comparative Example 1-1, except that the compound of Table 1 was used instead of Compound A1 in Comparative Example 1-1.

For the organic light emitting devices of Experimental Examples 1-1 to 1-11 and Comparative Example 1-1, the driving voltage (V) and current efficiency (cd/A) measured at a current density of 10 mA/cm 2 , at 3000 cd/m ² The time until the brightness is reduced to 95% (T ₉₅ ) was measured, and is shown in Table 1 below.

division compound
(Light emitting layer) Voltage
(V) efficiency
(cd/A) T ₉₅
(hr) Experimental Example 1-1 One 4.0 35 118 Experimental Example 1-2 2 4.1 32 115 Experimental Example 1-3 3 4.0 35 114 Experimental Example 1-4 4 3.9 35 113 Experimental Example 1-5 5 3.9 34 114 Experimental Example 1-6 6 4.2 33 112 Experimental Example 1-7 7 4.0 31 112 Experimental Example 1-8 8 4.1 36 110 Experimental Example 1-9 9 4.1 36 110 Experimental Example 1-10 10 4.0 32 113 Experimental Example 1-11 11 4.0 32 113 Comparative Example 1-1 A1 4.9 11 80

As shown in Table 1, the devices of Experimental Examples 1-1 to 1-11 using the compound of Formula 1 had lower voltages, and improved efficiency and lifespan than the devices using the material of Compound A1 in Comparative Example 1-1. improved

In particular, with electron acceptor properties at N of spiro [diindolo[3,2-b:3',2',1'-de]acridine-10,9'-fluorene] with electron donor properties It maximizes the CT (Charge Transfer) characteristic by combining the substituents. As the substituent having an electron accepting property, an N-containing monocyclic ring such as triazine and pyrimidine, an aryl group substituted with a nitrile group, a heteroaryl group substituted with a nitrile group, etc. may be used.

In the case of Compound A1 used in Comparative Example 1-1, the position at which the substituent is substituted on the core is different from the present invention. In the case of Compound A1, a substituent is bonded to the benzene ring of the core, and in this case, the CT characteristics are weaker than that of Compounds 1 to 11 used in Examples 1-1 to 1-11.

Therefore, it was confirmed that the compound according to the present invention has excellent light emitting ability and has a long lifespan, so that it can be applied to delayed fluorescent organic light emitting devices.

< comparative example 2-1>

A glass substrate coated with a thin film of ITO (Indium Tin Oxide) to a thickness of 1,000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone and methanol, dried, and transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator. Each thin film was laminated on the prepared ITO transparent electrode by vacuum deposition at a vacuum degree of 5.0Х10 ^-4 Pa. First, hexaazatriphenylene-hexanitrile (HAT-CN) was thermally vacuum deposited to a thickness of 500 Å on ITO to form a hole injection layer.

The following compound NPB was vacuum-deposited on the hole injection layer to form a hole transport layer (300 Å).

An electron blocking layer (100 Å) was formed by vacuum-depositing the following compound EB1 to a thickness of 100 Å on the hole transport layer.

Then, the following compounds m-CBP, A1, and GD1 to a thickness of 300 Å were vacuum-deposited on the electron blocking layer in a weight ratio of 68:30:2 to form a light emitting layer.

A hole blocking layer was formed by vacuum-depositing the following compound HB1 to a thickness of 100 Å on the light emitting layer.

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

In the above process, the deposition rate of the organic material was maintained at 0.4 Å to 0.7 Å, the lithium fluoride of the negative electrode was maintained at a deposition rate of 0.3 Å and the aluminum was maintained at a deposition rate of 2 Å, and the vacuum degree during deposition was 2x10 ^-7 torr to 5x10 ^-6 torr. Maintained, an organic light emitting device was manufactured.

< Experimental example 2-1 to 2-11>

An organic light emitting diode was manufactured in the same manner as in Comparative Example 2-1, except that the compound of Table 2 was used instead of Compound A1 in Comparative Example 2-1.

The driving voltage (V) and current efficiency (cd/A) measured at a current density of 10 mA/cm 2 for the organic light emitting devices of Experimental Examples 2-1 to 2-11 and Comparative Example 2-1, at 3000 cd/m ² The time until the brightness is reduced to 95% (T ₉₅ ) was measured, and is shown in Table 2 below.

division compound
(Light emitting layer) Voltage
(V) efficiency
(cd/A) T ₉₅
(hr) Experimental Example 2-1 One 4.1 37 125 Experimental Example 2-2 2 4.2 33 120 Experimental Example 2-3 3 4.1 35 125 Experimental Example 2-4 4 4.0 36 126 Experimental Example 2-5 5 4.0 35 123 Experimental Example 2-6 6 4.3 36 124 Experimental Example 2-7 7 4.0 32 124 Experimental Example 2-8 8 4.1 37 118 Experimental Example 2-9 9 4.1 38 121 Experimental Example 2-10 10 4.0 34 127 Experimental Example 2-11 11 4.0 34 127 Comparative Example 2-1 A1 5.0 10 80

As shown in Table 2, compounds 1 to 11 used in the devices of Experimental Examples 2-1 to 2-11 are spiro [diindolo [3,2-b: 3 ', 2', 1'-de]acridine-10,9'-fluorene] is bonded to a substituent with electron accepting properties to nitrogen, maximizing CT (Charge Transfer) properties. In compounds 1 to 11, a triazine group, a pyrimidine group, a pyrimidine group substituted with a nitrile group, etc. were used as substituents having electron accepting properties .

Examples 2-1 to 2-11 are HF (Hyper-fluorescent) in which a light emitting layer is formed by depositing a host material, a TADF dopant material, and a fluorescent dopant material. Compounds 1 to 11 show good TADF characteristics even in the HF device. . The compounds 1 to 11 materials are not nitrogen of spiro [diindolo [3,2-b: 3 ', 2', 1'-de] acridine-10,9'-fluorene] even in HF devices, It shows better efficiency increase and lifetime increase than compound A1 in which a substituent is bonded to a benzene ring.

Therefore, it was confirmed that the compound according to the present invention has excellent light emitting ability and has a long lifespan, so that it can be applied to delayed fluorescent organic light emitting devices.

Although 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 detailed description of the invention, and this also falls within 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 blocking layer
8: hole blocking layer
9: Electron injection and transport layer

Claims (8)

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

In Formula 1,
R ₁ To R ₆ Are the same as or different from each other, and are each independently hydrogen, or deuterium;
L is a direct bond, a C6-C20 arylene group unsubstituted or substituted with a nitrile group, or a C3-C20 heteroarylene group,
A is a trivalent monocyclic N-containing heteroaryl group unsubstituted or substituted with a nitrile group,
B ₁ and B ₂ are the same as or different from each other, and are each independently an aryl group having 6 to 30 carbon atoms, or a heteroaryl group having 3 to 20 carbon atoms, unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms,
a to e are integers from 0 to 4,
When a is plural, R ₁ are the same as or different from each other,
When b is plural, R ₂ are the same as or different from each other,
When c is plural, R ₃ are the same as or different from each other,
When d is plural, R ₄ are the same as or different from each other,
When e is plural, R ₅ is the same as or different from each other. The compound according to claim 1, wherein A is a trivalent triazine group, a trivalent pyrimidine group unsubstituted or substituted with a nitrile group, or a trivalent pyridine group unsubstituted or substituted with a nitrile group. The method according to claim 1, wherein B ₁ and B ₂ are the same as or different from each other, and each independently a phenyl group, biphenyl group, terphenyl group, anthracene group, phenanthrene group, triphenyl unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms. A compound that is a ren group, a pyrene group, a fluorene group, a dibenzofuran group, or a dibenzothiophene group. The compound according to claim 1, wherein the compound represented by Formula 1 has a delayed fluorescence characteristic of 0.3 eV or less. The method according to claim 1, wherein L is a phenylene group unsubstituted or substituted with a nitrile group; a divalent dibenzofuran group; or a divalent dibenzothiophene group. The compound according to claim 1, wherein Formula 1 is any one selected from the following compounds:

a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein one or more of the organic material layers comprises the compound of any one of claims 1 to 6 light emitting element. The organic light emitting device of claim 7 , wherein the organic material layer includes a light emitting layer, and the light emitting layer includes the compound.

Images