WO2023022480A1

WO2023022480A1 - Heterocyclic compound, organic light-emitting device comprising same, and composition for organic layer of organic light-emitting device

Info

Publication number: WO2023022480A1
Application number: PCT/KR2022/012207
Authority: WO
Inventors: 이현주; 노영석; 김동준
Original assignee: 엘티소재주식회사
Priority date: 2021-08-17
Filing date: 2022-08-16
Publication date: 2023-02-23
Also published as: TW202321225A; KR20230026579A

Abstract

The present application provides: a heterocyclic compound which can significantly improve the service life, efficiency, electrochemical stability, and thermal stability of an organic light-emitting device; an organic light-emitting device comprising the heterocyclic compound; and a composition, comprising the heterocyclic compound, for an organic layer of an organic light-emitting device.

Description

Heterocyclic compound, an organic light emitting device including the same, and a composition for an organic material layer of the organic light emitting device

This application claims the benefit of the filing date of Korean Patent Application No. 10-2021-0108023 filed with the Korean Intellectual Property Office on August 17, 2021, all of which are incorporated herein.

The present specification relates to a heterocyclic compound, an organic light emitting device including the same, and a composition for an organic material layer of the organic light emitting device.

The electroluminescent device is a type of self-luminous display device, and has advantages such as a wide viewing angle, excellent contrast, and fast response speed.

The organic light emitting device has a structure in which an organic thin film is disposed between two electrodes. When voltage is applied to the organic light emitting device having such a structure, electrons and holes injected from the two electrodes are combined in the organic thin film to form a pair, and then emit light while disappearing. The organic thin film may be composed of a single layer or multiple layers as needed.

The material of the organic thin film may have a light emitting function as needed. For example, as the organic thin film material, a compound capable of constituting the light emitting layer by itself may be used, or a compound capable of serving as a host or dopant of the host-dopant type light emitting layer may be used. In addition, as a material for the organic thin film, a compound capable of performing functions such as hole injection, hole transport, electron blocking, hole blocking, electron transport, and electron injection may be used.

In order to improve the performance, lifespan or efficiency of organic light emitting devices, the development of materials for organic thin films is continuously required.

The present invention is to provide a heterocyclic compound, an organic light emitting device including the same, and a composition for an organic material layer of the organic light emitting device.

An exemplary embodiment of the present application is an organic light emitting device including an anode, a cathode, and one or more organic material layers provided between the anode and the cathode, wherein at least one layer of the organic material layer is a heterocyclic compound represented by Formula 1 and the following An organic light emitting device including the heterocyclic compound represented by Formula 2 is provided.

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

X1 is O; S; CRaRb; or NRc;

R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; -CN; Or a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms,

a is an integer from 0 to 5, and when a is 2 or more, R1 in parentheses are the same as or different from each other;

b is an integer from 0 to 4, and when b is 2 or more, R2 in parentheses are the same as or different from each other;

c is an integer from 0 to 3, and when c is 2 or more, R3 in parentheses are the same as or different from each other;

d is an integer from 0 to 2, and when d is 2, R4 in parentheses are the same as or different from each other;

Rm is hydrogen; or deuterium;

Ar1 is a substituted or unsubstituted biphenyl group; A substituted or unsubstituted dibenzofuran group; Or a substituted or unsubstituted dimethylfluorene group,

Ar2 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms;

Wherein Ra to Rc are the same as or different from each other, and each independently, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms;

Rd and Re are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms; A substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted heterocycloalkyl group having 2 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; -SiR31R32R33; -P(=0)R31R32; and a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms and a substituted or unsubstituted amine group selected from the group consisting of Or, two or more groups adjacent to each other bond to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,

R21 and R22 are the same as or different from each other, and each independently -SiR31R32R33; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

R31, R32, and R33 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

r and s are integers from 0 to 7, and when r and s are integers of 2 or more, the substituents in parentheses are the same as or different from each other.

In addition, another exemplary embodiment of the present application provides a heterocyclic compound represented by Formula 1-2 below.

[Formula 1-2]

In Formula 1-2,

X1, R1 to R4, a to d. The definitions of Rm, Ar1 and Ar2 are the same as those in Formula 1 above.

Finally, an exemplary embodiment of the present application provides a composition for an organic material layer of an organic light emitting device including the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2.

The heterocyclic compound according to an exemplary embodiment of the present application may be used as a material for an organic material layer of an organic light emitting device. The heterocyclic compound may be used as a material for a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, or a charge generating layer in an organic light emitting device. In particular, the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 may be used as a material for a light emitting layer of an organic light emitting device. In addition, when the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 are used in an organic light emitting device, the driving voltage of the device is lowered, the light efficiency is improved, and the life of the device is increased due to the thermal stability of the compound. characteristics can be improved.

1 to 3 are diagrams schematically illustrating a stacked structure of an organic light emitting device according to an exemplary embodiment of the present application.

100: substrate

200: anode

300: organic material layer

301: hole injection layer

302: hole transport layer

303: light emitting layer

304: hole blocking layer

305: electron transport layer

306: electron injection layer

400: cathode

Hereinafter, this application will be described in detail.

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

X1 is O; S; CRaRb; or NRc;

Rm is hydrogen; or deuterium;

Ar2 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms;

Since the molecular structure of the host used in the light emitting layer (EML) of the organic light emitting device device must have electron injection/transport characteristics and hole injection/transport characteristics at the same time, it is essential to have bipolarity. Since the balance of electrons/holes in these bipolar molecules is quite difficult, recently, p-type molecules with hole characteristics and n-type molecules with electronic characteristics are used to adjust the ratio to control the balance of electrons and holes in the light emitting layer. are doing Although this method can easily control the balance of electrons and electrons, there is a difficulty in uniformly depositing organic materials on the device.

The compound represented by Chemical Formula 1 is an n-type compound that has excellent lifespan and efficiency of devices even when used as a single host, and has the advantage of facilitating uniform deposition of organic materials.

Therefore, the heterocyclic compound represented by Formula 1 is an n-type compound, and the heterocyclic compound represented by Formula 2 is a p-type compound, and the heterocyclic compound represented by Formula 1 is And it is easy to uniformly deposit the heterocyclic compound represented by Formula 2.

In addition, when the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 are used in an organic light emitting device, performance and lifetime of the device may be increased. In addition, the driving voltage of the device can be lowered and the efficiency of the device can be increased. In particular, when used in the light emitting layer of an organic light emitting device, the device can show more excellent performance.

This result can be expected that an exciplex phenomenon occurs when the two compounds are included at the same time. The exciplex phenomenon is an electron exchange between two molecules, and the HOMO level (highest occupied molecular orbital level) of the donor (donor, p-host function) and the LUMO level (lowest unoccupied molecular orbital level) of the acceptor (acceptor, n-host function) level) is a phenomenon in which energy is released.

When an exciplex between two molecules occurs, RISC (Reverse Intersystem Crossing) occurs, and this can increase the internal quantum efficiency of fluorescence to 100%.

That is, when a donor with good hole transport ability and an acceptor with good electron transport capability are used as the host of the light emitting layer, the driving voltage can be lowered because holes are injected into the p-host and electrons are injected into the n-host. , thereby helping to improve lifespan.

In the organic light emitting device of the present application, the organic material layer includes a light emitting layer, and the light emitting layer may include a heterocyclic compound represented by Chemical Formula 1 or a heterocyclic compound represented by Chemical Formula 2 as a host material.

In the organic light emitting device of the present application, the light emitting layer may include two or more host materials, and at least one of the host materials emits light from the heterocyclic compound represented by Formula 1 or the heterocyclic compound represented by Formula 2. It may be included as a host material of the material.

In the organic light emitting device of the present application, the organic material layer includes a light emitting layer, and the light emitting layer may include the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 as host materials of the light emitting material.

In the organic light emitting device of the present application, the light emitting layer may include two or more host materials, and at least one of the host materials includes a heterocyclic compound represented by Chemical Formula 1 and a heterocyclic compound represented by Chemical Formula 2 as a host. material may be included.

As a structural feature of the compound represented by Formula 1, a geometry similar to an excited state is formed by overlapping the HOMO level and the LUMO level, thereby increasing efficiency.

More specifically, due to a linear substituent such as biphenyl, the efficiency is increased by extending the HOMO to the dibenzofuran core. In the case of LUMO, the triazine substituent extends in a linear form, so that it is delocalized in the dibenzofuran core.

This structural feature exhibits fast electron transfer (ET) characteristics, so when the heterocyclic compound represented by Chemical Formula 1 is used in an organic light emitting device, the device has an effect of having a low driving voltage.

In addition, as the compound represented by Formula 1 uses a compound having good hole transport capability as shown in Formula 2, the lifetime of the device is improved due to appropriate movement of the light emitting zone in the light emitting layer.

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

In the present specification, "substituted or unsubstituted" deuterium; cyano group; halogen group; straight-chain or branched-chain alkyl having 1 to 60 carbon atoms; straight-chain or branched-chain alkenyl having 2 to 60 carbon atoms; straight or branched alkynyl having 2 to 60 carbon atoms; monocyclic or polycyclic cycloalkyl having 3 to 60 carbon atoms; monocyclic or polycyclic heterocycloalkyl having 2 to 60 carbon atoms; monocyclic or polycyclic aryl having 6 to 60 carbon atoms; monocyclic or polycyclic heteroaryl having 2 to 60 carbon atoms; -SiRR'R"; -P(=O)RR'; alkylamines having 1 to 20 carbon atoms; monocyclic or polycyclic arylamines having 6 to 60 carbon atoms; and monocyclic or polycyclic heteroarylamines having 2 to 60 carbon atoms. It means substituted or unsubstituted with one or more substituents selected from the group, or substituted or unsubstituted with a substituent connected to two or more substituents selected from the above exemplified substituents, wherein R, R' and R" are the same as or different from each other, independently substituted or unsubstituted alkyl having 1 to 60 carbon atoms; substituted or unsubstituted aryl having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroaryl having 2 to 60 carbon atoms.

In the present specification, "when no substituent is shown in the chemical formula or compound structure" means that a hydrogen atom is bonded to a carbon atom. However, since deuterium ( ² H, Deuterium) is an isotope of hydrogen, some hydrogen atoms may be deuterium.

In an exemplary embodiment of the present application, "when no substituent is indicated in the chemical formula or compound structure" may mean that all possible positions of the substituent are hydrogen or deuterium. That is, deuterium is an isotope of hydrogen, and some hydrogen atoms may be an isotope of deuterium, and in this case, the content of deuterium may be 0% to 100%.

In one embodiment of the present application, in "when no substituent is indicated in the chemical formula or compound structure", the content of deuterium is 0%, the content of hydrogen is 100%, and all substituents explicitly exclude deuterium such as hydrogen. If not, hydrogen and deuterium may be mixed and used in the compound.

In one embodiment of the present application, deuterium is one of the isotopes of hydrogen, and is an element having a deuteron composed of one proton and one neutron as an atomic nucleus, hydrogen- It can be expressed as 2, and the element symbol can also be written as D or 2H.

In an exemplary embodiment of the present application, isotopes, which mean atoms having the same atomic number (Z) but different mass numbers (A), have the same number of protons, but have neutrons It can also be interpreted as an element with a different number of neutrons.

In an exemplary embodiment of the present application, the meaning of the content T% of a specific substituent is to define the total number of substituents that a base compound can have as T1, and the number of specific substituents among them is defined as T2. It can be defined as /T1×100 = T%.

That is, in one example,

In the phenyl group represented by 20% of the deuterium content means that the total number of substituents that the phenyl group can have is 5 (T1 in the formula), and if the number of deuterium is 1 (T2 in the formula), it will be represented by 20% can That is, it can be represented by the following structural formula that the content of deuterium in the phenyl group is 20%.

In addition, in an exemplary embodiment of the present application, in the case of "a phenyl group having a deuterium content of 0%", it may mean a phenyl group without deuterium atoms, that is, having 5 hydrogen atoms.

In the present specification, the halogen may be fluorine, chlorine, bromine or iodine.

In the present specification, the alkyl group includes a straight or branched chain having 1 to 60 carbon atoms, and may be further substituted by other substituents. The number of carbon atoms of the alkyl group may be 1 to 60, specifically 1 to 40, and more specifically, 1 to 20. Specific examples include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, sec-butyl group, 1-methyl-butyl group, 1- Ethyl-butyl group, pentyl group, n-pentyl group, isopentyl group, neopentyl group, tert-pentyl group, hexyl group, n-hexyl group, 1-methylpentyl group, 2-methylpentyl group, 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-ethyl-propyl group, 1,1-dimethyl-propyl group , Isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, etc., but is not limited thereto.

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

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

In the present specification, the alkoxy group may be straight chain, branched chain or cyclic chain. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n -hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. It is not limited.

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

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

In the present specification, the aryl group includes a monocyclic or polycyclic ring having 6 to 60 carbon atoms, and may be further substituted with other substituents. Here, the polycyclic means a group in which an aryl group is directly connected or condensed with another cyclic group. Here, the other ring group may be an aryl group, but may also be another type of ring group, such as a cycloalkyl group, a heterocycloalkyl group, a heteroaryl group, and the like. The aryl group includes a spiro group. The number of carbon atoms of the aryl group may be 6 to 60, specifically 6 to 40, and more specifically 6 to 25. Specific examples of the aryl group include a phenyl group, a biphenyl group, a triphenyl group, a naphthyl group, anthryl group, a chrysenyl group, a phenanthrenyl group, a perylenyl group, a fluoranthenyl group, a triphenylenyl group, a phenalenyl group, and a pyrene group. Nyl group, tetracenyl group, pentacenyl group, fluorenyl group, indenyl group, acenaphthylenyl group, benzofluorenyl group, spirobifluorenyl group, 2,3-dihydro-1H-indenyl group, condensed ring groups thereof and the like, but is not limited thereto.

In the present specification, the phosphine oxide group is represented by -P(=O)R101R102, R101 and R102 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; an alkyl group; alkenyl group; alkoxy group; cycloalkyl group; aryl group; And it may be a substituent consisting of at least one of a heterocyclic group. The phosphine oxide group specifically includes a diphenylphosphine oxide group, dinaphthylphosphine oxide, and the like, but is not limited thereto.

In the present specification, the silyl group includes Si and is a substituent to which the Si atom is directly connected as a radical, represented by -SiR104R105R106, R104 to R106 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; an alkyl group; alkenyl group; alkoxy group; cycloalkyl group; aryl group; And it may be a substituent consisting of at least one of a heterocyclic group. Specific examples of the silyl group include a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like. It is not limited.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may bond to each other to form a ring.

In the present specification, the spiro group is a group including a spiro structure, and may have 15 to 60 carbon atoms. For example, the spiro group may include a structure in which a 2,3-dihydro-1H-indene group or a cyclohexane group is spiro bonded to a fluorenyl group. Specifically, the following spiro group may include any one of groups of the following structural formula.

In the present specification, the heteroaryl group includes S, O, Se, N or Si as a hetero atom, and includes a monocyclic or polycyclic group having 2 to 60 carbon atoms, and may be further substituted by other substituents. Here, the polycyclic means a group in which a heteroaryl group is directly connected or condensed with another ring group. Here, the other ring group may be a heteroaryl group, but may also be another type of ring group, such as a cycloalkyl group, a heterocycloalkyl group, an aryl group, and the like. The heteroaryl group may have 2 to 60 carbon atoms, specifically 2 to 40, and more specifically 3 to 25 carbon atoms. Specific examples of the heteroaryl group include a pyridyl group, a pyrrolyl group, a pyrimidyl group, a pyridazinyl group, a furanyl group, a thiophene group, an imidazolyl group, a pyrazolyl group, an oxazolyl group, an isoxazolyl group, and a thiazolyl group. group, isothiazolyl group, triazolyl group, furazanyl group, oxadiazolyl group, thiadiazolyl group, dithiazolyl group, tetrazolyl group, pyranyl group, thiopyranyl group, diazinyl group, oxazinyl group , thiazinyl group, dioxynyl group, triazinyl group, tetrazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, isoquinazolinyl group, quinozolilyl group, naphthyridyl group, acridinyl group, phenanthridi Nyl group, imidazopyridinyl group, diazanaphthalenyl group, triazaindene group, indolyl group, indolizinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiophene group, benzofuran group , Dibenzothiophene group, dibenzofuran group, carbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, phenazinyl group, dibenzosilol group, spirobi (dibenzosilol), dihydrophenazinyl group, A phenoxazinyl group, a phenanthridyl group, an imidazopyridinyl group, a thienyl group, an indolo[2,3-a]carbazolyl group, an indolo[2,3-b]carbazolyl group, an indolinyl group, 10, 11-dihydro-dibenzo[b,f]azepine group, 9,10-dihydroacridinyl group, phenantrazinyl group, phenothiathiazinyl group, phthalazinyl group, naphthylidinyl group, phenanthrolinyl group, Benzo [c] [1,2,5] thiadiazolyl group, 5,10-dihydrodibenzo [b, e] [1,4] azasilinyl group, pyrazolo [1,5-c] quinazolinyl group , pyrido [1,2-b] indazolyl group, pyrido [1,2-a] imidazo [1,2-e] indolinyl group, 5,11-dihydroindeno [1,2-b ] carbazolyl group and the like, but is not limited thereto.

In the present specification, the amine group is a monoalkylamine group; monoarylamine group; Monoheteroarylamine group; -NH ₂ ; Dialkylamine group; Diaryl amine group; Diheteroarylamine group; an alkyl arylamine group; Alkylheteroarylamine group; And it may be selected from the group consisting of an arylheteroarylamine 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, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, a dibiphenylamine group, an anthracenylamine group, a 9- Methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, biphenylnaphthylamine group, phenylbiphenylamine group, biphenylfluorene Examples include a ylamine group, a phenyltriphenylenylamine group, a biphenyltriphenylenylamine group, and the like, but are not limited thereto.

In the present specification, the arylene group means that the aryl group has two bonding sites, that is, a divalent group. The description of the aryl group described above can be applied except that each is a divalent group. In addition, the heteroarylene group means a heteroaryl group having two bonding sites, that is, a divalent group. The above description of the heteroaryl group may be applied except that each is a divalent group.

As used herein, "adjacent" refers to a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent located sterically closest to the substituent, or another substituent substituted on the atom on which the substituent is substituted. can For example, two substituents substituted at ortho positions in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as “adjacent” to each other.

The heterocyclic compound represented by Chemical Formula 1 according to an exemplary embodiment of the present application may be used as a material for an organic material layer of an organic light emitting device.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Chemical Formula 1 may be 0% to 100%.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Chemical Formula 1 may be 10% or more and 100% or less.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Chemical Formula 1 may be 20% or more and 100% or less.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Chemical Formula 1 may be 30% or more and 100% or less.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Chemical Formula 1 may be 40% or more and 100% or less.

When the compound represented by Formula 1 contains deuterium, compared to the case where deuterium is not included, the photochemical characteristics are similar, but when deposited on a thin film, the material containing deuterium packs a narrower intermolecular distance ( packing). Accordingly, compounds containing deuterium exhibit more balanced charge transport characteristics. These characteristics can be confirmed through a method of manufacturing an EOD (Electron Only Device) and a HOD (Hole Only Device) and checking the current density according to the voltage.

In addition, the higher the content of deuterium, that is, the higher the substitution rate of deuterium, the better the performance of the device using the deuterium. In addition, when deuterium is partially substituted, the device performance is superior when the triazine group is substituted with deuterium than when the biphenyl group is substituted with deuterium, and the device performance is better than when the biphenyl group or triazine group is partially substituted throughout the compound. When the element performance is better.

That is, the structure in which deuterium is substituted in the dibenzofuran core part is more effective in improving the performance of the device than in the hole transfer unit (HTU) or electron transfer unit (ETU) where deuterium is partially substituted. It is advantageous.

In an exemplary embodiment of the present application, Ar1 of Formula 1 is a substituted or unsubstituted biphenyl group; A substituted or unsubstituted dibenzofuran group; Or it may be a substituted or unsubstituted dimethylfluorene group.

In an exemplary embodiment of the present application, Ar1 is a biphenyl group unsubstituted or substituted with one or more deuterium; A dibenzofuran group unsubstituted or substituted with one or more deuterium; Alternatively, it may be a dimethylfluorene group unsubstituted or substituted with one or more deuterium atoms.

In an exemplary embodiment of the present application, Ar2 of Formula 1 may be a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

In one embodiment of the present application, Ar2 may be a substituted or unsubstituted aryl group having 6 to 40 carbon atoms.

In an exemplary embodiment of the present application, Ar2 may be a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

In an exemplary embodiment of the present application, Ar2 is a substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; Or it may be a substituted or unsubstituted naphthyl group.

In an exemplary embodiment of the present application, Ar2 is a phenyl group unsubstituted or substituted with one or more deuterium; A biphenyl group unsubstituted or substituted with one or more deuterium; Or it may be a naphthyl group unsubstituted or substituted with at least one deuterium.

In an exemplary embodiment of the present application, X1 in Formula 1 is O; S; CRaRb; or NRc.

In one embodiment of the present application, X1 is O.

In one embodiment of the present application, X1 is S.

In one embodiment of the present application, X1 is CRaRb.

In one embodiment of the present application, X1 is NRc.

In an exemplary embodiment of the present application, the Ra to Rc are the same as or different from each other, and each independently, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; Or it may be a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

In an exemplary embodiment of the present application, the Ra to Rc are the same as or different from each other, and each independently, a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms; Or it may be a substituted or unsubstituted aryl group having 6 to 40 carbon atoms.

In an exemplary embodiment of the present application, the Ra to Rc are the same as or different from each other, and each independently, a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; Or it may be a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

In an exemplary embodiment of the present application, Ra and Rb are the same as or different from each other, and each independently may be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

In an exemplary embodiment of the present application, Ra and Rb are the same as or different from each other, and each independently may be a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

In an exemplary embodiment of the present application, Ra and Rb are the same as or different from each other, and each independently represents a substituted or unsubstituted methyl group.

In an exemplary embodiment of the present application, Ra and Rb are the same as or different from each other, and each independently represents a methyl group unsubstituted or substituted with one or more deuterium atoms.

In an exemplary embodiment of the present application, Rc may be a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

In an exemplary embodiment of the present application, Rc may be a substituted or unsubstituted phenyl group.

In an exemplary embodiment of the present application, Rc may be a phenyl group unsubstituted or substituted with one or more deuterium atoms.

In an exemplary embodiment of the present application, R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; -CN; Or it may be a substituted or unsubstituted alkyl group having 1 to 40 carbon atoms.

In an exemplary embodiment of the present application, R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; -CN; Alternatively, it may be a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

In an exemplary embodiment of the present application, R1 to R4 are the same as or different from each other, and each independently hydrogen; or deuterium.

In an exemplary embodiment of the present application, Formula 1 may be represented by any one of Formulas 3 to 5 below.

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 3 to 5,

R5 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

e is an integer from 0 to 4, and when e is 2 or more, R5 in parentheses are the same as or different from each other;

f is an integer from 0 to 5, and when f is 2 or more, R6 in parentheses are the same as or different from each other;

g and h are each an integer from 0 to 7, and when g is 2 or more, R7 in parentheses are the same as or different from each other, and when h is 2 or more, R8 in parentheses are the same as or different from each other,

The definitions of X1, R1 to R4, a to d, Rm, and Ar2 are the same as those of Formula 1.

As described above, the compounds represented by Formulas 3 to 5 extend the HOMO to the dibenzofuran core due to the linear substituent such as biphenyl, thereby increasing the efficiency. do. In addition, in the case of LUMO, the triazine substituents are delocalized in the dibenzofuran core as the biphenyl, dibenzofuran, and dimethylfluonel groups extend in a linear form, respectively. .

Due to this, a geometry similar to an excited state is formed by overlapping the HOMO level and the LUMO level, resulting in an effect of increasing efficiency.

In addition, hydrogen of the heterocyclic compounds represented by Chemical Formulas 3 to 5 may be unsubstituted or substituted with deuterium.

In an exemplary embodiment of the present application, R5 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; -CN; A substituted or unsubstituted alkyl group having 1 to 40 carbon atoms; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; Or it may be a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms.

In an exemplary embodiment of the present application, R5 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; -CN; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or it may be a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

In an exemplary embodiment of the present application, R5 to R8 are the same as or different from each other, and each independently hydrogen; or deuterium.

In an exemplary embodiment of the present application, Chemical Formula 1 may be represented by any one of Chemical Formulas 1-1 to 1-3.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3,

The definitions of X1, R1 to R4, a to d, Rm, Ar1 and Ar2 are the same as those in Formula 1 above.

In addition, hydrogen of the heterocyclic compounds represented by Chemical Formulas 1-1 to 1-3 may be unsubstituted or substituted with heavy hydrogen.

Ar1 in Formulas 1-1 to 1-3 may be a group represented by one of the following Formulas A to C.

[Formula A]

[Formula B]

[Formula C]

In the above formulas A to C,

* means a position bonded to Formula 1,

The definitions of R5, R6, e and f are the same as those in Formula 3,

The definitions of R7 and e are the same as those in Formula 4 above,

The definitions of R8 and h are the same as those in Formula 5 above.

In an exemplary embodiment of the present application, the heterocyclic compound represented by Chemical Formula 1-2 may be provided.

The compound represented by Formula 1 may show a difference in bonding dissociation energy depending on the substituted position of the triazine. At this time, when the triazine group is substituted at the 3-position of the dibenzofuran core as shown in Chemical Formula 1-2, it may have the highest bonding dissociation energy. For this reason, among the compounds represented by Chemical Formula 1, the compounds represented by Chemical Formulas 1-2 have more excellent material stability, and thus have an effect of further increasing the lifespan of the device when used in a device.

In the present specification, position 3 of the dibenzofuran core is the same as position 3 of Formula D below. That is, the position of the number n shown in Formula D below means the position n, and n is an integer from 1 to 4.

[Formula D]

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Chemical Formula 1-2 may be 0% to 100%.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Chemical Formula 1-2 may be 10% or more and 100% or less.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Chemical Formula 1-2 may be 20% or more and 100% or less.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Chemical Formula 1-2 may be 30% or more and 100% or less.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Chemical Formula 1-2 may be 40% or more and 100% or less.

When the compound represented by Chemical Formula 1-2 contains deuterium, the description of the case in which the compound represented by Chemical Formula 1 contains deuterium may be applied.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Chemical Formula 2 may be 0% to 100%.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Chemical Formula 2 may be 10% or more and 100% or less.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Chemical Formula 2 may be 20% or more and 100% or less.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Chemical Formula 2 may be 30% or more and 100% or less.

In an exemplary embodiment of the present application, the content of deuterium in the heterocyclic compound represented by Chemical Formula 2 may be 40% or more and 100% or less.

When the compound represented by Formula 2 contains deuterium, compared to the case without deuterium, the photochemical characteristics are similar, but when deposited on a thin film, the material containing deuterium packs a narrower intermolecular distance ( packing). Accordingly, compounds containing deuterium exhibit more balanced charge transport characteristics. These characteristics can be confirmed through a method of manufacturing an EOD (Electron Only Device) and a HOD (Hole Only Device) and checking the current density according to the voltage.

In addition, the higher the content of deuterium, that is, the higher the substitution rate of deuterium, the better the performance of the device using the deuterium. In addition, when deuterium is partially substituted, the case where biscarbazole is deuterium-substituted rather than the aryl group (meaning R21 and R22 in Formula 2) of Formula 2 is deuterium-substituted. The device's performance is better.

According to an exemplary embodiment of the present application, Rd and Re in Chemical Formula 2 are hydrogen; or deuterium.

In another exemplary embodiment, R21 and R22 in Formula 2 are the same as or different from each other, and each independently -SiR31R32R33; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, R31, R32, and R33 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or it may be a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In another exemplary embodiment, R21 and R22 are the same as or different from each other, and each independently -SiR31R32R33; A substituted or unsubstituted aryl group having 6 to 40 carbon atoms; Or it may be a substituted or unsubstituted heteroaryl group having 2 to 40 carbon atoms.

In another exemplary embodiment, R21 and R22 are the same as or different from each other, and each independently -SiR31R32R33; A substituted or unsubstituted aryl group having 6 to 20 carbon atoms; Or it may be a substituted or unsubstituted heteroaryl group having 2 to 20 carbon atoms.

In another exemplary embodiment, R21 and R22 are the same as or different from each other, and each independently -SiR31R32R33; A substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted triphenyl group; A substituted or unsubstituted terphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted fluorene group; A substituted or unsubstituted spirobifluorene group; A substituted or unsubstituted dibenzofuran group; Or it may be a substituted or unsubstituted dibenzothiophene group.

In another exemplary embodiment, R21 and R22 are the same as or different from each other, and each independently -SiR31R32R33; A phenyl group unsubstituted or substituted with at least one selected from the group consisting of deuterium and -CN; A biphenyl group unsubstituted or substituted with heavy hydrogen; A triphenyl group unsubstituted or substituted with heavy hydrogen; A terphenyl group unsubstituted or substituted with heavy hydrogen; A naphthyl group unsubstituted or substituted with heavy hydrogen; A fluorene group unsubstituted or substituted with at least one selected from the group consisting of deuterium, a phenyl group unsubstituted or substituted with deuterium, and a methyl group unsubstituted or substituted with deuterium; A substituted or unsubstituted spirobifluorene group with heavy hydrogen; A dibenzofuran group unsubstituted or substituted with heavy hydrogen; Or it may be a dibenzothiophene group unsubstituted or substituted with deuterium.

In another exemplary embodiment, R21 and R22 are the same as or different from each other, and each independently -SiR31R32R33; A phenyl group unsubstituted or substituted with at least one selected from the group consisting of deuterium and -CN; A biphenyl group unsubstituted or substituted with heavy hydrogen; A triphenyl group unsubstituted or substituted with heavy hydrogen; A terphenyl group unsubstituted or substituted with heavy hydrogen; A naphthyl group unsubstituted or substituted with heavy hydrogen; A dimethylfluorene group unsubstituted or substituted with heavy hydrogen; A diphenylfluorene group unsubstituted or substituted with heavy hydrogen; A substituted or unsubstituted spirobifluorene group with heavy hydrogen; A dibenzofuran group unsubstituted or substituted with heavy hydrogen; Or it may be a dibenzothiophene group unsubstituted or substituted with deuterium.

In another exemplary embodiment, R31, R32, and R33 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or it may be a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In another exemplary embodiment, R31, R32, and R33 are the same as or different from each other, and each independently may be a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

In another exemplary embodiment, R31, R32, and R33 are the same as or different from each other, and each independently may be a substituted or unsubstituted aryl group having 6 to 40 carbon atoms.

In another exemplary embodiment, R31, R32, and R33 are the same as or different from each other, and each independently may be a substituted or unsubstituted aryl group having 6 to 20 carbon atoms.

In another exemplary embodiment, R31, R32, and R33 are the same as or different from each other, and each independently may be a phenyl group unsubstituted or substituted with deuterium.

According to an exemplary embodiment of the present application, Formula 1 may be represented by any one of the following compounds, but is not limited thereto.

According to an exemplary embodiment of the present application, Formula 2 may be represented by any one of the following compounds, but is not limited thereto.

In addition, by introducing various substituents into the structures of Chemical Formulas 1 and 2, compounds having unique characteristics of the introduced substituents can be synthesized. For example, by introducing substituents mainly used in hole injection layer materials, hole transport materials, light emitting layer materials, electron transport layer materials, and charge generation layer materials used in the manufacture of organic light emitting devices into the core structure, the requirements of each organic layer are met. substances can be synthesized.

In addition, by introducing various substituents into the structures of Chemical Formulas 1 and 2, it is possible to finely control the energy band gap, and on the other hand, it is possible to improve the properties at the interface between organic materials and to diversify the use of materials. there is.

Meanwhile, the heterocyclic compounds of Chemical Formulas 1 and 2 have high glass transition temperatures (Tg) and excellent thermal stability. This increase in thermal stability is an important factor in providing driving stability to the device.

The heterocyclic compound according to an exemplary embodiment of the present application may be prepared through a multi-step chemical reaction. Some intermediate compounds are prepared first, and the compounds of Formulas 1 and 2 can be prepared from the intermediate compounds. More specifically, the heterocyclic compound according to an exemplary embodiment of the present application may be prepared based on Preparation Examples described below.

Another exemplary embodiment of the present application provides an organic light emitting device including the heterocyclic compounds represented by Chemical Formulas 1 and 2 above. The "organic light emitting device" may be expressed in terms such as "organic light emitting diode", "organic light emitting diodes (OLED)", "OLED device", and "organic electroluminescent device".

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

The organic light emitting device of the present invention may further include one or two or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a hole auxiliary layer, and a hole blocking layer.

The organic material layer includes one or more light emitting layers, and the light emitting layer includes the heterocyclic compounds represented by Chemical Formulas 1 and 2 above. Among the organic material layers, when the light emitting layer includes the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2, the organic light emitting device has better light emitting efficiency and lifespan.

When the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 are included as the host material, the organic light emitting device has more excellent light emitting efficiency and lifetime.

In addition, another exemplary embodiment of the present application provides a composition for an organic layer of an organic light emitting device comprising the heterocyclic compound represented by Formula 1 and the compound represented by Formula 2 at the same time.

Details of the heterocyclic compound represented by Chemical Formula 1 and the heterocyclic compound represented by Chemical Formula 2 are the same as described above.

The weight ratio of the heterocyclic compound represented by Formula 1 in the composition to the heterocyclic compound represented by Formula 2 may be 1: 10 to 10: 1, 1: 8 to 8: 1, or 1: 5 to 5:1, or 1:2 to 2:1, but is not limited thereto.

In one embodiment of the present application, preparing a substrate; forming a first electrode on the substrate; forming one or more organic material layers on the first electrode; and forming a second electrode on the organic material layer, wherein the forming of the organic material layer includes forming one or more organic material layers using the composition for an organic material layer according to an exemplary embodiment of the present application. A method for manufacturing an organic light emitting device is provided.

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

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

In one embodiment of the present application, the forming of the organic material layer is performed by supplying the heterocyclic compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 to individual sources, and then using a thermal vacuum deposition method. It provides a method of manufacturing an organic light emitting device that is formed.

In an exemplary embodiment of the present application, the forming of the organic material layer is performed by pre-mixing the heterocyclic compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 using a thermal vacuum deposition method. It provides a method for manufacturing an organic light emitting device that is to do.

The pre-mixing means that the heterocyclic compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 are first mixed and mixed in one park before depositing the compound represented by Chemical Formula 2 on the organic material layer.

When depositing through pre-mixing, it is possible to improve the uniformity and characteristics of thin films because multiple depositions are not performed, simplifying the process, reducing costs, and improving efficiency and lifespan. can form

The premixed material may be referred to as a composition for an organic layer according to an exemplary embodiment of the present application.

An organic light emitting device according to an exemplary embodiment of the present application may be manufactured by a conventional organic light emitting device manufacturing method and material, except for forming an organic material layer using the aforementioned heterocyclic compound.

1 to 3 illustrate the stacking order of the electrode and the organic material layer of the organic light emitting device according to an exemplary embodiment of the present application. However, it is not intended that the scope of the present application be limited by these drawings, and structures of organic light emitting devices known in the art may be applied to the present application as well.

According to FIG. 1 , an organic light emitting device in which an anode 200, an organic material layer 300, and a cathode 400 are sequentially stacked on a substrate 100 is shown. However, it is not limited to such a structure, and as shown in FIG. 2, an organic light emitting device in which a cathode, an organic material layer, and an anode are sequentially stacked on a substrate may be implemented.

3 illustrates a case where the organic material layer is multi-layered. The organic light emitting device according to FIG. 3 includes a hole injection layer 301, a hole transport layer 302, an emission layer 303, a hole blocking layer 304, an electron transport layer 305, and an electron injection layer 306. However, the scope of the present application is not limited by such a laminated structure, and layers other than the light emitting layer may be omitted as necessary, and other necessary functional layers may be further added.

In the organic light emitting device according to an exemplary embodiment of the present application, materials other than the heterocyclic compound of Chemical Formula 1 are exemplified below, but these are for illustrative purposes only and are not intended to limit the scope of the present application. may be substituted with known materials.

Materials having a relatively high work function may be used as the anode material, and transparent conductive oxides, metals, or conductive polymers may be used. Specific examples of the anode material include metals such as vanadium, chromium, copper, zinc, and gold or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); 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] (PEDT), polypyrrole, and polyaniline, but are not limited thereto.

Materials having a relatively low work function may be used as the cathode material, and metals, metal oxides, or conductive polymers may be used. Specific examples of the anode material include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin, and lead, or alloys thereof; There are multi-layered materials such as LiF/Al or LiO ₂ /Al, but are not limited thereto.

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

As the hole transport material, pyrazoline derivatives, arylamine derivatives, stilbene derivatives, triphenyldiamine derivatives, and the like may be used, and low molecular weight or high molecular weight materials may also be used.

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

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

A red, green or blue light emitting material may be used as the light emitting material, and if necessary, two or more light emitting materials may be mixed and used. In addition, a fluorescent material can be used as a light emitting material, but it can also be used as a phosphorescent material. As the light emitting material, a material that emits light by combining holes and electrons respectively injected from the anode and the cathode may be used, but materials in which a host material and a dopant material are involved in light emission may also be used.

An organic light emitting device according to an exemplary embodiment of the present application may be a top emission type, a bottom emission type, or a double side emission type depending on materials used.

The heterocyclic compound according to an exemplary embodiment of the present application may act on a principle similar to that applied to an organic light emitting device in an organic electronic device including an organic solar cell, an organic photoreceptor, and an organic transistor.

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

<제조예 1> 화합물 1-1(D)의 제조<Preparation Example 1> Preparation of compound 1-1 (D)

1) 중간체 1의 합성법1) Synthesis of Intermediate 1

6-bromo-3-chlorodibenzo[b,d]furan (A) (20.g, 70.69mmol), [ 1,1'-biphenyl]-4-ylboronic acid (B) (16.8g, 84.82mmol), tetrakis(triphenylphosphine)palladium (0) (Tetrakis(triphenylphosphine)palladium(0)) (4.08g, 3.53mmol), Potassium carbonate (30.21g, 212.06mmol), and 1,4-dioxane/distilled water (1,4-dioxane/water) (100ml/25ml) was refluxed at 120°C for 3 hours (h). After completion of the reaction, the temperature was lowered to room temperature, and the resulting solid was washed with distilled water and methanol (MeOH) to obtain intermediate 1. (22g, 87%)

2) 중간체 2의 합성법2) Synthesis of Intermediate 2

In a reaction flask, intermediate 1 (22.g, 62mmol), bis(pinacolate)diboron (31.49g, 124mmol), Sphos (5.09g, 12.4mmol), potassium acetate (KOAc ) (18.26 g, 186 mmol), and Pd ₂ (dba) ₃ (5.68 g, 6.2 mmol). Thereafter, 220 ml of 1,4-dioxane was added to the reaction flask and heated at 120° C. for 4 hours. After the reaction was completed, the base was removed and the solvent was concentrated. Intermediate 2 was obtained by recrystallizing with methylene chloride (MC) and hexane (Hex) to precipitate solids and filtering. (21g, 75%)

3) 화합물 1-1(D)의 합성방법3) Synthesis of Compound 1-1 (D)

In a reaction flask, intermediate 2 (21.g, 47.05 mmol), 2-([1,1′-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-tri Azine (2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine) (C) (19.41 g, 56.46 mmol), Pd (PPh ₃ ) ₄ (2.72 g, 2.35 mmol), and K ₂ CO ₃ (19.51 g, 134.09 mmol). Thereafter, a mixture of 1,4-dioxane/distilled water (1,4-dioxane/water) (100ml/25ml) was heated at 120° C. for 4 hours. After completion of the reaction, the temperature was lowered to room temperature, and the formed solid was washed with distilled water and methanol (MeOH) to obtain compound 1-1 (D). (25g, 84%)

In Preparation Example 1, 6-bromo-3-chlorodibenzo [b, d] furan (6-bromo-3-chlorodibenzo [b, d] furan), [1,1'-biphenyl] -4 ylboronic acid ([1,1'-biphenyl]-4-ylboronic acid) and 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine) using Compound A, Compound B, and Compound C in Table 1 instead The target compound D of Table 1 was synthesized in the same manner as in Preparation Example 1 except for the above.

<제조예 2> 화합물 1-29(E)의 제조방법<Preparation Example 2> Method for preparing compound 1-29 (E)

1) 중간체 3의 합성방법1) Synthesis method of intermediate 3

In a reaction flask, 6-bromo-3-chlorodibenzo[b,d]furan (A) (20g, 70.69mmol), bis(pina) Cholate)diboron (bis(pinacolate)diboron) (35.8g, 141.4mmol), Pd(dppf)Cl ₂ (2.58g, 3.35mmol), and potassium acetate (KOAc) (20.8g, 212mmol) were added. Thereafter, 200 ml of 1,4-dioxane was added and refluxed at 120° C. for 3 hours. After completion of the reaction, the temperature was lowered to room temperature, followed by extraction with MC and distilled water (H ₂ O), followed by column purification to obtain Intermediate 3. (20g, 87%)

2) 중간체 5의 합성방법2) Synthesis method of Intermediate 5

In a reaction flask, intermediate 3 (20.g, 60.86mmol), intermediate 4 (17.6g, 73mmol), Pd(PPh ₃ ) ₄ (3.52g, 3.04mmol), K ₂ CO ₃ (25.2g, 182.6mmol) ), and a mixture of 1,4-dioxane/distilled water (1,4-dioxane/water) (200ml/50ml) was refluxed at 120°C for 3 hours. After completion of the reaction, the temperature was lowered to room temperature, and the resulting solid was washed with distilled water and methanol (MeOH) to obtain Intermediate 5. (18g, 81%)

3) 중간체 6의 합성방법3) Synthesis of Intermediate 6

To a reaction flask were placed intermediate 5 (18.g, 49.7mmol), bis(pinacolate)diboron (25.1g, 98.9mmol), Sphos (4g, 9.89mmol), and potassium acetate. (KOAc) (14.56 g, 148.4 mmol), and Pd ₂ (dba) ₃ (4.5 g, 4.59 mol) were added. After this, 1,4-dioxane (1,4-dioxane) was put into (1,4-dioxane) was heated for 4 hours at 120 ℃. After the reaction was completed, the base was removed and the solvent was concentrated. This was recrystallized with MC and Hex to precipitate a solid and filtered to obtain Intermediate 6. (20g, 88%)

4) 화합물 1-29(E)의 합성방법4) Synthesis of Compound 1-29 (E)

In a reaction flask, intermediate 6 (20.g, 43mmol), 2-([1,1′-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine (2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine) (C) (18.12, 52.7 mmol), Pd(PPh ₃ ) ₄ (2.54g, 2.2mmol), and K ₂ CO ₃ (18.21g, 131.75mmol). Thereafter, 1,4-dioxane/distilled water (1,4-dioxane/water) (200ml/50ml) was added, and the mixture was heated at 120° C. for 4 hours. After completion of the reaction, the temperature was lowered to room temperature, and the resulting solid was washed with distilled water and methanol (MeOH) to obtain compound 1-29 (E). (23g, 82%)

In Preparation Example 2, 6-bromo-3-chlorodibenzo [b, d] furan (6-bromo-3-chlorodibenzo [b, d] furan), intermediates 4 and 2-([1,1'-b Phenyl] -4-yl) -4-chloro-6-phenyl-1,3,5-triazine (2-([1,1'-biphenyl] -4-yl) -4-chloro-6-phenyl- 1,3,5-triazine) was synthesized in the same manner as in Preparation Example 2, except for using Compound A, Intermediate 4, and Compound C in Table 2, respectively, in Table 2 below.

<제조예 3> 화합물 1-31(F)의 제조방법<Preparation Example 3> Method for preparing compound 1-31 (F)

1)One) 화합물 C-4의 제조방법Method for preparing compound C-4

After putting compound C-2 (10g 54.2mmol) and compound C-3 (15.6g, 54.2mmol) in a reaction flask, Pd(OAc) ₂ (0.6g, 2.7mmol), and K ₃ PO ₄ ( 23 g, 108.4 mmol) was added. Thereafter, a mixture of DMF/H ₂ O=5:1 (100ml/20ml) was added and heated at 130°C. After completion of the reaction, the resulting solid was filtered to obtain compound C-4. (13g, 77%)

Here, DMF is dimethylformamide, and is hereinafter also referred to as DMF.

2) 중간체 7의 합성2) Synthesis of Intermediate 7 방법method

Compound C-4 (13 g, 41.7 mmol), compound C-5 (12 g, 41.7 mmol), Pd(PPh ₃ ) ₄ (2.41 g, 2.08 mmol), and K ₂ CO ₃ (11.5 g) were added to a reaction flask. , 83.4 mmol), and then a mixture of THF/H ₂ O = 5:1 (130ml/26ml) was added and stirred at 85°C for 1 hour. After completion of the reaction, the resulting solid was filtered to obtain Intermediate 7. (13g, 72%)

Here, THF is tetrahydrofuran, and is hereinafter also referred to as THF.

3) 화합물 1-31(F)의 합성 방법3) Method for synthesizing compound 1-31 (F)

In the synthesis method of Compound 1-1 (D) of Preparation Example 1, 2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine Compound 1- of Preparation Example 1, except for using Intermediate 7 instead of (2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine) Compound 1-31 (F) was synthesized in the same manner as the synthesis method of 1 (D).

In Preparation Example 3, Compound A of Table 3 was used instead of 6-bromo-3-chlorodibenzo [b, d] furan, and Preparation Example 3 In [1,1'-biphenyl] -4-ylboronic acid ([1,1'-biphenyl] -4-ylboronic acid) instead of using Compound B or Intermediate 4-1 in Table 3, Intermediate in Preparation Example 3 The target compound F in Table 3 was synthesized in the same manner as in Preparation Example 3, except that Intermediate 7 in Table 3 was used instead of 7.

Here, the synthesis method of Intermediate 4-1 is as follows.

1) 중간체 4의 합성법1) Synthesis of Intermediate 4

Synthesis of Intermediate 4 was repeated by reacting Compound C-1 with a solvent in a reaction flask under the conditions of Tables A and B below. As a result, it was confirmed that the yield of intermediate 4 was the highest when synthesized under condition 9 of Table B below.

[Table A]

[Table B]

2) 중간체 4-1의 합성법2) Synthesis of Intermediate 4-1

In a reaction flask, intermediate 4 (10 g, 41.3 mmol), bis (pinacolate) diboron (20.9, 82.5 mmol), Pd (dppf) Cl ₂ (1.5 g, 2.06 mmol), and potassium acetate (KOAc) (12.1 g, 123.8 mmol). Thereafter, 100 ml of 1,4-dioxane was added and refluxed at 120° C. for 3 hours. After completion of the reaction, the temperature was lowered to room temperature, followed by extraction with MC and distilled water (H ₂ O), followed by column purification to obtain intermediate 4-1. (9.7g, 81%)

<제조예 4> 화합물 1-35(G)의 합성 방법<Preparation Example 4> Synthesis method of compound 1-35 (G)

1) 중간체 8의 합성법1) Synthesis of Intermediate 8

Compound C-6 (1g, 1eq.), benzene-D ₆ (benzene-D ₆ ) (50g, 210.8eq.), and CF ₃ SO ₃ H (14.4g, 32.4eq.) were added to the reaction flask and then 50 It reacted for 1 hour at °C. After the reaction was completed, H ₂ O was added to neutralize the mixture, followed by extraction with MC and H ₂ O, and the organic layer was column-purified to obtain Intermediate 8. (0.65g, 62%)

This corresponds to the method with the highest yield as a result of synthesizing Intermediate 8 under the conditions 1 to 8 of Table C below.

[Table C]

2) 중간체 9의 합성법2) Synthesis of Intermediate 9

In a reaction flask, intermediate 8 (10.g, 27mmol), bis(pinacolate)diboron (13.7g, 54mmol), Sphos (2.21g, 5.4mmol), and potassium acetate ( KOAc) (7.9 g, 81 mmol), and Pd ₂ (dba) ₃ (2.47 g, 2.7 mol). Thereafter, 100 ml of 1,4-dioxane was added and heated at 120° C. for 4 hours. After the reaction was completed, the base was removed and the solvent was concentrated. This was recrystallized with MC and Hex to precipitate a solid and filtered to obtain Intermediate 9. (20g, 88%)

3) 화합물 1-35(G)의 합성법 3) Synthesis of Compound 1-35 (G)

In the synthesis method of Compound 1-1 (D) of Preparation Example 1, Intermediate 9 was used instead of Intermediate 2, and 2-([1,1'-biphenyl] -4-yl) -4-chloro-6-phenyl Except for using Intermediate 10 instead of -1,3,5-triazine (2-([1,1'-biphenyl]-4-yl)-4-chloro-6-phenyl-1,3,5-triazine) And, Compound 1-35 (G) was synthesized in the same manner as in Preparation Example 1 for synthesizing Compound 1-1 (D).

In Preparation Example 4, Compound A of Table 4 was used instead of 6-bromo-3-chlorodibenzo [b, d] furan, and Preparation Example 4 In place of [1,1'-biphenyl] -4-ylboronic acid ([1,1'-biphenyl] -4-ylboronic acid), Intermediate 4-2 of Table 4 was used, and Intermediate 10 in Preparation Example 4 was replaced by the following The target compound G in Table 4 was synthesized in the same manner as in Preparation Example 4, except that Intermediate 10 in Table 4 was used.

<제조예 5><Production Example 5> 화합물 2-1(C)의 제조Preparation of compound 2-1 (C)

1) 중간체 11 합성방법1) Intermediate 11 synthesis method

In a reaction flask, 3-bromo-9H-carbazole (10.g, 49.59mmol), 2-bromobenzene-1-ylium ) (A) (24.2g, 148.77mmol), Pd ₂ (dba) ₃ (2.27g, 2.48mmol), P(t-Bu) ₃ (2.42mL, 9.92mmol), and NaOtBu (9.53g, 99.18mmol) After adding, toluene (100mL) was added and heated at 135 ° C. for 15 hours. When the reaction is complete, the mixture is extracted with MC and distilled water (H ₂ O), followed by column purification to obtain Intermediate 11. (14g, 98%)

2) 화합물 2-1(C) 합성방법2) Synthesis method of compound 2-1 (C)

In a reaction flask, intermediate 1 (14 g, 43.4 mmol), (9-phenyl-9H-carbazol-3-yl) boronic acid ((9-phenyl-9H-carbazol-3-yl) boronic acid) (B ) (14.9g, 52mmol), Pd(PPh ₃ ) ₄ (2.5g, 2.17mmol), and K ₂ CO ₃ (17.9g, 130mmol) were added. Thereafter, a mixture of 1,4-dioxane/distilled water (1,4-dioxane/water) (140ml/35ml) was added and heated at 120° C. for 4 hours. After completion of the reaction, the temperature was lowered to room temperature, and the formed solid was washed with distilled water and MeOH to obtain compound 2-1 (C). (17g, 80%)

In Preparation Example 5, 2-bromobenzene-1-ylium (2-bromobenzene-1-ylium) and (9-phenyl-9H-carbazol-3-yl) boronic acid ((9-phenyl-9H-carbazol-3 -yl) boronic acid), except that A and B in Table 5 were used, respectively, and the target compound (C) of 5 below was synthesized in the same manner as in Preparation Example 5.

<제조예 6> 화합물 2-61(F)의 제조<Preparation Example 6> Preparation of compound 2-61 (F)

1) 중간체 12 합성방법1) Intermediate 12 synthesis method

3-bromo-9H-carbazole (10 g, 40.23 mmol) and 1000 ml of D ₆ -benzene were added _to a reaction flask. Thereafter, CF ₃ SO ₃ H (170 g, 1075 mmol) was added and stirred at 50 °C. Upon completion of the reaction, the mixture was neutralized with D ₂ O, extracted with MC and an aqueous solution of Na ₂ CO ₃ , and then purified by column to obtain Intermediate 12. (10g, 98%)

2) 중간체 13 합성방법2) Intermediate 13 synthesis method

Intermediate 12 (10 g, 39.5 mmol), Bromobenzene (12.4 g, 79 mmol), Pd ₂ (dba) ₃ (1.81 g, 1.98 mmol), P (t-Bu) ₃ ( 1.93mL, 7.9mmol) and NaOtBu (11.4g, 118.51mmol) were added. Thereafter, toluene (100mL) was added and heated at 135°C for 10 hours. Upon completion of the reaction, the mixture was extracted with MC and H ₂ O and then purified by column to obtain Intermediate 13. (11g, 84%)

3) 중간체 14 합성방법3) Intermediate 14 synthesis method

9H-carbazol-3-ylboronic acid (10 g, 47.3 mmol) and 1000 ml of D ₆ -benzene were added _to a reaction flask. Thereafter, CF ₃ SO ₃ H (170 g, 1075 mmol) was added and stirred at 50°C. Upon completion of the reaction, the mixture was neutralized with D ₂ O, extracted with MC and an aqueous solution of Na ₂ CO ₃ , and purified by column to obtain Intermediate 14. (9g, 87%)

4) 중간체 15 합성방법4) Intermediate 15 synthesis method

Intermediate 14 (9g, 41.3mmol), Bromobenzene (12.9g, 82.5mmol), Pd ₂ (dba) ₃ (1.89g, 2.06mmol), P(t-Bu) ₃ were added to a reaction flask. (2mL, 8.25mmol) and NaOtBu (7.93g, 82.54mmol) were added. Thereafter, toluene (100mL) was added and heated at 135°C for 10 hours. Upon completion of the reaction, the mixture was extracted with MC and H ₂ O and then purified by column to obtain Intermediate 15. (10g, 82%)

5) 화합물 2-61(F) 합성방법5) Synthesis method of compound 2-61(F)

Intermediate 13 (10 g, 30.37 mmol), intermediate 15 (17.87 g, 60.75 mmol), Pd(PPh ₃ ) ₄ (1.39, 1.52 mmol), and K ₂ CO ₃ (12.59 g, 91.13 mmol) were added to a reaction flask. put in Then, a mixture of 1,4-dioxane/distilled water (1,4-dioxane/water) (140ml/35ml) was added and heated at 120°C for 4 hours. After completion of the reaction, the temperature was lowered to room temperature, and the formed solid was washed with distilled water and methanol (MeOH) to obtain compound 2-61 (F). (13g, 85%)

Table 6 in the same manner as in Preparation Example 6, except that Compounds D and E of Table 6 were used instead of bromobenzene used in the synthesis method of Intermediate 13 and Intermediate 15 of Preparation Example 6, respectively. The target compound F of was synthesized.

<제조예 7> 화합물 2-81(H)의 제조방법<Preparation Example 7> Method for preparing compound 2-81 (H)

After adding compound G ( _10g , 1eq.), D ₆ -benzene (500g, 287.93eq.), and CF ₃ SO ₃ H (245g, 75.04eq.) to a reaction flask, 50 It reacted for 1 hour at °C. After the reaction was completed, H ₂ O was added to neutralize the mixture, followed by extraction with MC and H ₂ O, and the organic layer was column-purified to obtain compound 2-81 (H). (7g, 66%)

The target compound H in Table 7 was synthesized in the same manner as in Preparation Example 7, except that Compound G in Table 7 was used instead of Compound G in the preparation method of Compound 2-81(H) in Preparation Example 7.

Compounds were prepared in the same manner as in the above preparations, and the synthesis confirmation results are shown in Tables 8 and 9 below. Specifically, Table 8 is a measurement value of ¹ H NMR (CDCl ₃ , 300 Mz), and Table 9 is a measurement value of FD-mass spectrometer (FD-MS: Field desorption mass spectrometry).

<실험예 1><Experimental Example 1>

(1) 유기 발광 소자의 제작(1) Fabrication of organic light emitting device

A glass substrate coated with ITO thin film to a thickness of 1,500 Å was washed with distilled water and ultrasonic waves. After washing with distilled water, it was ultrasonically washed with solvents such as acetone, methanol, and isopropyl alcohol, dried, and then treated with UVO for 5 minutes using UV in a UV cleaner. Thereafter, the substrate was transferred to a plasma cleaner (PT), plasma treated to remove the ITO work function and residual film in a vacuum state, and then transferred to a thermal evaporation equipment for organic deposition.

A hole injection layer 2-TNATA (4,4', 4''-Tris [2-naphthyl (phenyl) amino] triphenylamine) and a hole transport layer NPB (N, N'-Di) as a common layer on the ITO transparent electrode (anode) (1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine) was formed.

A light emitting layer was thermally vacuum deposited thereon as follows. The light emitting layer was deposited with 400 Å of the compound of Table 10 as a host, and a green phosphorescent dopant was deposited by doping 7% of Ir(ppy) ₃ . Thereafter, 60 Å of BCP was deposited as a hole blocking layer, and 200 Å of Alq ₃ was deposited thereon as an electron transport layer. Finally, lithium fluoride (LiF) is deposited on the electron transport layer to a thickness of 10 Å to form an electron injection layer, and then an aluminum (Al) cathode is deposited on the electron injection layer to a thickness of 1,200 Å to form a cathode. Organic light emitting diodes of Examples 1 to 104 and Comparative Examples 1 to 12 were prepared.

On the other hand, all organic compounds required for OLED device fabrication were purified by vacuum sublimation under 10 ⁻⁶ to 10 ⁻⁸ torr for each material and used for OLED fabrication.

(2) 유기 발광 소자의 평가(2) Evaluation of organic light emitting devices

Electroluminescence (EL) characteristics of the organic light emitting devices of Examples 1 to 116 and Comparative Examples 1 to 12 prepared as described above were measured with McScience's M7000, respectively, and with the measurement results, McScience manufactured T ₉₀ was measured when the standard luminance was 700 cd/m ² through a lifetime measuring device (M6000).

Table 10 shows the results of measuring the driving voltage, luminous efficiency, color coordinates (CIE), and lifetime (T ₉₀ . Unit: hours) of the blue organic light emitting device manufactured according to the present invention.

Compounds A to L in Table 10 were as follows.

As can be seen from the results of Table 10, it can be seen that the organic light emitting device using the compound according to the present application has a lower driving voltage and higher efficiency and lifetime than the organic light emitting device using the compounds A to L of Comparative Examples.

That is, it was confirmed that the organic light emitting device using the compound according to the present application has excellent effects.

Specifically, when Comparative Examples Compounds A, F, H and I were used in the device, it was confirmed that they had high driving voltage and low efficiency. This is because the Comparative Examples Compounds A, F, H and I have a high triplet energy level (T1 energy level) of about 2.5 eV or more, so energy transfer from the host to the dopant is easy, but according to the present application This is because the electron distribution of the HOMO level is not extended to the core, rather than the compound, and the degree of overlap of the HOMO and LUMO of the compound is lowered.

In addition, it was confirmed that the operation, efficiency, and lifespan of the device were superior to the case of using the compound according to the present application as compared to the case of using Comparative Examples Compounds C, D, E, and J in the device. This is because Comparative Example Compounds C, D, E, and J are compounds substituted with a substituent (a substituent having more than 12 carbon atoms) such as a terphenyl group and a triphenyl group, and, like the compound of the present application, a biphenyl group (a substituent having 12 carbon atoms) is substituted. This is because it has a lower triplet energy level (T1 energy level) than the compound, so there is a disadvantage in that the deposition temperature increases during the manufacture of the organic material layer of the device. That is, when a compound substituted with a substituent having 12 or less carbon atoms, such as the compound according to the present application, is used in an organic light emitting device, excellent characteristics are exhibited in driving, efficiency, and lifespan of the device.

In addition, it can be seen that when Comparative Examples Compounds B and G were used in the device, lifespan characteristics were not as good as those in the case where the compound according to the present application was used in the organic light emitting device. This is because a compound in which a biphenyl group corresponding to an unsubstituted aryl group has a high T1 energy, such as the compound according to the present application.

That is, the compound according to the present application has a higher luminous efficiency than the comparative example compound.

In addition, when the N-containing ring is substituted with an unsubstituted aryl group, such as in Comparative Examples Compounds B and G, the substituent having hole transfer (HT) characteristics and the dibenzofuran core bond are composed of C-N bonds will lose The C-N bond dissociation energy is 2.52 eV, which is lower than the C-C bond dissociation energy of 4.9 eV, like the compound of the present invention.

That is, since the compound according to the present application has a higher bonding dissociation energy than Comparative Examples Compounds B and G, the stability of the material is more excellent, and when used in an organic light emitting device, the device has a high lifetime have

The compound according to the present application depends on where triazine is substituted in the dibenzofuran core, that is, according to the bonding position of triazine, and the operation, efficiency and efficiency of the device using the same It shows the difference in life expectancy. This effect was confirmed through the characteristics of the devices of Examples 28 to 51 and 75 to 80 in Table 9 above.

In particular, when triazine is substituted at the 3-position of the dibenzofuran core, it can have the highest bonding dissociation energy, so the stability of the material is the best and the lifespan of the device using it is the best. It was found to be the best.

In addition, among the compounds according to the present application, the compound containing deuterium is packed with a narrower distance between molecules when deposited than the compound without deuterium among the compounds of the present application, so that it is easy to transport charges, so that the device using the same has higher efficiency and It was confirmed that it had a lifespan.

<실험예 2><Experimental Example 2>

A light emitting layer was thermally vacuum deposited thereon as follows. The light emitting layer was deposited at 400 Å in one park after preliminary mixing according to the weight ratio of the compounds listed in Table 11 below as a host, and the green phosphorescent dopant was deposited by doping 7% of Ir(ppy) ₃ . Thereafter, 60 Å of BCP was deposited as a hole blocking layer, and 200 Å of Alq ₃ was deposited thereon as an electron transport layer. Finally, lithium fluoride (LiF) is deposited on the electron transport layer to a thickness of 10 Å to form an electron injection layer, and then an aluminum (Al) cathode is deposited on the electron injection layer to a thickness of 1,200 Å to form a cathode. Organic light-emitting devices of Examples 105 to 305 and Comparative Examples 13 to 78 were prepared.

For the organic light emitting devices of Examples 105 to 305 and Comparative Examples 13 to 78 prepared as described above, electroluminescence (EL) characteristics were measured with McScience's M7000, respectively, and with the measurement results, McScience manufactured When the standard luminance is 6,000 cd/m ² through the life measurement equipment (M6000), the lifetime T ₉₀ (unit: h, time), which is the time to reach 90% of the initial luminance, was measured, and the measurement results are shown in Table 11 below. was

Compounds A to L and Compounds A-1 to A-4 in Table 11 were as follows.

As can be seen from the results of Table 11, the case where the heterocyclic compound represented by Formula 1 of the present application is used in the device together with the compound represented by Formula 2 of the present application is higher than the case of using the compound represented by Formula 1 alone in the device. It was confirmed that the efficiency and lifespan exhibited more excellent performance.

These results are considered to be due to the occurrence of exciplex when the heterocyclic compound represented by Chemical Formula 1 and the compound represented by Chemical Formula 2 are simultaneously used.

The exciplex phenomenon is, when an N-type HOST compound and a P-type HOST compound are simultaneously used, an electron exchange between the molecules of the compounds results in a donor ( It is a phenomenon in which energy is emitted in the size of the HOMO level (highest occupied molecular orbital level) of the donor, p-host function and the LUMO level (lowest unoccupied molecular orbital level) of the acceptor (acceptor, n-host function).

That is, when a donor with good hole transport ability and an acceptor with good electron transport ability are used as hosts of the light emitting layer at the same time, holes are injected into the P-type host, and electrons are injected into N Since it is injected into the -type host (N-type HOST), the driving voltage can be lowered, thereby helping to improve the lifespan.

In the present application, the heterocyclic compound represented by Formula 1 is used as an N-type host (N-type HOST) compound, and the heterocyclic compound represented by Formula 2 is used as a P-type host (P-type HOST) compound. It became.

In addition, in this case, among the heterocyclic compounds represented by Formula 1 of the present application, triazine is substituted at position 3 of the dibenzofuran core in which the biphenyl group, which is a linear substituent, is substituted. It was confirmed that the prepared compound had a better effect.

This can be attributed to the highest bond dissociation energy (BDE) when triazine is substituted at position 3 of the dibenzofuran core.

Here, position 3 of the dibenzofuran core is as described above.

In addition, among the compounds represented by Formulas 1 and 2, compounds containing deuterium show superior effects in driving, efficiency, and lifespan compared to compounds not containing deuterium, respectively, and the higher the content of deuterium, the more excellent the effect. I was able to see what I was seeing.

That is, it was confirmed that the operation, efficiency, and lifespan of the organic light emitting device were further increased when the compound in which all deuterium was substituted with deuterium was used in the organic light emitting device rather than the compound in which deuterium was partially substituted.

In addition, Examples 143 to 198, 231 to 245, 254 to 259, 264, 265, 270 to 278, 285 to 288, and 294 to 299 of Table 11 show that the compound represented by Formula 1 of the present application does not contain deuterium. This is an example showing the effect when the compound represented by Formula 2 of the present application and when it contains deuterium.

Through this, it was confirmed that when the compound represented by Chemical Formula 2 of the present application contains deuterium, when used in a device, the performance of the device is superior to that when it does not contain deuterium.

More specifically, when Formula 2 of the present application is partially substituted with deuterium, hydrogen of biscarbazole is deuterium than when hydrogen of the aryl group corresponding to R21 and R22 in Formula 2 is substituted with deuterium. It was confirmed that the performance of the device using it was better when it was substituted with, and the performance of the device using it was better as the content of deuterium was higher.

In addition, referring to Examples 199 to 230, 246 to 253, 260 to 263, 266 to 269, 279 to 284, 289 to 293, and 300 to 305 of Table 11, when the compound represented by Formula 1 is substituted with deuterium Even in the case where the compound represented by Formula 2 contains deuterium, it was confirmed that the effect is superior to the case where the compound represented by Formula 2 does not contain deuterium.

In addition, among cases in which the compound of Formula 1 was substituted with deuterium, it was confirmed that the performance of the device was excellent when only the biphenyl group portion or the triazine group portion was substituted with deuterium, and when the biphenyl portion was substituted with deuterium.

Finally, it was confirmed that the compound represented by Formula 1 and the compound represented by Formula 2 showed excellent results as the deuterium substitution ratio increased.

Claims

An organic light emitting device comprising an anode, a cathode, and one or more organic material layers provided between the anode and the cathode, wherein at least one of the organic material layers is a heterocyclic compound represented by Formula 1 below and a heterocyclic compound represented by Formula 2 below. An organic light emitting device comprising:

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

X1 is O; S; CRaRb; or NRc;

R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; -CN; Or a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms,

a is an integer from 0 to 5, and when a is 2 or more, R1 in parentheses are the same as or different from each other;

b is an integer from 0 to 4, and when b is 2 or more, R2 in parentheses are the same as or different from each other;

c is an integer from 0 to 3, and when c is 2 or more, R3 in parentheses are the same as or different from each other;

d is an integer from 0 to 2, and when d is 2, R4 in parentheses are the same as or different from each other;

Rm is hydrogen; or deuterium;

Ar1 is a substituted or unsubstituted biphenyl group; A substituted or unsubstituted dibenzofuran group; Or a substituted or unsubstituted dimethylfluorene group,

Ar2 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms;

Wherein Ra to Rc are the same as or different from each other, and each independently, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms;

Rd and Re are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms; A substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted heterocycloalkyl group having 2 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; -SiR31R32R33; -P(=0)R31R32; and a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms and a substituted or unsubstituted amine group selected from the group consisting of Or, two or more groups adjacent to each other bond to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,

R21 and R22 are the same as or different from each other, and each independently -SiR31R32R33; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

R31, R32, and R33 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

r and s are integers from 0 to 7, and when r and s are integers of 2 or more, the substituents in parentheses are the same as or different from each other.
The organic light emitting device of claim 1, wherein Chemical Formula 1 is represented by any one of the following Chemical Formulas 3 to 5:

[Formula 3]

[Formula 4]

[Formula 5]

In Formulas 3 to 5,

R5 to R8 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

e is an integer from 0 to 4, and when e is 2 or more, R5 in parentheses are the same as or different from each other;

f is an integer from 0 to 5, and when f is 2 or more, R6 in parentheses are the same as or different from each other;

g and h are each an integer from 0 to 7, and when g is 2 or more, R7 in parentheses are the same as or different from each other, and when h is 2 or more, R8 in parentheses are the same as or different from each other,

The definitions of X1, R1 to R4, a to d, Rm, and Ar2 are the same as those of Formula 1.
The organic light emitting device of claim 1, wherein the content of deuterium in the heterocyclic compound represented by Chemical Formula 1 is 10% or more and 100% or less.
The organic light emitting device of claim 1, wherein the deuterium content of the heterocyclic compound represented by Chemical Formula 2 is 10% or more and 100% or less.
The organic light emitting device of claim 1, wherein Chemical Formula 1 is represented by any one of the following compounds:
The organic light emitting device of claim 1, wherein Chemical Formula 2 is represented by any one of the following compounds:
The organic light emitting device of claim 1, wherein the organic material layer includes one or more light emitting layers, and the light emitting layer includes a heterocyclic compound represented by Chemical Formula 1 and a heterocyclic compound represented by Chemical Formula 2.
The organic light emitting device of claim 7, wherein the light emitting layer includes a host material, and includes a heterocyclic compound represented by Chemical Formula 1 and a heterocyclic compound represented by Chemical Formula 2 as host materials.
The method according to claim 1, wherein the organic light emitting device further comprises one layer or two or more layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a hole auxiliary layer, and a hole blocking layer. phosphorus organic light emitting device.
A heterocyclic compound represented by Formula 1-2:

[Formula 1-2]

In Formula 1-2,

X1 is O; S; CRaRb; or NRc;

R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; -CN; Or a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms,

a is an integer from 0 to 5, and when a is 2 or more, R1 in parentheses are the same as or different from each other;

b is an integer from 0 to 4, and when b is 2 or more, R2 in parentheses are the same as or different from each other;

c is an integer from 0 to 3, and when c is 2 or more, R3 in parentheses are the same as or different from each other;

d is an integer from 0 to 2, and when d is 2, R4 in parentheses are the same as or different from each other;

Rm is hydrogen; or deuterium;

Ar1 is a substituted or unsubstituted biphenyl group; A substituted or unsubstituted dibenzofuran group; Or a substituted or unsubstituted dimethylfluorene group,

Ar2 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms;

Wherein Ra to Rc are the same as or different from each other, and each independently, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.
The heterocyclic compound according to claim 10, wherein the deuterium content of the heterocyclic compound represented by Formula 1-2 is 10% or more and 100% or less.
A composition for an organic material layer of an organic light emitting device comprising a heterocyclic compound represented by Formula 1 below and a heterocyclic compound represented by Formula 2 below:

[Formula 1]

[Formula 2]

In Formulas 1 and 2,

X1 is O; S; CRaRb; or NRc;

R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; -CN; Or a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms,

a is an integer from 0 to 5, and when a is 2 or more, R1 in parentheses are the same as or different from each other;

b is an integer from 0 to 4, and when b is 2 or more, R2 in parentheses are the same as or different from each other;

c is an integer from 0 to 3, and when c is 2 or more, R3 in parentheses are the same as or different from each other;

d is an integer from 0 to 2, and when d is 2, R4 in parentheses are the same as or different from each other;

Rm is hydrogen; or deuterium;

Ar1 is a substituted or unsubstituted biphenyl group; A substituted or unsubstituted dibenzofuran group; Or a substituted or unsubstituted dimethylfluorene group,

Ar2 is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms;

Wherein Ra to Rc are the same as or different from each other, and each independently, a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms;

Rd and Re are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted alkenyl group having 2 to 60 carbon atoms; A substituted or unsubstituted alkynyl group having 2 to 60 carbon atoms; A substituted or unsubstituted alkoxy group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted heterocycloalkyl group having 2 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; A substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms; -SiR31R32R33; -P(=0)R31R32; and a substituted or unsubstituted alkyl group having 1 to 60 carbon atoms, a substituted or unsubstituted aryl group having 6 to 60 carbon atoms, or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms and a substituted or unsubstituted amine group. Or, two or more groups adjacent to each other bond to each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,

R21 and R22 are the same as or different from each other, and each independently -SiR31R32R33; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

R31, R32, and R33 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; -CN; A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 60 carbon atoms; A substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms,

r and s are integers from 0 to 7, and when r and s are integers of 2 or more, the substituents in parentheses are the same as or different from each other.
The method according to claim 12, The weight ratio of the heterocyclic compound represented by the formula (1): the heterocyclic compound represented by the formula (2) in the composition is 1: 10 to 10: 1 of the organic material layer composition of the organic light emitting device.