KR20240057483A - Heterocyclic compound, organic light-emitting device and composition for organic material layer of organic light-emitting device comprising same - Google Patents

Abstract

The present specification provides a heterocyclic compound, an organic light-emitting device containing the same, and a composition for the organic material layer of the organic light-emitting device.

Description

Heterocyclic compound, organic light-emitting device containing the same, and composition for the organic material layer of the organic light-emitting device {HETEROCYCLIC COMPOUND, ORGANIC LIGHT-EMITTING DEVICE AND COMPOSITION FOR ORGANIC MATERIAL LAYER OF ORGANIC LIGHT-EMITTING DEVICE COMPRISING SAME}

The present invention relates to heterocyclic compounds, organic light-emitting devices containing the same, and compositions for organic material layers of organic light-emitting devices.

An electroluminescent device is a type of self-luminous display device and has the advantage of a wide viewing angle, excellent contrast, and fast response speed.

Organic light-emitting devices have a structure in which an organic thin film is placed between two electrodes. When voltage is applied to an organic light emitting device with this structure, electrons and holes injected from two electrodes combine in the organic thin film to form a pair and then annihilate, emitting light. The organic thin film may be composed of a single layer or multiple layers, depending on need.

The material of the organic thin film may have a light-emitting function as needed. For example, as an organic thin film material, a compound that can independently form a light-emitting layer may be used, or a compound that can act as a host or dopant of a host-dopant-based light-emitting layer may be used. In addition, as a material for the organic thin film, compounds that can perform 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, efficiency, and lifespan of organic light-emitting devices, the development of organic thin film materials is continuously required.

US Patent No. 4,356,429

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

In an exemplary embodiment of the present application, a heterocyclic compound represented by the following formula (1) is provided.

[Formula 1]

In Formula 1,

X is O, S or -C(Ra)(Rb), and Ra and Rb are substituted or unsubstituted C1 to C60 alkyl groups,

L is a direct bond; Or a substituted or unsubstituted C6 to C60 arylene group,

n is an integer from 1 to 3, and when n is 2 or more, the substituents in parentheses are the same or different from each other,

Y1 is CR11 or N, Y2 is CR12 or N, Y3 is CR13 or N, Y4 is CR14 or N, Y5 is CR15 or N, and at least one of Y1 to Y5 is N,

R11 to R15 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heterocyclic group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C2 to C60 heterocycle,

R1 and R2 are the same or different from each other and are each independently hydrogen; heavy hydrogen; halogen group; Cyano group; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C3 to C60 cycloalkyl group; Substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heterocyclic group,

a is an integer from 0 to 4, and when a is 2 or more, the substituents in parentheses are the same or different,

b is an integer from 0 to 4, and when b is 2 or more, the substituents in parentheses are the same or different,

Ar1 is a substituted or unsubstituted aryl group of C6 to C60, or any one of the following formulas A and B,

[Formula A]

[Formula B]

In Formula A and Formula B,

X1 is O, S or N(R10),

R10 is hydrogen; Substituted or unsubstituted C1 to C60 alkyl group; Or a substituted or unsubstituted aryl group of C6 to C60,

R3 and R4 are hydrogen; heavy hydrogen; halogen group; Cyano group; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C3 to C60 cycloalkyl group; Substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heterocyclic group,

c is an integer from 0 to 7, and when c is 2 or more, the substituents in parentheses are the same or different,

d is an integer from 0 to 8, and when d is 2 or more, the substituents in parentheses are the same or different.

Additionally, in an exemplary embodiment of the present application, a first electrode; a second electrode provided opposite to the first electrode; and an organic light-emitting device comprising at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a heterocyclic compound represented by Formula 1. provides.

In addition, in an exemplary embodiment of the present application, an organic light-emitting device is provided wherein the organic material layer further includes a heterocyclic compound represented by the following formula (2).

[Formula 2]

In Formula 2,

R21 and R22 are the same or different from each other, and are each independently a substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heterocyclic group,

Rc and Rd are the same or different from each other and are each independently hydrogen; heavy hydrogen; halogen group; Cyano group; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C2 to C60 alkenyl group; Substituted or unsubstituted C2 to C60 alkynyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted C3 to C60 cycloalkyl group; Substituted or unsubstituted C2 to C60 heterocycloalkyl group; Substituted or unsubstituted C6 to C60 aryl group; Substituted or unsubstituted C2 to C60 heteroaryl group; -SiR31R32R33; -P(=O)R31R32; and a substituted or unsubstituted C1 to C60 alkyl group, a substituted or unsubstituted C6 to C60 aryl group, or a substituted or unsubstituted C2 to C60 heteroaryl group, or a substituted or unsubstituted amine group, or each other. Two or more adjacent groups combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,

R31, R32 and R33 are the same or different from each other and are each independently hydrogen; heavy hydrogen; -CN; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,

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 or different from each other.

Additionally, in an exemplary embodiment of the present application, a heterocyclic compound represented by Formula 1; and a composition for an organic material layer of an organic light-emitting device comprising a heterocyclic compound represented by Formula 2.

The heterocyclic compounds described herein can be used as organic layer materials for organic light-emitting devices. In other words, it can serve as a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. in an organic light emitting device. In particular, it can be used as a light-emitting layer material for organic light-emitting devices.

Specifically, one or two or more types of heterocyclic compounds represented by Formula 1 may be used, and may be used as a material for the light-emitting layer. In particular, it can be used as a host material for the light-emitting layer of an organic light-emitting device by introducing various substituents and changing the bonding positions of the substituents to adjust the bandgap.

The heterocyclic compound of the present invention has a disubstituted structure in which (1) an azine-based substituent and (2) an aryl group or a tricyclic heterocyclic group are introduced into the core skeleton, and at the same time, the above-mentioned (1) and (2) By combining the substituents at specific positions, structural stability is superior to that of a 1- or 3-substituted structure, and hole mobility is also faster than that of a 1- or 3-substituted structure.

In particular, when the heterocyclic compound of the present invention is used in the light-emitting layer of an organic light-emitting device, the driving voltage of the device is lowered, the efficiency of the device is increased, and the lifespan is extended.

The heterocyclic compound described herein can be used as an organic layer material for an organic light-emitting device. In other words, it can serve as a light emitting material, a hole injection material, a hole transport material, an electron transport material, an electron injection material, etc. in an organic light emitting device. In particular, it can be used as a light-emitting layer material for organic light-emitting devices.
Specifically, one or two or more types of heterocyclic compounds represented by Formula 1 may be used, and may be used as a material for the light-emitting layer. In particular, it can be used as a host material for the light-emitting layer of an organic light-emitting device by introducing various substituents and changing the bonding positions of the substituents to adjust the bandgap.
The heterocyclic compound of the present invention has a disubstituted structure in which (1) an azine-based substituent and (2) an aryl group or a tricyclic heterocyclic group are introduced into the core skeleton, and the above-mentioned (1) and (2) By combining the substituents at specific positions, structural stability is superior to that of a 1- or 3-substituted structure, and hole mobility is also faster than that of a 1- or 3-substituted structure.
In particular, when the heterocyclic compound of the present invention is used in the light-emitting layer of an organic light-emitting device, the driving voltage of the device is lowered, the efficiency of the device is increased, and the lifespan is extended.

Hereinafter, this specification will be described in more detail.

In this specification, when a part “includes” a certain component, this means that it may further include other components rather than excluding other components unless specifically stated to the contrary.

In this specification, the chemical formula means the position where it is combined.

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

In this specification, “substituted or unsubstituted” means deuterium; halogen group; -CN; C1 to C60 alkyl group; C2 to C60 alkenyl group; C2 to C60 alkynyl group; C1 to C60 haloalkyl group; C1 to C60 alkoxy group; Aryloxy group of C6 to C60; C1 to C60 alkylthioxy group; Arylthioxy group of C6 to C60; C1 to C60 alkyl sulfoxy group; C6 to C60 aryl sulfoxy group; C3 to C60 cycloalkyl group; C2 to C60 heterocycloalkyl group; Aryl group of C6 to C60; C2 to C60 heteroaryl group; -SiRR'R"; -P(=O)RR'; means that one or more substituents selected from the group consisting of -NRR', or two or more substituents selected from the above exemplified substituents are substituted or unsubstituted with a connected substituent; , R, R' and R" are each independently hydrogen; heavy hydrogen; halogen group; Alkyl group; alkenyl group; Alkoxy group; Cycloalkyl group; heterocycloalkyl group; Aryl group; and a substituent consisting of at least one of a heteroaryl group.

In this specification, “when a substituent is not indicated in the chemical formula or compound structure” means that a hydrogen atom is bonded to a carbon atom. However, since deuterium ( ^2H , Deuterium) is an isotope of hydrogen, some hydrogen atoms may be deuterium.

In an exemplary embodiment of the present application, “when a substituent is not indicated in the chemical formula or compound structure” may mean that all positions that can appear as substituents are hydrogen or deuterium. That is, in the case of deuterium, it is an isotope of hydrogen, and some hydrogen atoms may be the isotope deuterium, and in this case, the content of deuterium may be 0% to 100%.

In an exemplary embodiment of the present application, in “cases where substituents are not indicated in the chemical formula or compound structure,” the content of deuterium is 0%, the content of hydrogen is 100%, and all substituents are hydrogen, etc., explicitly excluding deuterium. Otherwise, hydrogen and deuterium can be used together in compounds.

In an exemplary embodiment of the present application, deuterium is one of the isotopes of hydrogen and is an element that has a deuteron, consisting of one proton and one neutron, as its nucleus. Hydrogen- It can be expressed as 2, and the element symbol can also be written as D or ² H.

In an exemplary embodiment of the present application, isotopes refer to atoms having the same atomic number (Z) but different mass numbers (A). Isotopes have the same number of protons but do not contain 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 means that the total number of substituents that the basic compound can have is defined as T1, and the number of specific substituents among them is defined as T2. It can be defined as /T1Х100 = T%.

That is, in one example, The deuterium content of 20% in the phenyl group represented by means that the total number of substituents that the phenyl group can have is 5 (T1 in the formula), and if the number of deuteriums among them is 1 (T2 in the formula), it will be expressed as 20%. You can. That is, the deuterium content of 20% in the phenyl group can be expressed by the following structural formula.

Additionally, in an exemplary embodiment of the present application, “a phenyl group with a deuterium content of 0%” may mean a phenyl group that does not contain deuterium atoms, that is, has 5 hydrogen atoms.

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

In the present specification, the alkyl group includes a straight chain or branched chain having 1 to 60 carbon atoms, and may be further substituted by another substituent. The carbon number 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, octyl group, n-octyl group, tert-octyl group, 1-methylheptyl group Tyl 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-methyl Examples include pentyl group, 4-methylhexyl group, and 5-methylhexyl group, but it is not limited thereto.

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

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 another substituent. The carbon number of the alkynyl group may be 2 to 60, specifically 2 to 40, and more specifically, 2 to 20.

In this specification, a haloalkyl group refers to an alkyl group substituted with a halogen group, and specific examples include -CF ₃ and -CF ₂ CF ₃ , but are not limited thereto.

In this specification, the alkoxy group is represented by -O(R101), and examples of the above-described alkyl group may be applied to R101.

In the present specification, the aryloxy group is represented by -O(R102), and examples of the above-described aryl groups may be applied to R102.

In this specification, the alkylthioxy group is represented by -S(R103), and examples of the alkyl groups described above may be applied to R103.

In the present specification, the arylthioxy group is represented by -S(R104), and examples of the above-described aryl groups may be applied to R104.

In this specification, the alkylsulfoxy group is represented by -S(=0) ₂ (R105), and examples of the alkyl groups described above may be applied to R105.

In the present specification, the arylsulfoxy group is represented by -S(=0) ₂ (R106), and examples of the above-described aryl groups may be applied to R106.

In the present specification, the cycloalkyl group includes a monocyclic or polycyclic ring having 3 to 60 carbon atoms and may be further substituted by another substituent. Here, polycyclic refers to a group in which a cycloalkyl group is directly connected to 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, or a heteroaryl group. The carbon number of 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 is not limited thereto.

In the present specification, the heterocycloalkyl group contains O, S, Se, N or Si as a hetero atom, contains a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by another substituent. Here, polycyclic refers to a group in which a heterocycloalkyl group is directly connected to 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, or a heteroaryl group. The carbon number of the heterocycloalkyl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 20.

In the present specification, the aryl group includes a monocyclic or polycyclic ring having 6 to 60 carbon atoms, and may be further substituted by another substituent. Here, polycyclic refers to a group in which an aryl group is directly connected to or condensed with another ring 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, heterocycloalkyl group, heteroaryl group, etc. The aryl group includes a spiro group. The aryl group may have 6 to 60 carbon atoms, specifically 6 to 40 carbon atoms, and more specifically 6 to 25 carbon atoms. Specific examples of the aryl group include phenyl group, biphenyl group, terphenyl group, naphthyl group, anthryl group, chrysenyl group, phenanthrenyl group, perylenyl group, fluoranthenyl group, triphenylenyl group, and phenalenyl group. , pyrenyl group, tetracenyl group, pentacenyl group, fluorenyl group, indenyl group, acenaphthylenyl group, benzofluorenyl group, spirobifluorenyl group, 2,3-dihydro-1H-indenyl group, these Condensation ring groups, etc. may be included, but are not limited thereto.

In the present specification, the terphenyl group may be selected from the following structures.

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

When the fluorenyl group is substituted, , , , , , It may be, but is not limited to this.

In the present specification, the heteroaryl group contains S, O, Se, N or Si as a hetero atom, contains a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by another substituent. Here, the polycyclic refers to a group in which a heteroaryl group is directly connected to 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, heterocycloalkyl group, or aryl group. The carbon number of the heteroaryl group may be 2 to 60, specifically 2 to 40, and more specifically 3 to 25. Specific examples of the heteroaryl group include pyridine group, pyrrole group, pyrimidine group, pyridazine group, furan group, thiophene group, imidazole group, pyrazole group, oxazole group, isoxazole group, thiazole group, isothiazole group, Triazole group, furazine group, oxadiazole group, thiadiazole group, dithiazole group, tetrazolyl group, pyran group, thiopyran group, diazine group, oxazine group, thiazine group, dioxine group, triazine group, tetrazine group, quinoline group, Isoquinoline group, quinazoline group, isoquinazoline group, quinozoline group, naphthyridine group, acridine group, phenanthridine group, imidazopyridine group, diazanaphthalene group, triazindene group, indole group, indolizine group, Benzothiazole group, benzoxazole group, benzimidazole group, benzothiophene group, benzofuran group, dibenzothiophene group, dibenzofuran group, carbazole group, benzocarbazole group, dibenzocarbazole group, phenazine group, dibenzo Sylol group, spirobi (dibenzosilol), dihydrophenazine group, phenoxazine group, phenanthridine group, thienyl group, indolo [2,3-a] carbazole group, indolo [2,3-b] carbazole group, Indoline group, 10,11-dihydro-dibenzo[b,f]azepine group, 9,10-dihydroacridine group, phenanthrazine group, phenothiathiazine group, phthalazine group, phenanthroline group, naphthobenzofuran group, naphthobenzothiophene group, benzo[c][1,2,5]thiadiazole group, 2,3-dihydrobenzo[b]thiophene group, 2,3-dihydrobenzofuran group, 5, 10-dihydrodibenzo[b,e][1,4]azacillin group, pyrazolo[1,5-c]quinazoline group, pyrido[1,2-b]indazole group, pyrido[1, Examples include, but are not limited to, 2-a]imidazo[1,2-e]indoline group and 5,11-dihydroindeno[1,2-b]carbazole group.

In this specification, when the substituent is a carbazole group, it means bonding with the nitrogen or carbon of carbazole.

In this specification, when a carbazole group is substituted, an additional substituent may be substituted on the nitrogen or carbon of the carbazole.

In the present specification, the benzocarbazole group may have any one of the following structures.

In the present specification, the dibenzocarbazole group may have any one of the following structures.

In the present specification, the naphthobenzofuran group may have any of the following structures.

In the present specification, the naphthobenzothiophene group may have any one of the following structures.

In the present specification, the silyl group is a substituent that contains Si and is directly connected to the Si atom as a radical, and is represented by -Si(R107)(R108)(R109), and R107 to R109 are the same or different from each other, and each independently hydrogen; heavy hydrogen; halogen group; Alkyl group; alkenyl group; Alkoxy group; Cycloalkyl group; heterocycloalkyl group; Aryl group; And it may be a substituent consisting of at least one of a heteroaryl group. Specific examples of silyl groups include: (trimethylsilyl group), (triethylsilyl group), (t-butyldimethylsilyl group), (vinyldimethylsilyl group), (propyldimethylsilyl group), (triphenylsilyl group), (diphenylsilyl group), (phenylsilyl group), etc., but is not limited thereto.

In the present specification, the phosphine oxide group is represented by -P(=O)(R110)(R111), and R110 and R111 are the same or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; Alkyl group; alkenyl group; Alkoxy group; Cycloalkyl group; heterocycloalkyl group; Aryl group; And it may be a substituent consisting of at least one of a heteroaryl group. Specifically, it may be substituted with an alkyl group or an aryl group, and the examples described above may be applied to the alkyl group and the aryl group. For example, phosphine oxide groups include dimethylphosphine oxide, diphenylphosphine oxide, and dinaphthylphosphine oxide, but are not limited thereto.

In this specification, the amine group is represented by -N(R112)(R113), and R112 and R113 are the same or different from each other and are each independently hydrogen; heavy hydrogen; halogen group; Alkyl group; alkenyl group; Alkoxy group; Cycloalkyl group; heterocycloalkyl group; Aryl group; And it may be a substituent consisting of at least one of a heteroaryl group. The amine group is -NH ₂ ; Monoalkylamine group; monoarylamine group; Monoheteroarylamine group; dialkylamine group; Diarylamine group; Diheteroarylamine group; Alkylarylamine group; Alkylheteroarylamine group; and 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 methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, dibiphenylamine group, anthracenylamine group, 9- Methyl-anthracenylamine group, diphenylamine group, phenylnaphthylamine group, ditolylamine group, phenyltolylamine group, triphenylamine group, biphenylnaphthylamine group, phenylbiphenylamine group, biphenyl fluores Examples include a nylamine group, phenyltriphenylenylamine group, and biphenyltriphenylenylamine group, but are not limited to these.

In the present specification, the examples of the aryl group described above may be applied, except that the arylene group is a divalent group.

In the present specification, the examples of the heteroaryl group described above may be applied, except that the heteroarylene group is a divalent group.

As used herein, an “adjacent” group may mean a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent located closest to the substituent in terms of structure, or another substituent substituted on the atom on which the substituent is substituted. You 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 can be interpreted as “adjacent” groups.

Hydrocarbon rings and heterocycles that can be formed by adjacent groups include aliphatic hydrocarbon rings, aromatic hydrocarbon rings, aliphatic heterocycles, and aromatic heterocycles, and the rings are each of the above-described cycloalkyl groups and aryl groups, except that they are not monovalent. Structures exemplified by groups, heterocycloalkyl groups, and heteroaryl groups can be applied.

In an exemplary embodiment of the present application, a group not indicated as a substituent; Alternatively, it may mean that all groups represented by hydrogen can be replaced by deuterium. i.e. hydrogen; Alternatively, it may indicate that deuterium can be substituted for each other.

In general, compounds bonded with hydrogen and compounds substituted with deuterium show differences in thermodynamic behavior. This is because the mass of a deuterium atom is twice that of hydrogen, and due to the difference in the masses of the atoms, deuterium has the characteristic of having a lower vibration energy.

Additionally, the single bond dissociation energy of carbon and deuterium is higher than that of carbon and hydrogen. Therefore, the structure substituted with deuterium increases the thermal stability of the molecule, which has the effect of improving the lifespan of the device using it.

When a compound is deposited on a silicon wafer, materials containing deuterium tend to be packed with narrower intermolecular distances. In addition, when looking at the surface of the thin film using an atomic force microscope (AFM), it can be seen that the thin film made from a compound containing deuterium is deposited on a more uniform surface without any aggregates.

The heterocyclic compound of Formula 1 of the present application has a deuterium substitution rate of 0% or 30% to 100% or less. When deuterium is substituted, the ground state energy is lower than that of a hydrogen-substituted compound, and as the bond length between carbon and deuterium becomes shorter, the molecular core volume decreases. This can reduce electrical polarizability and make intermolecular interactions weaker, resulting in a more stable stacking structure when manufacturing devices.

These characteristics create an amorphous state in the thin film, leading to the effect of lowering the degree of crystallinity. In other words, the heterocyclic compound of Formula 1 can be effective in improving the heat resistance of OLED devices, which can improve lifespan and driving characteristics.

In an exemplary embodiment of the present application, a heterocyclic compound represented by the following formula (1) is provided.

[Formula 1]

In Formula 1,

X is O, S or -C(Ra)(Rb), and Ra and Rb are substituted or unsubstituted C1 to C60 alkyl groups,

L is a direct bond; Or a substituted or unsubstituted C6 to C60 arylene group,

n is an integer from 1 to 3, and when n is 2 or more, the substituents in parentheses are the same or different from each other,

Y1 is CR11 or N, Y2 is CR12 or N, Y3 is CR13 or N, Y4 is CR14 or N, Y5 is CR15 or N, and at least one of Y1 to Y5 is N,

R11 to R15 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heterocyclic group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C2 to C60 heterocycle,

R1 and R2 are the same or different from each other and are each independently hydrogen; heavy hydrogen; halogen group; Cyano group; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C3 to C60 cycloalkyl group; Substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heterocyclic group,

a is an integer from 0 to 4, and when a is 2 or more, the substituents in parentheses are the same or different,

b is an integer from 0 to 4, and when b is 2 or more, the substituents in parentheses are the same or different,

Ar1 is a substituted or unsubstituted aryl group of C6 to C60, or any one of the following formulas A and B,

[Formula A]

[Formula B]

In Formula A and Formula B,

X1 is O, S or N(R10),

R10 is hydrogen; Substituted or unsubstituted C1 to C60 alkyl group; Or a substituted or unsubstituted aryl group of C6 to C60,

R3 and R4 are hydrogen; heavy hydrogen; halogen group; Cyano group; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C3 to C60 cycloalkyl group; Substituted or unsubstituted C2 to C60 heterocycloalkyl group; Substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heterocyclic group,

c is an integer from 0 to 7, and when c is 2 or more, the substituents in parentheses are the same or different,

d is an integer from 0 to 8, and when d is 2 or more, the substituents in parentheses are the same or different.

In an exemplary embodiment of the present application, the formula A may be represented by any one of the following formulas A-1 to A-4.

[Formula A-1]

[Formula A-2]

[Formula A-3]

[Formula A-4]

In the above formulas A-1 to A-4,

The definitions of X1, R3 and c are the same as those in Formula A above.

In an exemplary embodiment of the present application, Formula 1 may be represented by any of the following Formulas 1-1 and 1-2.

[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,

The definitions of X, L, Ar1, R1, R2, Y1 to Y5, a, b, and n are the same as those in Formula 1 above.

In an exemplary embodiment of the present application, Formula 1 may be expressed as the following Formula 1-3.

[Formula 1-3]

In Formula 1-3,

The definitions of X, L, Ar1, R1, R2, Y2, Y4, a, b and n are the same as those in Formula 1 above.

In an exemplary embodiment of the present application, X is O, S, or -C(Ra)(Rb), and Ra and Rb may be substituted or unsubstituted C1 to C40 alkyl groups.

In another embodiment, X is O, S, or -C(Ra)(Rb), and Ra and Rb may be substituted or unsubstituted C1 to C20 alkyl groups.

In another embodiment, X is O, S, or -C(Ra)(Rb), and Ra and Rb are a substituted or unsubstituted methyl group; Substituted or unsubstituted ethyl group; Or it may be a substituted or unsubstituted propyl group.

In another embodiment, X is O, S, or -C(Ra)(Rb), and Ra and Rb are methyl groups; ethyl group; Or it may be a profile group.

In another embodiment, X is O, S, or -C(Ra)(Rb), and Ra and Rb may be methyl groups.

In another exemplary embodiment, X may be O or S.

In another embodiment, X is -C(Ra)(Rb), and Ra and Rb may be methyl groups.

In an exemplary embodiment of the present application, L is a direct bond; Or, it may be a substituted or unsubstituted C6 to C40 arylene group.

In another embodiment, L is a direct bond; Or, it may be a substituted or unsubstituted C6 to C20 arylene group.

In another embodiment, L is a direct bond; Substituted or unsubstituted phenylene group; Substituted or unsubstituted naphthylene group; Or it may be a substituted or unsubstituted biphenylene group.

In another embodiment, L is a direct bond; phenylene group; naphthylene group; Or it may be a biphenylene group.

In another embodiment, L may be a direct bond or a phenylene group.

In another embodiment, L may be a direct bond.

In an exemplary embodiment of the present application, n is an integer of 1 to 2, and when n is 2 or more, the substituents in parentheses may be the same or different from each other.

In another embodiment, n is 2, and the substituents in parentheses may be the same or different from each other.

In another exemplary embodiment, n may be 1.

In an exemplary embodiment of the present application, Y1 is CR11 or N, Y2 is CR12 or N, Y3 is CR13 or N, Y4 is CR14 or N, Y5 is CR15 or N, and among Y1 to Y5 At least two can be N.

In another embodiment, Y1 is CR11 or N, Y2 is CR12 or N, Y3 is CR13 or N, Y4 is CR14 or N, Y5 is CR15 or N, and Y1, Y3, and Y5 At least two of them may be N.

In another embodiment, Y1 is CR11 or N, Y2 is CR12, Y3 is CR13 or N, Y4 is N, Y5 is CR15 or N, and at least two of Y1, Y3, and Y5 are It could be N.

In another embodiment, Y1 and Y5 may be N, Y2 may be CR12, Y3 may be CR13, and Y4 may be CR14.

In another embodiment, Y1 and Y3 may be N, Y2 may be CR12, Y4 may be CR14, and Y5 may be CR15.

In another embodiment, Y1 may be CR11, Y2 may be CR12, Y3 and Y5 may be N, and Y4 may be CR14.

In another embodiment, Y1, Y3, and Y5 may be N, Y2 may be CR12, and Y4 may be CR14.

In an exemplary embodiment of the present application, R11 to R15 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C6 to C40 aryl group; Alternatively, it may be a substituted or unsubstituted C2 to C40 heterocyclic group, or two or more groups adjacent to each other may be bonded to each other to form a substituted or unsubstituted C2 to C40 heterocycle.

In another exemplary embodiment, R11 to R15 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C6 to C20 aryl group; Alternatively, it may be a substituted or unsubstituted C2 to C20 heterocyclic group, or two or more groups adjacent to each other may be bonded to each other to form a substituted or unsubstituted C2 to C20 heterocycle.

In another exemplary embodiment, R11 to R15 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted phenyl group; Substituted or unsubstituted naphthyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted terphenyl group; Substituted or unsubstituted fluorenyl group; Substituted or unsubstituted triphenylenyl group; Substituted or unsubstituted phenanthrenyl group; Substituted or unsubstituted dibenzofuran group; Substituted or unsubstituted dibenzothiophene group; Alternatively, it may be a substituted or unsubstituted carbazole group, or two or more groups adjacent to each other may be combined to form a substituted or unsubstituted C2 to C20 heterocycle.

In another exemplary embodiment, R11 to R15 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; A phenyl group substituted or unsubstituted with deuterium or a C6 to C20 aryl group; A naphthyl group substituted or unsubstituted with deuterium or a C6 to C20 aryl group; Biphenyl group substituted or unsubstituted with deuterium; Terphenyl group substituted or unsubstituted with deuterium; A fluorenyl group unsubstituted or substituted with a C1 to C20 alkyl group; Triphenylenyl group substituted or unsubstituted with deuterium; A phenanthrenyl group substituted or unsubstituted with deuterium; Substituted or unsubstituted dibenzofuran group; Substituted or unsubstituted dibenzothiophene group; Alternatively, it may be a substituted or unsubstituted carbazole group, or two or more groups adjacent to each other may be bonded to each other to form a substituted or unsubstituted two-membered heteroring having 1 to 2 heteroatoms selected from O and S.

In another exemplary embodiment, R11 to R15 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; A phenyl group substituted or unsubstituted with deuterium or a naphthyl group substituted or unsubstituted with deuterium; A naphthyl group substituted or unsubstituted with deuterium or a phenyl group substituted or unsubstituted with deuterium; Biphenyl group substituted or unsubstituted with deuterium; Terphenyl group; A fluorenyl group substituted with a methyl group; Triphenylenyl group; phenanthrenyl group; Dibenzofuran group; Dibenzothiophene group; Alternatively, it may be a carbazole group, or two or more groups adjacent to each other may be bonded to each other to form a substituted or unsubstituted two-membered heterocycle having 1 to 2 heteroatoms selected from O and S.

In an exemplary embodiment of the present application, Ar1 may be a substituted or unsubstituted aryl group of C6 to C40, or any one of Formula A and Formula B.

In another embodiment, Ar1 may be a substituted or unsubstituted C6 to C20 aryl group, or any one of Formula A and Formula B.

In another embodiment, Ar1 is a substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Alternatively, it may be a substituted or unsubstituted terphenyl group, or any one of Formula A and Formula B above.

In another embodiment, Ar1 is a substituted or unsubstituted phenyl group; Alternatively, it may be a substituted or unsubstituted biphenyl group, or any one of Formula A and Formula B above.

In an exemplary embodiment of the present application, R10 is hydrogen; Substituted or unsubstituted C1 to C40 alkyl group; Or it may be a substituted or unsubstituted C6 to C40 aryl group.

In an exemplary embodiment of the present application, R10 is hydrogen; Substituted or unsubstituted C1 to C20 alkyl group; Or it may be a substituted or unsubstituted C6 to C20 aryl group.

In an exemplary embodiment of the present application, R10 is hydrogen; Or it may be a substituted or unsubstituted C6 to C20 aryl group.

In an exemplary embodiment of the present application, R10 is hydrogen; Or a substituted or unsubstituted phenyl group; Or it may be a substituted or unsubstituted biphenyl group.

In an exemplary embodiment of the present application, R10 is hydrogen or a phenyl group.

In an exemplary embodiment of the present application, R3 and R4 are hydrogen; heavy hydrogen; halogen group; Cyano group; Substituted or unsubstituted C1 to C40 alkyl group; Substituted or unsubstituted C6 to C40 aryl group; Or, it may be a substituted or unsubstituted C2 to C40 heterocyclic group.

In another embodiment, R3 and R4 are hydrogen; heavy hydrogen; Substituted or unsubstituted C1 to C20 alkyl group; Substituted or unsubstituted C6 to C20 aryl group; Or, it may be a substituted or unsubstituted C2 to C20 heterocyclic group.

In another embodiment, R3 and R4 are hydrogen; heavy hydrogen; Substituted or unsubstituted methyl group; Substituted or unsubstituted ethyl group; Substituted or unsubstituted propyl group; Substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted fluorenyl group; Substituted or unsubstituted dibenzofuran group; Substituted or unsubstituted dibenzothiophene group; Or it may be a substituted or unsubstituted carbazole group.

In another embodiment, R3 and R4 are hydrogen; Or it may be deuterium.

In an exemplary embodiment of the present application, R1 and R2 are the same or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; Cyano group; Substituted or unsubstituted C1 to C40 alkyl group; Substituted or unsubstituted C3 to C40 cycloalkyl group; Substituted or unsubstituted C2 to C40 heterocycloalkyl group; Substituted or unsubstituted C6 to C40 aryl group; Or, it may be a substituted or unsubstituted C2 to C40 heterocyclic group.

In another exemplary embodiment, R1 and R2 are the same or different from each other, and are each independently hydrogen; heavy hydrogen; halogen group; Cyano group; Substituted or unsubstituted C1 to C20 alkyl group; Substituted or unsubstituted C3 to C20 cycloalkyl group; Substituted or unsubstituted C2 to C20 heterocycloalkyl group; Substituted or unsubstituted C6 to C20 aryl group; Or, it may be a substituted or unsubstituted C2 to C20 heterocyclic group.

In another exemplary embodiment, R1 and R2 are the same or different from each other, and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C1 to C20 alkyl group; Substituted or unsubstituted C6 to C20 aryl group; Or, it may be a substituted or unsubstituted C2 to C20 heterocyclic group.

In another exemplary embodiment, R1 and R2 are the same or different from each other, and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted methyl group; Substituted or unsubstituted ethyl group; Substituted or unsubstituted propyl group; Substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted terphenyl group; Substituted or unsubstituted naphthyl group; Substituted or unsubstituted phenanthrene group; Substituted or unsubstituted triphenylene group; Substituted or unsubstituted dibenzofuran group; Substituted or unsubstituted dibenzothiophene group; Or it may be a substituted or unsubstituted carbazole group.

In another exemplary embodiment, R1 and R2 are the same or different from each other, and are each independently hydrogen; heavy hydrogen; methyl group; ethyl group; profiler; phenyl group; Biphenyl group; Terphenyl group; naphthyl group; phenanthrene group; triphenylene group; Dibenzofuran group; Dibenzothiophene group; Or it may be a carbazole group.

In another exemplary embodiment, R1 and R2 are hydrogen; Or it may be deuterium.

In another exemplary embodiment, R1 and R2 may be hydrogen.

In another exemplary embodiment, R1 and R2 may be deuterium.

In an exemplary embodiment of the present application, a is an integer from 0 to 4, and when a is 2 or more, the substituents in parentheses may be the same or different.

In an exemplary embodiment of the present application, a is an integer from 0 to 3, and when a is 2 or more, the substituents in parentheses may be the same or different.

In an exemplary embodiment of the present application, a is an integer from 0 to 2, and when a is 2 or more, the substituents in parentheses may be the same or different.

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

In one embodiment of the present application, a is 1.

In an exemplary embodiment of the present application, b is an integer from 0 to 4, and when b is 2 or more, the substituents in parentheses may be the same or different.

In an exemplary embodiment of the present application, b is an integer from 0 to 3, and when b is 2 or more, the substituents in parentheses may be the same or different.

In an exemplary embodiment of the present application, b is an integer from 0 to 2, and when b is 2 or more, the substituents in parentheses may be the same or different.

In one embodiment of the present application, b is 1.

In an exemplary embodiment of the present application, the deuterium content of the heterocyclic compound of Formula 1 may be 0% or 10% to 100%.

In an exemplary embodiment of the present application, the deuterium content of the heterocyclic compound of Formula 1 may be 0% or 30% to 100%.

In an exemplary embodiment of the present application, the deuterium content of the heterocyclic compound of Formula 1 may be 0% or 50% to 100%.

In an exemplary embodiment of the present application, the deuterium content of the heterocyclic compound of Formula 1 may be 0% or 70% to 100%.

In an exemplary embodiment of the present application, the deuterium content of the heterocyclic compound of Formula 1 may be 0% or 90% to 100%.

In an exemplary embodiment of the present application, the deuterium content of the heterocyclic compound of Formula 1 may be 0%.

In an exemplary embodiment of the present application, the deuterium content of the heterocyclic compound of Formula 1 may be 30% to 100%.

In an exemplary embodiment of the present application, the deuterium content of the heterocyclic compound of Formula 1 may be 50% to 100%.

In an exemplary embodiment of the present application, the deuterium content of the heterocyclic compound of Formula 1 may be 70% to 100%.

In an exemplary embodiment of the present application, the deuterium content of the heterocyclic compound of Formula 1 may be 90% to 100%.

In an exemplary embodiment of the present application, Formula 1 provides a heterocyclic compound represented by any one of the following compounds.

In an exemplary embodiment of the present application, the compound is an example, and is not limited thereto, and may include other compounds included in Formula 1 containing additional substituents. In addition, specific positions of deuterium substitution in the above compounds are excluded during the deuterium substitution and synthesis process, and hydrogen and deuterium may coexist.

Additionally, by introducing various substituents into the structure of Formula 1, a compound having the unique properties of the introduced substituents can be synthesized. For example, by introducing substituents mainly used in hole injection materials, hole transport materials, light-emitting materials, electron transport materials, and electron injection materials used in the manufacture of organic light-emitting devices into the core structure, a material that satisfies the conditions required for each organic layer can be created. It can be synthesized.

In addition, the band gap can be finely adjusted by introducing various substituents into the structure of Formula 1 or changing the bonding position, and on the other hand, the characteristics at the interface between organic layers can be improved.

In addition, the compound of Formula 1 has excellent thermal stability, and this thermal stability provides driving stability to the organic light-emitting device and improves lifespan characteristics.

In an exemplary embodiment of the present application, a first electrode; a second electrode provided opposite to the first electrode; and an organic light-emitting device comprising at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes a heterocyclic compound represented by Formula 1. provides.

In another exemplary embodiment, a first electrode; a second electrode provided opposite to the first electrode; And an organic light-emitting device comprising at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes one type of heterocyclic compound represented by Formula 1 above. A light emitting device is provided.

In another exemplary embodiment, a first electrode; a second electrode provided opposite to the first electrode; And an organic light-emitting device comprising at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes two or more types of heterocyclic compounds represented by Formula 1. An organic light emitting device is provided.

In another embodiment, the heterocyclic compound represented by Formula 1 may be used as a light-emitting material for the light-emitting layer of an organic light-emitting device.

In another embodiment, the heterocyclic compound represented by Formula 1 may be used as a host material for the light-emitting layer of an organic light-emitting device.

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

In another exemplary embodiment, the first electrode may be a cathode, and the second electrode may be an anode.

In an exemplary embodiment of the present application, the organic light-emitting device may be a blue organic light-emitting device, and the heterocyclic compound according to Formula 1 may be used as a material for the blue organic light-emitting device.

In an exemplary embodiment of the present application, the organic light-emitting device may be a green organic light-emitting device, and the heterocyclic compound represented by Formula 1 may be used as a material for the green organic light-emitting device.

In an exemplary embodiment of the present application, the organic light-emitting device may be a red organic light-emitting device, and the heterocyclic compound represented by Formula 1 may be used as a material for the red organic light-emitting device.

In an exemplary embodiment of the present application, the organic light-emitting device may be a blue organic light-emitting device, and the heterocyclic compound according to Formula 1 may be used as a light-emitting layer material of the blue organic light-emitting device.

In an exemplary embodiment of the present application, the organic light-emitting device may be a green organic light-emitting device, and the heterocyclic compound represented by Formula 1 may be used as a light-emitting layer material of the green organic light-emitting device.

In an exemplary embodiment of the present application, the organic light-emitting device may be a red organic light-emitting device, and the heterocyclic compound represented by Formula 1 may be used as a light-emitting layer material of the red organic light-emitting device.

In an exemplary embodiment of the present application, specific details about the heterocyclic compound represented by Formula 1 are the same as those described above.

The organic light-emitting device of the present invention can be manufactured using conventional organic light-emitting device manufacturing methods and materials, except that one or more organic material layers are formed using the heterocyclic compound described above.

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

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

In an exemplary embodiment of the present application, Ir(ppy) ₃ , a green phosphorescent dopant, may be used as the iridium-based dopant.

In an exemplary embodiment of the present application, (piq) ₂ (Ir) (acac), a red phosphorescent dopant, may be used as the iridium-based dopant.

In an exemplary embodiment of the present application, an organic light-emitting device is provided wherein the organic material layer of the organic light-emitting device includes a light-emitting layer, and the light-emitting layer includes the heterocyclic compound.

In an exemplary embodiment of the present application, an organic light-emitting device is provided wherein the organic material layer of the organic light-emitting device includes a light-emitting layer, the light-emitting layer includes a host material, and the host material includes the heterocyclic compound.

In the organic light emitting device of the present invention, the organic material layer includes an electron injection layer or an electron transport layer, and the electron injection layer or the electron transport layer may include the heterocyclic compound.

In another organic light emitting device, the organic material layer may include a hole blocking layer, and the hole blocking layer may include the heterocyclic compound.

In another organic light emitting device, the organic material layer may include an electron blocking layer, and the electron blocking layer may include the heterocyclic compound.

In another organic light emitting device, the organic material layer includes a hole transport layer, a light emitting layer, or an electron blocking layer, and the hole transport layer, a light emitting layer, or an electron blocking layer may include the heterocyclic compound.

In another organic light emitting device, the organic material layer includes a hole transport layer or a hole transport auxiliary layer, and the hole transport layer or the hole transport auxiliary layer may include the heterocyclic compound.

In the organic light emitting device of the present application, materials with a relatively high work function can be used as the anode material, and transparent conductive oxides, metals, or conductive polymers can 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); Combination of metal and oxide such as ZnO:Al or SnO ₂ :Sb; Conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline are included, but are not limited to these.

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

As the hole injection material, known hole injection materials may be used, for example, phthalocyanine compounds such as copper phthalocyanine disclosed in U.S. Patent No. 4,356,429 or described in Advanced Material, 6, p.677 (1994). Starburst type 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), Polyaniline/Camphor sulfonic acid or polyaniline/ Poly(4-styrenesulfonate) (Polyaniline/Poly(4-styrene-sulfonate)) can be used.

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

Electron transport materials include oxadiazole derivatives, anthraquinodimethane and its derivatives, benzoquinone and its derivatives, naphthoquinone and its derivatives, anthraquinone and its derivatives, tetracyanoanthraquinodimethane and its derivatives, and fluorenone. Derivatives, diphenyldicyanoethylene and its derivatives, diphenoquinone derivatives, metal complexes of 8-hydroxyquinoline and its derivatives, etc. may be used, and not only low molecular substances but also high molecular substances may be used.

For example, LiF is typically used as an electron injection material in the industry, but the present application is not limited thereto.

Red, green, or blue light-emitting materials may be used as the light-emitting material, and if necessary, two or more light-emitting materials may be mixed. At this time, two or more light emitting materials can be deposited and used from individual sources, or they can be premixed and deposited from a single source. Additionally, a fluorescent material can be used as a light-emitting material, but it can also be used as a phosphorescent material. As a light-emitting material, a material that emits light by combining holes and electrons injected from an anode and a cathode, respectively, may be used, but materials that participate in light emission together with a host material and a dopant material may also be used.

When using a mixture of hosts of a light emitting material, hosts of the same series may be mixed and used, or hosts of different series may be mixed and used. For example, any two or more types of materials, such as an n-type host material or a p-type host material, can be selected and used as a host material for the light emitting layer.

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

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

The organic light emitting device of the present invention includes a light emitting layer, a hole injection layer, a hole transport layer, a hole transport auxiliary layer,

It may further include one or two or more layers selected from the group consisting of an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

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 blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer.

1 to 3 illustrate the stacking order of electrodes and organic material layers of an 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 also be applied to the present application.

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

Figures 3 and 4 illustrate the 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, a light emitting layer 303, a hole blocking layer 304, an electron transport layer 305, and an electron injection layer 306.

In an exemplary embodiment of the present application, an organic light-emitting device is provided in which the organic material layer of the organic light-emitting device including the heterocyclic compound represented by Formula 1 further includes a heterocyclic compound represented by Formula 2 below.

[Formula 2]

In Formula 2,

R21 and R22 are the same or different from each other, and are each independently a substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,

Rc and Rd are the same or different from each other and are each independently hydrogen; heavy hydrogen; halogen group; Cyano group; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C2 to C60 alkenyl group; Substituted or unsubstituted C2 to C60 alkynyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted C3 to C60 cycloalkyl group; Substituted or unsubstituted C2 to C60 heterocycloalkyl group; Substituted or unsubstituted C6 to C60 aryl group; Substituted or unsubstituted C2 to C60 heteroaryl group; -SiR31R32R33; -P(=O)R31R32; and a substituted or unsubstituted C1 to C60 alkyl group, a substituted or unsubstituted C6 to C60 aryl group, or a substituted or unsubstituted C2 to C60 heteroaryl group, or a substituted or unsubstituted amine group, or each other. Two or more adjacent groups combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,

R31, R32 and R33 are the same or different from each other and are each independently hydrogen; heavy hydrogen; -CN; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C3 to C60 cycloalkyl group; Substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,

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 or different from each other.

In an exemplary embodiment of the present application, R21 and R22 may be the same or different from each other, and may each independently be a substituted or unsubstituted C6 to C40 aryl group or a substituted or unsubstituted C2 to C40 heteroaryl group.

In an exemplary embodiment of the present application, R21 and R22 may be the same or different from each other, and may each independently be a substituted or unsubstituted C6 to C20 aryl group or a substituted or unsubstituted C2 to C20 heteroaryl group.

In an exemplary embodiment of the present application, R21 and R22 are the same or different from each other, and are each independently selected from the group consisting of deuterium, a C1 to C20 alkyl group, a C6 to C20 aryl group, -SiR31R32R33, and a cyano group. A C6 to C20 aryl group substituted or unsubstituted with the above substituents; Substituted or unsubstituted dibenzofuran group; Or it may be a substituted or unsubstituted dibenzothiophene group.

In an exemplary embodiment of the present application, R21 and R22 are the same or different from each other, and are each independently a substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted terphenyl group; Substituted or unsubstituted naphthyl group; Substituted or unsubstituted triphenylenyl group; Substituted or unsubstituted dimethylfluorenyl group; Substituted or unsubstituted diphenylfluorenyl group; A substituted or unsubstituted spirobifluorenyl group; Substituted or unsubstituted dibenzofuran group; Or it may be a substituted or unsubstituted dibenzothiophene group.

In an exemplary embodiment of the present application, R21 and R22 are the same or different from each other, and are each independently a phenyl group substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, -SiR31R32R33, and cyano group; A biphenyl group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium and phenyl groups; Terphenyl group substituted or unsubstituted with deuterium; Naphthyl group substituted or unsubstituted with deuterium; Triphenylenyl group substituted or unsubstituted with deuterium; Dimethylfluorenyl group substituted or unsubstituted with deuterium; A diphenylfluorenyl group substituted or unsubstituted with deuterium; Spirobifluorenyl group substituted or unsubstituted with deuterium; Dibenzofuran group substituted or unsubstituted with deuterium; Alternatively, it may be a dibenzothiophene group substituted or unsubstituted.

In an exemplary embodiment of the present application, Rc and Rd are the same or different from each other and are each independently hydrogen; heavy hydrogen; halogen group; Cyano group; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C2 to C60 alkenyl group; Substituted or unsubstituted C2 to C60 alkynyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted C3 to C60 cycloalkyl group; Substituted or unsubstituted C2 to C60 heterocycloalkyl group; Substituted or unsubstituted C6 to C60 aryl group; Substituted or unsubstituted C2 to C60 heteroaryl group; -SiR31R32R33; -P(=O)R31R32; and a substituted or unsubstituted C1 to C60 alkyl group, a substituted or unsubstituted C6 to C60 aryl group, or a substituted or unsubstituted C2 to C60 heteroaryl group, or a substituted or unsubstituted amine group, or each other. Two or more adjacent groups may be combined with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring.

In an exemplary embodiment of the present application, Rc and Rd are the same or different from each other and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C1 to C60 alkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group;

In an exemplary embodiment of the present application, Rc and Rd are the same or different from each other and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C1 to C40 alkyl group; Substituted or unsubstituted C6 to C40 aryl group; Or a substituted or unsubstituted C2 to C40 heteroaryl group.

In an exemplary embodiment of the present application, Rc and Rd are the same or different from each other and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C1 to C20 alkyl group; Substituted or unsubstituted C6 to C20 aryl group; Or a substituted or unsubstituted C2 to C20 heteroaryl group.

In an exemplary embodiment of the present application, Rc and Rd are the same or different from each other and are each independently hydrogen; or deuterium;

In an exemplary embodiment of the present application, the deuterium content of Formula 2 may be 0% to 100%.

In another exemplary embodiment, the deuterium content of Formula 2 may be 0% or 10% to 100%.

In another exemplary embodiment, the deuterium content of Formula 2 may be 0% or 20% to 100%.

In another exemplary embodiment, the deuterium content of Formula 2 may be 0% or 40% to 100%.

In another exemplary embodiment, the deuterium content of Formula 2 may be 0% or 60% to 100%.

In another exemplary embodiment, the deuterium content of Formula 2 may be 0% or 80% to 100%.

In another embodiment, the deuterium content of Formula 2 may be 0% or 100%.

In one embodiment of the present invention, Formula 2 provides an organic light-emitting device represented by any one of the following compounds.

The organic light-emitting device further containing the heterocyclic compound represented by Formula 2 may be applied to the organic light-emitting device containing the heterocyclic compound represented by Formula 1 described above.

In another embodiment, the heterocyclic compound represented by Formula 2 may be used as a light-emitting material for the light-emitting layer of an organic light-emitting device.

In another embodiment, the heterocyclic compound represented by Formula 2 may be used as a light-emitting material for the light-emitting layer of an organic light-emitting device and may be used as a p-type host material.

In the organic light emitting device of the present invention, the organic material layer may include a heterocyclic compound represented by Formula 1 and a heterocyclic compound represented by Formula 2. The organic material layer can be formed by pre-mixing the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 using a thermal vacuum deposition method.

In another organic light-emitting device, the organic material layer includes a light-emitting layer, the light-emitting layer includes a host material, and the host material may include a heterocyclic compound represented by Formula 1 and a heterocyclic compound represented by Formula 2. You can.

In another organic light emitting device, the organic material layer includes a light emitting layer, the n-type host material of the light emitting layer includes a heterocyclic compound represented by Formula 1, and the p-type host material includes a heterocyclic compound represented by Formula 2. It may contain a ring compound.

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

In an exemplary embodiment of the present application, the step of forming the organic material layer includes supplying the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 to each individual source, and then using a thermal vacuum deposition method. A method for manufacturing an organic light-emitting device is provided.

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

The organic light-emitting device according to an exemplary embodiment of the present application can be manufactured using conventional organic light-emitting device manufacturing methods and materials, except that the organic material layer is formed using the heterocyclic compound described above.

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 blocking layer, an electron injection layer, an electron transport layer, a hole auxiliary layer, and a hole blocking layer. You can.

In an exemplary embodiment of the present application, a composition for an organic material layer of an organic light-emitting device comprising a heterocyclic compound represented by Formula 1 and a heterocyclic compound represented by Formula 2 is provided.

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

The composition can be used when forming an organic material layer of an organic light-emitting device, and can be particularly preferably used as a host material for the light-emitting layer.

The composition is a simple mixture of two or more compounds, and powdered materials may be mixed before forming the organic material layer of the organic light-emitting device, or compounds in a liquid state at an appropriate temperature or higher may be mixed. The composition is in a solid state below the melting point of each material, and can be maintained in a liquid state by adjusting the temperature.

The composition may further include materials known in the art, such as solvents and additives.

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

<Synthesis example>

[Preparation Example 1] Preparation of Compound A

Preparation of compound [A]-iv

In a one neck round bottom flask, 2-methoxyphenyl)boronic acid (30g, 0.20mol), 2-bromo-3-chloro-1-fluoronaphthalene (51.2g, 0.20mol) Pd(PPh ₃ ) ₄ (11.4g, 0.0010mol), K ₂ CO ₃ (54.5, 0.40mol) and Dioxane 300mL/water (100mL) mixture was refluxed at 100°C for 3 hours. After cooling, it was extracted twice with MC/H ₂ O, concentrated, and crystals were precipitated through MeOH slurry and filtered to obtain compound [A]-iv. (47.6g, 83%)

Preparation of compound [A]-iii

In a one neck round bottom flask, 3-chloro-1-fluoro-2-(2-methoxyphenyl)naphthalene (47.6g, 0.16mol) was dissolved in 300ml of DCM and then added to boron tribromide (BBR ₃ , 45.7). g, 0.18 mol) and proceed with the reaction at room temperature (RT) for 3 hours. Water was slowly added to the reaction vessel, extracted twice with MC/H ₂ O, and the organic layer was filtered and concentrated to obtain a yellow oil compound [A]-iii. (32.6g 72%)

Preparation of compound [A]-ii

In a one neck round bottom flask, 2-(3-chloro-1-fluoronaphthalen-2-yl)phenol (32.6g, 0.12mol) was dissolved in 300ml of DMA and then Cs ₂ CO ₃ (58.6g, 0.24 mol) was added and refluxed for 3 hours. Water was slowly added to the reaction vessel, extracted twice with MC/H ₂ O, and the organic layer was filtered and concentrated. Crystals were precipitated through MeOH Slurry and filtered to obtain compound [A]. got -ii. (26.7g, 88%)

Preparation of compound [A]-i

Dissolve 6-chloronaphtho[1,2-b]benzofuran (26.7g, 0.11mol) in 200ml of DMF in a one neck round bottom flask, add NBS (22.6, 0.13mol), and incubate at 60°C for 3 hours. Stirred at ℃. Water was slowly added to the reaction vessel, the precipitated solid was filtered, and then thoroughly washed with water and methanol to obtain compound [A]-i. (27.3g, 78%)

Preparation of compound [A]

5-bromo-6-chloronaphtho[1,2-b]benzofuran (27.3g 0.08mol), Pd(dppf)Cl ₂ (3g, 0.0004mol), and Potassium acetate in a one neck round bottom flask. (16g, 0.16mol) and B ₂ (pin) ₂ (31g, 0.12mol) were dissolved in 250ml of 1,4-Dioxane and refluxed for 3 hours. The reaction solution was sufficiently cooled to room temperature, filtered, washed with MC, and concentrated. The concentrated material was dissolved again in MC and then passed through a silicagel filter through MC. The filtered solution was concentrated and the solid was precipitated with MeOH slurry to obtain compound [A]. (21g, 67%)

[Preparation Example 2] Preparation of Compound A-677

Preparation of compound [A]-677-i

Dissolve 5-bromo-6-chloronaphtho[1,2-b]benzofuran (10g, 0.03mol) in 100ml of DCB in a one neck round bottom flask and add 100ml of D6-benzene. Afterwards, trifluoromethansulfonicacid (19.5ml, 0.21mol) was slowly added and the reaction proceeded at room temperature for 3H. After the reaction solution is sufficiently cooled using an ice bath, K ₃ PO ₄ aqueous solution is slowly added to complete the reaction. Afterwards, extraction is performed twice with MC/H ₂ O, and the extracted solution is concentrated. The concentrated material was dissolved again in MC and then passed through a silicagel filter at Hex:MC 1:1. The filtered solution was concentrated and the solid was precipitated with MeOH slurry to obtain compound [A]-677-i. (10g, 97%)

Preparation of compound [A]-677

5-bromo-5-bromo-6-chloro-1,2,3,4,7,8,9,10-octadeuterio-naphtho[1,2-b) in a one neck round bottom flask. ]Dissolve benzofuran, Pd(dppf)Cl ₂ (1.1g, 0.0002mol), Potassium acetate (5.8g, 0.059mol), and B ₂ (pin) ₂ (11.5g, 0.044mol) in 100ml of 1,4-Dioxane. It was refluxed for 3 hours. The reaction solution was sufficiently cooled to RT, filtered, washed with MC, and concentrated. The concentrated material was dissolved again in MC and then passed through a silicagel filter through MC. The filtered solution was concentrated and the solid was precipitated with MeOH slurry to obtain compound [A]-677. (10g, 88%)

[Preparation Example 3] Preparation of compound [C]-677

Preparation of compound [C]-677-i

Add magnesium (3.4g, 0.14mol) and iodine (0.4g, 0.002mol) to 100ml of THF in a one neck round bottom flask and stir at 0 degrees. Benzene-1,2,3,4,5-d5, 6-bromo- (33g, 0.20mol) is added to 100ml of THF, swirled, and when sufficiently dispersed, added to the flask containing Magnesium and iodine. When the reaction solution becomes transparent, add cyanuric chloride (30g, 0.16mol) and proceed with the reaction at room temperature for 12H. The reaction solution is extracted twice with MC/H ₂ O, and the extracted solution is concentrated. Afterwards, the column was processed with MC/HEX 3:1 to obtain compound [C]-677-i. (25.4g, 67%)

Preparation of compound [C]-677

Add magnesium (4.7g, 0.195mol) and iodine (0.6g, 0.003mol) to 100ml of THF in a one neck round bottom flask and stir at 0 degrees. 1-bromo-2,3,5,6-tetradeuterio-4-(2,3,4,5,6-pentadeuteriophenyl)benzene (35g, 0.14mol) is added to 100ml of THF, and when sufficiently dispersed, magnesium and iodine are dissolved. Put it into the flask that came with it. When the reaction solution becomes transparent, add 2,4-dichloro-6-(2,3,4,5,6-pentadeuteriophenyl)-1,3,5-triazine (25.4g, 0.11mol) and proceed with the reaction at room temperature for 12H. do. The reaction solution is extracted twice with MC/H ₂ O, and the extracted solution is concentrated. Afterwards, the column was processed with MC:HEX 1:3 to obtain compound [C]-677. (22.8g, 58%)

[Preparation Example 4] Preparation of compound [C]-729

Preparation of compound [C]-729-2

Dissolve 3-dibenzofuran (30g, 0.12mol) in 300ml of DCB in a one neck round bottom flask and add 300ml of D6-benzene. Afterwards, trifluoromethansulfonicacid (78ml, 0.84mol) was slowly added and the reaction proceeded at RT for 3H. After the reaction solution is sufficiently cooled using an ice bath, K ₃ PO ₄ aqueous solution is slowly added to complete the reaction. Afterwards, extraction is performed twice with MC/H ₂ O, and the extracted solution is concentrated. The concentrated material was again dissolved in MC and then filtered through a silicagel filter at Hex:MC 1:1, and the filtered solution was used to obtain concentrated compound [C]-729-2. (28g, 91%)

Preparation of compound [C]-729-1

3-bromo-1,2,4,6,7,8,9-heptadeuterio-dibenzofuran (28.0g 0.10mol), Pd(dppf)Cl ₂ (4.2g) in a one neck round bottom flask , 0.0005mol), Potassium acetate (20g, 0.20mol), and B ₂ (pin) ₂ (40g, 0.15mol) were dissolved in 300ml of 1,4-Dioxane and refluxed for 3 hours. The reaction solution was sufficiently cooled to room temperature, filtered, washed with MC, and concentrated. The concentrated material was dissolved again in MC and then passed through a silicagel filter through MC. The filtered solution was concentrated and the solid was precipitated with MeOH slurry to obtain compound [C]-729-1. (26g, 78%)

Preparation of compound [C]-729

[C]-729-1 (26g 0.086mol), [C]-729-i (20g, 0.086mol), K ₂ CO ₃ (24g, 0.17mol) in a one neck round bottom flask. , Pd(PPH3)4 (5g, 0.004mol) was dissolved in 300ml of THF and 60ml of H ₂ O and refluxed for 2 hours. After the reaction solution was sufficiently cooled to room temperature, the precipitated solid was filtered and washed with methanol. The filtered material was then columned with MC:HEX 1:3 to obtain compound [C]-729. (17.0g, 53%)

Compound C was synthesized in the same manner as above, except that other intermediates bromo phenyl, bromo biphenyl, and bromo heteroaryl were used in Preparation Examples 3 and 4.

[Preparation Example 5] Preparation of compound D-677

Preparation of compound [D]-677-i

Dissolve 3-dibenzofuran (30g, 0.12mol) in 300ml of DCB in a one neck round bottom flask and add 300ml of D6-benzene. Afterwards, trifluoromethansulfonicacid (78ml, 0.84mol) was slowly added and the reaction proceeded at RT for 3H. After the reaction solution is sufficiently cooled using an ice bath, K ₃ PO ₄ aqueous solution is slowly added to terminate the reaction. Afterwards, extraction is performed twice with MC/H2O and the extracted solution is concentrated. The concentrated material was again dissolved in MC, and then silicagel filtered at Hex:MC 1:1, and the filtered solution was used to obtain concentrated compound [D]-677-i. (29g, 94%)

Preparation of compound [D]-677

3-bromo-1,2,4,6,7,8,9-heptadeuterio-dibenzofuran (29.0g 0.11mol), Pd(dppf)Cl ₂ (4.2g) in a one neck round bottom flask , 0.0005mol), Potassium acetate (22.4g, 0.22mol), and B ₂ (pin) ₂ (43g, 0.165mol) were dissolved in 300ml of 1,4-Dioxane and refluxed for 3 hours. The reaction solution was sufficiently cooled to RT, filtered, washed with MC, and concentrated. The concentrated material was dissolved again in MC and then passed through a silicagel filter through MC. The filtered solution was concentrated and the solid was precipitated with MeOH slurry to obtain compound [D]-677. (26g, 78%)

Compound D was synthesized in the same manner as above, except that other intermediates bromo phenyl, bromo biphenyl, and bromo heteroaryl were used in Preparation Example 5.

[Preparation Example 6] Preparation of Compound 1-5

Preparation of compound 1-5-i

In a one neck round bottom flask, compound A (10g, 0.026mol), compound C (9g, 0.026 mol), Pd(PPh ₃ ) ₄ (1.5g, 0.0013mol), K ₂ CO ₃ (5.6g, 0.53mol) was added to Dioxane 100mL/water (30mL) solution and refluxed at 100°C for 3 hours. After cooling, it was extracted twice with MC/H ₂ O, concentrated, and crystals were precipitated through MeOH slurry and filtered to obtain compound 1-5-i. (13g, 87%)

Preparation of Compounds 1-5

In a one neck round bottom flask, compound 1-5-i (13g, 0.023mol), compound D (5.4g, 0.026 mol) and Pd(PPh ₃ ) ₄ (1.3g, 0.0016mol) , K ₂ CO ₃ (4.9g, 0.046mol), and SPhos (0.95g, 0.002mol) were added to Dioxane 100mL/water (30mL) solution and refluxed at 100°C for 3 hours. After cooling, filter the precipitated crystals and wash thoroughly with water and MeOH. The filtered crystals were dissolved in CF and passed through a silica filter, the solution was concentrated, and the solid was precipitated with acetone slurry to obtain compound 1-5. (12g, 75%)

[Preparation Example 7] Preparation of compound 1-677

Preparation of compound 1-677-i

In a one neck round bottom flask, compound A (10g, 0.026mol), compound C (9g, 0.026 mol), Pd(PPh ₃ ) ₄ (1.5g, 0.0013mol), K ₂ CO ₃ (5.6g, 0.53mol) was added to Dioxane 100mL/water (30mL) solution and refluxed at 100°C for 4 hours. After cooling, it was extracted twice with MC/H ₂ O, concentrated, and crystals were precipitated through MeOH slurry and filtered to obtain compound 1-677-i. (12.6g, 83%)

Preparation of compound 1-677

In a one neck round bottom flask, compound 1-677-i (12.6g, 0.022mol), compound D (5.2g, 0.024 mol) and Pd(PPh ₃ ) ₄ (1.2g, 0.0015mol) ), K ₂ CO ₃ (4.8g, 0.046mol), and SPhos (0.95g, 0.002mol) were added to Dioxane 100mL/water (30mL) solution and refluxed at 100°C for 4 hours. After cooling, filter the precipitated crystals and wash thoroughly with water and MeOH. The filtered crystals were dissolved in CF, passed through a silica filter, the solution was concentrated, and the solid was precipitated with acetone slurry to obtain compound 1-677. (14g, 90%)

The following target compounds were synthesized in the same manner as in Preparation Example 6 or 7, except that other intermediates C and D shown in Table 1 were used.

[Table 1]

[Preparation Example 8] Preparation of Compound 1-7

Preparation of compound 1-7-ii

In a one neck round bottom flask, compound A (10g, 0.026mol), compound C (5.6g, 0.026 mol), Pd(PPh ₃ ) ₄ (1.5g, 0.0013mol), K ₂ CO ₃ (5.6g, 0.53mol) was added to Dioxane 100mL/water (30mL) solution and refluxed at 100°C for 3 hours. After cooling, it was extracted twice with MC/H ₂ O, concentrated, and crystals were precipitated through MeOH slurry and filtered to obtain compound 1-7-ii. (10g, 90%)

Preparation of compound 1-7-i

In a one neck round bottom flask, compound 1-7-ii (10g, 0.024mol), B2(pin)2 (9.1g, 0.036 mol) and Pd ₂ (dba) ₃ (1.1g, 0.0011mol), potassium acetate (4.7g, 0.048mol), and SPhos (0.98g, 0.0024mol) were added to 100mL of dioxane solution and refluxed at 100°C for 3 hours. The reaction solution was sufficiently cooled to RT, filtered, washed with MC, and concentrated. The concentrated material was dissolved again in MC and then passed through a silicagel filter through MC. The filtered solution was concentrated and the solid was precipitated with MeOH slurry to obtain compound 1-7-i. (9g, 74%)

Preparation of compounds 1-7

Compound 1-7-i (9g, 0.018mol), compound D (6.1g, 0.018 mol) and Pd(PPh ₃ ) ₄ (1.0g, 0.0009mol) were added to a one neck round bottom flask. , K ₂ CO ₃ (3.8 g, 0.036 mol) was added to Dioxane 100 mL / water (30 mL) solution and refluxed at 100°C for 3 hours. After cooling, filter the precipitated crystals and wash thoroughly with water and MeOH. The filtered crystals were dissolved in CF, passed through a silica filter, the solution was concentrated, and the solid was precipitated with acetone slurry to obtain compound 1-7. (8g, 65%)

[Preparation Example 9] Preparation of compound 1-683

Preparation of compound 1-683-ii

In a one neck round bottom flask, compound A (10g, 0.026mol), compound C (5.6g, 0.026 mol), Pd(PPh ₃ ) ₄ (1.5g, 0.0013mol), K ₂ CO ₃ (5.6g, 0.53mol) was added to Dioxane 100mL/water (30mL) solution and refluxed at 100°C for 2 hours. After cooling, it was extracted twice with MC/H ₂ O, concentrated, and crystals were precipitated through MeOH slurry and filtered to obtain compound 1-683-ii. (10.3g, 92%)

Preparation of compound 1-683-i

In a one neck round bottom flask, compound 1-683-ii (10.3g, 0.024mol), B2(pin)2 (9.1g, 0.036 mol), Pd ₂ (dba) ₃ (1.1g) , 0.0011 mol), potassium acetate (4.7 g, 0.048 mol), and SPhos (0.98 g, 0.0024 mol) were added to 100 mL of dioxane solution and refluxed at 100°C for 3 hours. The reaction solution was sufficiently cooled to RT, filtered, washed with MC, and concentrated. The concentrated material was dissolved again in MC and then passed through a silicagel filter through MC. The filtered solution was concentrated and the solid was precipitated with MeOH slurry to obtain compound 1-683-i. (11.5g, 92%)

Preparation of compound 1-683

In a one neck round bottom flask, compound 1-683-i (11.5g, 0.022mol), compound D (7.8g, 0.022 mol) and Pd(PPh ₃ ) ₄ (1.3g, 0.001mol) ), K ₂ CO ₃ (6.1g, 0.044mol) were added to Dioxane 150mL/water (30mL) solution and refluxed at 100°C for 3 hours. After cooling, filter the precipitated crystals and wash thoroughly with water and MeOH. The filtered crystals were dissolved in CF and passed through a silica filter, the solution was concentrated, and the solid was precipitated with acetone slurry to obtain compound 1-683. (10g, 63%)

The following target compounds were synthesized in the same manner as in Preparation Example 8 or 9, except that other intermediates C and D shown in Table 2 were used.

[Table 2]

[Preparation Example 10] Preparation of Compound B

Preparation of compound [B]-iv

In a one neck round bottom flask, (2-(methylthio)phenyl)boronic acid (30g, 0.18mol), 2-bromo-3-chloro-1-fluoronaphthalene (46.1g, 0.18mol) Pd ( A mixture of PPh ₃ ) ₄ (10.3g, 0.0009mol), K ₂ CO ₃ (49.1g, 0.36mol) and Dioxane 300mL/water (100mL) was refluxed at 100°C for 6 hours. After cooling, it was extracted twice with MC/H ₂ O, concentrated, and crystals were precipitated through MeOH slurry and filtered to obtain compound [B]-iv. (47.6g, 83%)

Preparation of compound [B]-iii

Dissolve 3-chloro-1-fluoro-2-(2-(2-(methylthio)phenyl))naphthalene (41.1g, 0.14mol) in 300ml of DCM in a one neck round bottom flask and then BBR. Add ₃ (35.4g, 0.14mol) and proceed with the reaction at RT for 2 hours. Water was slowly added to the reaction vessel, extracted twice with MC/H ₂ O, and the organic layer was filtered and concentrated to obtain yellow oil compound [B]-iii. (25.9g, 66%)

Preparation of compound [B]-ii

In a one neck round bottom flask, 2-(3-chloro-1-fluoronaphthalen-2-yl)benzenethiol (25.9g, 0.09mol) was dissolved in 200ml of DMA, then Cs ₂ CO ₃ (44.0g, 0.18 mol) was added and refluxed for 4 hours. Water was slowly added to the reaction vessel and extracted twice with MC/H ₂ O. The organic layer was filtered and concentrated, and crystals were precipitated through MeOH slurry and filtered to obtain compound [B]-ii. (22.1g, 92%)

Preparation of compound [B]-i

In a one neck round bottom flask, 6-chlorobenzo[b]naphtho[2,1-d]thiophene (22.1g, 0.08mol) was dissolved in 200ml of DMF and then NBS (17.4g, 0.10mol) was added. Added and stirred at 60°C for 2 hours. Water was slowly added to the reaction vessel, the precipitated solid was filtered, and then thoroughly washed with water and methanol to obtain compound [B]-i. (27.3g, 84%)

Preparation of compound [B]

5-bromo-6-chloronaphtho[1,2-b]benzofuran (24.1g 0.069mol), Pd(dppf)Cl ₂ (2.3g, 0.0003mol), Potassium in a one neck round bottom flask. Acetate (14g, 0.14mol) and B2(pin) ₂ (25g, 0.10mol) were dissolved in 250ml of 1,4-Dioxane and refluxed for 3 hours. The reaction solution was sufficiently cooled to RT, filtered, washed with MC, and concentrated. The concentrated material was dissolved again in MC and then passed through a silicagel filter through MC. The filtered solution was concentrated and the solid was precipitated with MeOH slurry to obtain yellow compound [B]. (19.6g, 72%)

[Preparation Example 11] Preparation of compound 1-22

Preparation of compound 1-22-i

In a one neck round bottom flask, compound B (10g, 0.025mol), compound C (8.7g, 0.025 mol), Pd(PPh ₃ ) ₄ (1.5g, 0.0013mol), K ₂ CO ₃ (54, 0.503 mol) was added to 100 mL of dioxane/water (30 mL) solution and refluxed at 100°C for 4 hours. After cooling, filter the precipitated crystals and wash thoroughly with water and MeOH. The filtered crystals were dissolved in CF and passed through a silica filter, the solution was concentrated, and the solid was precipitated with acetone slurry to obtain 1-22-i. (12g, 85%)

Preparation of compounds 1-22

Compound 1-22-i (12g, 0.021mol), compound D (4.4g, 0.021mol) and Pd(PPh ₃ ) ₄ (1.2g, 0.001mol) were added to a one neck round bottom flask. , K ₂ CO ₃ (4.4g, 0.042mol), and SPhos (0.86g, 0.002mol) were added to Dioxane 150mL/water (40mL) solution and refluxed at 100°C for 4 hours. After cooling, filter the precipitated crystals and wash thoroughly with water and MeOH. The filtered crystals were dissolved in CF, passed through a silica filter, the solution was concentrated, and the solid was precipitated with acetone slurry to obtain compound 1-22. (12g, 75%)

The following target compounds were synthesized in the same manner as in Preparation Example 11, except that other intermediates C and D shown in Table 3 were used.

[Table 3]

[Preparation Example 12] Preparation of compound 1-412

Preparation of compound 1-412-ii

In a one neck round bottom flask, compound A (10g, 0.025mol), compound C (6.3g, 0.025 mol), Pd(PPh ₃ ) ₄ (1.5g, 0.0013mol), K ₂ CO ₃ (5.4g, 0.51mol) was added to Dioxane 100mL/water (30mL) solution and refluxed at 100°C for 2 hours. After cooling, it was extracted twice with MC/H ₂ O, concentrated, crystals were precipitated through MeOH slurry, and filtered to obtain compound 1-412-ii. (8.4g, 76%)

Preparation of compound 1-412-i

In a one neck round bottom flask, compound 1-412-i (8.4g, 0.019mol), B ₂ (pin) ₂ (7.4g, 0.029 mol), Pd ₂ (dba) ₃ (0.9 g, 0.001 mol), potassium acetate (3.8 g, 0.039 mol), and SPhos (0.8 g, 0.002 mol) were added to 100 mL of dioxane solution and refluxed at 100°C for 4 hours. The reaction solution was sufficiently cooled to RT, filtered, washed with MC, and concentrated. The concentrated material was again dissolved in MC and then passed through a silicagel filter through MC. The filtered solution was concentrated and the solid was precipitated with MeOH slurry to obtain compound 1-412-i. (8.1g, 80%)

Preparation of Compound 1-412

In a one neck round bottom flask, compound 1-412-i (8.1g, 0.015mol), compound D (5.7g, 0.015 mol) and Pd(PPh ₃ ) ₄ (0.9g, 0.0008mol) ), K ₂ CO ₃ (3.2g, 0.030mol) were added to Dioxane 100mL/water (30mL) solution and refluxed at 100°C for 2 hours. After cooling, filter the precipitated crystals and wash thoroughly with water and MeOH. The filtered crystals were dissolved in CF and passed through a silica filter, the solution was concentrated, and the solid was precipitated with acetone slurry to obtain compound 1-412. (9.4g, 84%)

In Preparation Example 12, the following target compounds were synthesized in the same manner, except that other intermediates C and D shown in Table 4 were used.

[Table 4]

[Preparation Example 13] Preparation of compound 2-1

Preparation of compound 2-1-i

3-bromo-9H-carbazole (2-[A]-1) (10.g, 49.59mmol), 1- in a one neck round bottom flask Bromobenzene (1-bromobenzene,[A]) (24.2g, 148.77mmol), Pd ₂ (dba) ₃ (2.27g, 2.48mmol), P(t-Bu) ₃ (2.42mL, 9.92mmol), NaOtBu After adding (9.53g, 99.18mmol), add toluene (100mL) and heat at 135°C for 15 hours. When the reaction is completed, extraction is performed with MC and H2O and column purification is performed to obtain compound 2-1-i. (14g, 98%)

Preparation of Compound 2-1

2-1-1-i (14g, 43.4mmol), (9-phenyl-9H-carbazol-3-yl)boronic acid ((9-phenyl-9H) in a one neck round bottom flask -carbazol-3-yl)boronic acid, 2-[B]-1) (14.9g, 52mmol), Pd(PPh ₃ ) ₄ (2.5g, 2.17mmol), K ₂ CO ₃ (17.9g, 130mmol) After adding the 1,4-dioxane / water (140ml/35ml) mixture, heat it at 120°C for 4 hours. After the reaction was completed, the temperature was lowered to room temperature, and the resulting solid was washed with distilled water and MeOH to obtain compound 2-1. (17g, 80%)

The following target compounds were synthesized in the same manner, except that 2-A and 2-B of Table 5 below were used instead of [A] and 2-[B]-1 in Preparation Example 13.

[Table 5]

[Preparation Example 14] Preparation of compound 2-61

Preparation of compound 2-[A]-61-ii

After adding 3-bromo-9H-carbazole (10g, 40.23mmol) and 1000ml of D6-benzene to a one neck round bottom flask. Add CF ₃ SO ₃ H (170g, 1075mmol) and stir at 50°C. When the reaction is completed, it is neutralized with D ₂ O, extracted with MC and Na ₂ CO ₃ aqueous solution, and then column purified to obtain compound 2-[A]-61-ii. (10g, 98%)

Preparation of compound 2-[A]-61-i

2-[A]-61-ii (10g, 39.5mmol), Bromobenzene (2-[B]-61) (12.4g, 79mmol) in a one neck round bottom flask, Pd ₂ (dba) ₃ (1.81g, 1.98mmol), P(t-Bu) ₃ (1.93mL, 7.9mmol) and NaOtBu (11.4g, 118.51mmol) were added, then Toluene (100mL) was added and incubated for 10 minutes at 135°C. Heat time. When the reaction is completed, extraction is performed with MC and H2O and column purification is performed to obtain compound 2-[A]-61-i. (11g, 84%)

Preparation of compound 2-[A`]-61-ii

9H-carbazol-3-ylboronic acid (10g, 47.3mmol) and 1000ml of D6-benzene were added to a one neck round bottom flask. Then, CF ₃ SO ₃ H (170g, 1075mmol) was added and stirred at 50°C. When the reaction is completed, it is neutralized with D ₂ O, extracted with MC and Na ₂ CO ₃ aqueous solution, and then column purified to obtain 2-[A`]-61-ii. (9g, 87%)

Preparation of compound 2-[A`]-61-i

2-[A`]-61-ii (9g, 41.3mmol), Bromobenzene (2-[B]) (12.9g, 82.5mmol) in a one neck round bottom flask, Pd <sub>2</sub> (dba) <sub>3</sub> (1.89g, 2.06mmol), P(t-Bu) <sub>3</sub> (2mL, 8.25mmol) and NaOtBu (7.93g, 82.54mmol) were added, then toluene (100mL) was added and incubated at 135°C. Heat for 10 hours. When the reaction is completed, it is extracted with MC and H <sub>2</sub> O and then column purified to obtain 2-[A`]-61-i. (10g, 82%)

Preparation of compound 2-61

2-[A]-61-i (10g, 30.37mmol), 2-[A`]-61-i (17.87g, 60.75mmol), Pd(PPh) in a one neck round bottom flask ₃ ) After adding ₄ (1.39, 1.52mmol) and K ₂ CO ₃ (12.59g, 91.13mmol), the 1,4-dioxane / water (140ml/35ml) mixture was dissolved in 120ml. Heat at ℃ for 4 hours. After the reaction was completed, the temperature was lowered to room temperature, and the resulting solid was washed with distilled water and MeOH to obtain compound 2-61. (13g, 85%)

The following target compounds were synthesized in the same manner, except that A and B of Table 6 below were used instead of 2-[A]-61 and 2-[B]-61 in Preparation Example 14.

[Table 6]

[Preparation Example 15] Preparation of compound 2-81

Preparation of compound 2-[A]-81-ii

2-[A]-81-iii (10g, 39.5mmol), bromobenzene (2-[B]-61) (12.4g, 79mmol) in a one neck round bottom flask, Pd ₂ (dba) ₃ (1.81g, 1.98mmol), P(t-Bu) ₃ (1.93mL, 7.9mmol) and NaOtBu (11.4g, 118.51mmol) were added, then Toluene (100mL) was added and incubated for 10 minutes at 135°C. Heat time. When the reaction is completed, extraction is performed with MC and H ₂ O, followed by column purification to obtain compound 2-[A]-81-ii. (11g, 84%)

Preparation of compound 2-[A`]-81-ii

2-[A`]-81-iii (9g, 41.3mmol), Bromobenzene (2-[B]) (12.9g, 82.5mmol) in a one neck round bottom flask, Pd <sub>2</sub> (dba) <sub>3</sub> (1.89g, 2.06mmol), P(t-Bu) <sub>3</sub> (2mL, 8.25mmol) and NaOtBu (7.93g, 82.54mmol) were added, then toluene (100mL) was added and incubated at 135°C. Heat for 10 hours. When the reaction is completed, extraction is performed with MC and H <sub>2</sub> O, followed by column purification to obtain 2-[A`]-81-ii. (10g, 82%)

Preparation of compound 2-81-i

2-[A]-81-i (10g, 30.37mmol), 2-[A`]-81-i (17.87g, 60.75mmol), Pd(PPh) in a one neck round bottom flask ₃ ) After adding ₄ (1.39, 1.52mmol) and K ₂ CO ₃ (12.59g, 91.13mmol), the 1,4-dioxane / water (140ml/35ml) mixture was dissolved in 120ml. Heat at ℃ for 4 hours. After the reaction was completed, the temperature was lowered to room temperature, and the resulting solid was washed with distilled water and MeOH to obtain compound 2-81-i. (13g, 85%)

Preparation of Compound 2-81

Add 2-81-i (10g, 20.64mmol) and 1000ml of D6-benzene to a one neck round bottom flask, then add CF ₃ SO ₃ H (100g, 620mmol), Stir at 80°C. When the reaction is completed, it is neutralized with D ₂ O/ Na ₂ CO ₃ aqueous solution, extracted with MC and Na ₂ CO ₃ aqueous solution, and then subjected to column purification to obtain compound 2-81. (10g, 98%)

The following target compounds were synthesized in the same manner, except that A and B of Table 7 below were used instead of 2-[A]-81 and 2-[B]-81 in Preparation Example 15.

[Table 7]

Compounds were prepared in the same manner as in the above preparation examples, and the synthesis confirmation results are shown in Tables 8 to 11. Tables 8 and 9 are the measured values of FD-MS (Field desorption mass spectrometry), and Tables 10 and 11 are the measured values of ¹ H NMR (CDCl ₃ , 200Mz).

[Table 8]

[Table 9]

[Table 10]

[Table 11]

[Experimental example]

<Experimental Example 1> Production of organic light emitting device

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

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

A light emitting layer was thermally vacuum deposited thereon as follows. As a host, the light-emitting layer was deposited with 400 Å of a compound represented by Chemical Formula 1 in Table 12 below, and the green phosphorescent dopant was deposited by doping 7% of Ir(ppy) ₃ . Afterwards, 60Å of BCP was deposited as a hole blocking layer, and 200Å of Alq ₃ was deposited on top of it as an electron transport layer. Finally, lithium fluoride (LiF) was deposited to a thickness of 10Å on the electron transport layer to form an electron injection layer, and then an aluminum (Al) cathode was deposited to a thickness of 1,200Å on the electron injection layer to form the cathode, thereby forming an organic An electroluminescent device was manufactured.

Meanwhile, all organic compounds required for OLED device production were purified by vacuum sublimation under 10 ^-6 to 10 ^-8 torr for each material and used for OLED production.

The driving voltage, luminous efficiency, color coordinates, and lifespan results of the organic electroluminescent device of Experimental Example 1 are shown in Table 12 below.

[Table 12]

In the case of cores in which two or more benzenes are directly fused, such as naphthodibenzofuran, naphthodibenzothiophene, and naphthocarbazole, which contain an existing naphthyl structure, research and invention have been conducted as a material that emits red light. As the π-π conjugation of the core expands, the energy level of HOMO relatively increases, the band gap of the material narrows, and the T1 energy level also decreases, making it a material suitable for red light emission.

As in Comparative Examples 1 to 6, when it has one substituent or when two substituents are each substituted on different benzene rings in the core structure, the x value of the CIE color coordinate has a value of about 0.5 and emits red light. It is confirmed.

However, as in the present invention, when two substituents are bonded to the naphthyl core at the ortho position, a strong steric effect occurs, which increases the instability of the molecule, increasing the LUMO energy level, thereby widening the band gap, and also increasing the T1 energy level. It can be seen that it rises to become a suitable material with green light emission.

Looking at an embodiment of the present invention, it can be seen that the x value of the CIE color coordinate has a distribution below 0.3 and that the material actually emits green light.

Here, even in Comparative Examples 7 to 12, the two substituents have ortho positions. However, the part where the HOMO is located also has a structure with an expanded π-π conjugation like naphthyl, and a lot of electrons are distributed on this side, so the repulsion force is relatively reduced compared to the embodiment of the present invention and the band gap is not sufficiently increased. do. Therefore, it can be seen that the x value of the CIE color coordinates has a value of about 0.4. It was confirmed that this was not suitable as a device material with red-yellow light emission and green light emission.

In the case of the present invention, the driving voltage is in the range of 3.8 to 4.3 and the efficiency is in the range of 70 to 80. It can be confirmed that Comparative Examples 13 to 15, which are other phosphorescent green light-emitting bodies, have low driving and high efficiency compared to the driving power of about 5 and efficiency of about 70.

This is an ortho position, and when HOMO and LUMO are parallel at a short distance, this means that the electron transfer from HOMO to LUMO is not only the electron transfer of the π bond moving along the intramolecular plane, but also the electron transfer to the ð orbital overlapped along the y-axis. This generates higher efficiency and lower driving voltage than other existing materials.

<Experimental Example 2> Production of organic light emitting device

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

A common layer on the ITO transparent electrode (anode), a hole injection layer 2-TNATA (4,4',4''-Tris[2-naphthyl(phenyl)amino]triphenylamine) and a hole transport layer NPB(N,N'-Di (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 made by premixing one compound shown in Chemical Formula 1 and one compound shown in Chemical Formula 2 in Table 13 below as a host and depositing 400 Å in one park after premixing them using a vacuum chamber, and the green phosphorescent dopant was Ir(ppy) ₃ 7 % doped and deposited. Afterwards, 60Å of BCP was deposited as a hole blocking layer, and 200Å of Alq ₃ was deposited on top of it as an electron transport layer. Finally, lithium fluoride (LiF) was deposited to a thickness of 10Å on the electron transport layer to form an electron injection layer, and then an aluminum (Al) cathode was deposited to a thickness of 1,200Å on the electron injection layer to form the cathode, thereby forming an organic An electroluminescent device was manufactured.

Meanwhile, all organic compounds required for OLED device production were purified by vacuum sublimation under 10 ^-6 to 10 ^-8 torr for each material and used for OLED production.

The electroluminescence (EL) characteristics of the organic electroluminescent device manufactured as described above were measured using the M7000 from McScience, and the standard luminance was measured to be 6,000 using the lifespan measurement equipment (M6000) manufactured by McScience based on the measurement results. When cd/m ² , T ₉₀ was measured.

The driving voltage, luminous efficiency, and lifespan results of the organic electroluminescent device of Experimental Example 2 are shown in Table 13 below.

[Table 13]

Comparing Tables 12 and 13, when the compound of Formula 1 and the compound of Formula 2 are used simultaneously as an emitting layer of an organic light-emitting device, the results have superior efficiency, lifespan, and lower driving voltage than when Formula 1 is used alone. shows.

From these results, it can be expected that the exciplex phenomenon will occur when both compounds are used as a light-emitting layer at the same time.

The exciplex phenomenon is an electron exchange phenomenon between two molecules that releases energy equal to the HOMO level of the donor (p-host) and the LUMO level of the acceptor (n-host). When this phenomenon occurs, Reverse Intersystem Crossing (RISC) occurs, and as a result, the internal quantum efficiency of fluorescence can increase to 100%, indicating an increase in efficiency.

In addition, when a donor (p-host) with good hole transport ability and an acceptor (n-host) with good electron transport ability are used as hosts for the emitting layer, holes are injected into the p-host and electrons are injected into the n-host, so the drive is driven. The voltage can be lowered, which reduces the burden on the device, resulting in improved lifespan compared to previous results.

Comparing Examples 134 to 174 and Examples 175 to 216, it can be observed that the lifespan increases when hydrogen in the P-host molecule is replaced with deuterium (D). The electron transfer phenomenon between the donor (p-host) and the acceptor (n-host) in the light-emitting layer continues, and as the electrons move, the molecules that make up the light-emitting layer constantly vibrate. Due to molecular vibration, the molecules of the light-emitting layer are continuously stressed, which can cause a decrease in lifespan.

As the hydrogen in the molecule is replaced with deuterium, the molecular weight increases, reducing the vibration phenomenon and reducing the stress on the molecule. In addition, the bond energy between carbon and deuterium is higher than that of carbon hydrogen, making it more structurally stable and increasing its lifespan.

100: substrate
200: anode
300: Organic 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

Claims (17)

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

In Formula 1,
X is O, S or -C(Ra)(Rb), and Ra and Rb are substituted or unsubstituted C1 to C60 alkyl groups,
L is a direct bond; Or a substituted or unsubstituted C6 to C60 arylene group,
n is an integer from 1 to 3, and when n is 2 or more, the substituents in parentheses are the same or different from each other,
Y1 is CR11 or N, Y2 is CR12 or N, Y3 is CR13 or N, Y4 is CR14 or N, Y5 is CR15 or N, and at least one of Y1 to Y5 is N,
R11 to R15 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C6 to C60 aryl group; or a substituted or unsubstituted C2 to C60 heterocyclic group, or two or more groups adjacent to each other are bonded to each other to form a substituted or unsubstituted C2 to C60 heterocycle,
R1 and R2 are the same or different from each other and are each independently hydrogen; heavy hydrogen; halogen group; Cyano group; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C3 to C60 cycloalkyl group; Substituted or unsubstituted C2 to C60 heterocycloalkyl group; Substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heterocyclic group,
a is an integer from 0 to 4, and when a is 2 or more, the substituents in parentheses are the same or different,
b is an integer from 0 to 4, and when b is 2 or more, the substituents in parentheses are the same or different,
Ar1 is a substituted or unsubstituted aryl group of C6 to C60, or any one of the following formulas A and B,
[Formula A]

[Formula B]

In Formula A and Formula B,
X1 is O, S or N(R10),
R10 is hydrogen; Substituted or unsubstituted C1 to C60 alkyl group; Or a substituted or unsubstituted aryl group of C6 to C60,
R3 and R4 are hydrogen; heavy hydrogen; halogen group; Cyano group; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C3 to C60 cycloalkyl group; Substituted or unsubstituted C2 to C60 heterocycloalkyl group; Substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heterocyclic group,
c is an integer from 0 to 7, and when c is 2 or more, the substituents in parentheses are the same or different,
d is an integer from 0 to 8, and when d is 2 or more, the substituents in parentheses are the same or different. The method according to claim 1, wherein the formula 1 is a heterocyclic compound represented by any one of the following formulas 1-1 and 1-2:
[Formula 1-1]

[Formula 1-2]

In Formulas 1-1 and 1-2,
The definitions of X, L, Ar1, R1, R2, Y1 to Y5, a, b, and n are the same as those in Formula 1 above. The method according to claim 1, wherein the formula 1 is a heterocyclic compound represented by the following formula 1-3:
[Formula 1-3]

In Formula 1-3,
The definitions of X, L, Ar1, R1, R2, Y2, Y4, a, b and n are the same as those in Formula 1 above. The method according to claim 1, wherein Ar1 is a substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted terphenyl group, or a heterocyclic compound of any one of the following formulas (A) and (B):
[Formula A]

[Formula B]

In Formula A and Formula B,
X1 is O, S or N(R10),
R10 is hydrogen; Or a substituted or unsubstituted C6 to C20 aryl group,
R3 and R4 are hydrogen; heavy hydrogen; Substituted or unsubstituted C1 to C20 alkyl group; Substituted or unsubstituted C6 to C20 aryl group; Or a substituted or unsubstituted C2 to C20 heterocyclic group,
c is an integer from 0 to 7, and when c is 2 or more, the substituents in parentheses are the same or different,
d is an integer from 0 to 8, and when d is 2 or more, the substituents in parentheses are the same or different. The method according to claim 1, wherein L is a direct bond; Substituted or unsubstituted phenylene group; Substituted or unsubstituted naphthylene group; Or a heterocyclic compound that is a substituted or unsubstituted biphenylene group. The method according to claim 1, wherein R11 to R15 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted naphthyl group; Substituted or unsubstituted carbazole group; Substituted or unsubstituted dibenzofuran group; Or a substituted or unsubstituted dibenzothiophene group, or a heterocyclic compound in which two or more adjacent groups are bonded to each other to form a substituted or unsubstituted C2 to C20 heterocycle. The method according to claim 1, wherein the heterocyclic compound represented by Formula 1 has a deuterium content of 0% or 10% to 100%. The heterocyclic compound according to claim 1, wherein Formula 1 is represented by any one of the following compounds:

. first electrode; a second electrode provided opposite to the first electrode; And an organic light-emitting device comprising at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer contains the heterocyclic compound according to any one of claims 1 to 8. Phosphorus organic light emitting device. The organic light-emitting device of claim 9, wherein the organic material layer further includes a heterocyclic compound represented by the following formula (2):
[Formula 2]

In Formula 2,
R21 and R22 are the same or different from each other, and are each independently a substituted or unsubstituted aryl group of C6 to C60; Or a substituted or unsubstituted C2 to C60 heteroaryl group,
Rc and Rd are the same or different from each other and are each independently hydrogen; heavy hydrogen; halogen group; Cyano group; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C2 to C60 alkenyl group; Substituted or unsubstituted C2 to C60 alkynyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted C3 to C60 cycloalkyl group; Substituted or unsubstituted C2 to C60 heterocycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; Substituted or unsubstituted C2 to C60 heteroaryl group; -SiR31R32R33; -P(=O)R31R32; and a substituted or unsubstituted C1 to C60 alkyl group, a substituted or unsubstituted C6 to C60 aryl group, or a substituted or unsubstituted C2 to C60 heteroaryl group, or a substituted or unsubstituted amine group, or each other. Two or more adjacent groups combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,
R31, R32 and R33 are the same or different from each other and are each independently hydrogen; heavy hydrogen; -CN; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C3 to C60 cycloalkyl group; Substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,
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 or different from each other. The organic light-emitting device of claim 10, wherein the heterocyclic compound represented by Formula 2 has a deuterium content of 0% or 10% to 100%. The organic light-emitting device according to claim 10, wherein Formula 2 is represented by any one of the following compounds:

. The organic light-emitting device of claim 10, wherein the organic material layer includes a light-emitting layer, and the light-emitting layer includes a heterocyclic compound represented by Formula 1 and a heterocyclic compound represented by Formula 2. The method of claim 10, wherein the organic layer includes a light-emitting layer, the light-emitting layer includes a host material, and the host material includes a heterocyclic compound represented by Formula 1 and a heterocyclic compound represented by Formula 2. Organic light emitting device. The method of claim 9, wherein the organic light emitting device further comprises one or two layers selected from the group consisting of a light emitting layer, a hole injection layer, a hole transport layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer. Phosphorus organic light emitting device. A heterocyclic compound represented by Formula 1 according to any one of claims 1 to 8; and a composition for the organic material layer of an organic light-emitting device comprising a compound represented by the following formula (2):
[Formula 2]

In Formula 2,
R21 and R22 are the same or different from each other, and are each independently a substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heterocyclic group,
Rc and Rd are the same or different from each other and are each independently hydrogen; heavy hydrogen; halogen group; Cyano group; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C2 to C60 alkenyl group; Substituted or unsubstituted C2 to C60 alkynyl group; Substituted or unsubstituted alkoxy group; Substituted or unsubstituted C3 to C60 cycloalkyl group; Substituted or unsubstituted C2 to C60 heterocycloalkyl group; Substituted or unsubstituted C6 to C60 aryl group; Substituted or unsubstituted C2 to C60 heteroaryl group; -SiR31R32R33; -P(=O)R31R32; and a substituted or unsubstituted C1 to C60 alkyl group, a substituted or unsubstituted C6 to C60 aryl group, or a substituted or unsubstituted C2 to C60 heteroaryl group, or a substituted or unsubstituted amine group, or each other. Two or more adjacent groups combine with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring,
R31, R32 and R33 are the same or different from each other and are each independently hydrogen; heavy hydrogen; -CN; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C3 to C60 cycloalkyl group; A substituted or unsubstituted C6 to C60 aryl group; Or a substituted or unsubstituted C2 to C60 heteroaryl group,
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 or different from each other. The composition for an organic material layer of an organic light-emitting device according to claim 16, wherein the weight ratio of the heterocyclic compound represented by Formula 1 to the heterocyclic compound represented by Formula 2 in the composition is 1:10 to 10:1.

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