KR20240076262A - Heterocyclic compound, organic light emitting device comprising same and composition for organic layer of organic light emitting device - Google Patents

Abstract

This specification relates to a heterocyclic compound represented by Formula 1, an organic light-emitting device containing the same, and a composition for an organic material layer.

Description

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

This specification relates to heterocyclic compounds, organic light-emitting devices containing the same, and compositions for organic material layers.

Electroluminescent devices are a type of self-luminous display devices and have the advantages 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 disappear, 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 roles such as hole injection, hole transport, electron blocking, hole blocking, electron transport, and electron injection may be used.

In order to improve the performance, lifespan, or efficiency of organic light-emitting devices, the development of 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 an organic material layer.

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

[Formula 1]

In Formula 1,

R1 to R5 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; 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 C1 to C60 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; Substituted or unsubstituted phosphine oxide group; and two or more groups selected from the group consisting of a substituted or unsubstituted amine group, or two or more groups adjacent to each other are combined with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring,

X is O; S; NRa or CRbRc,

L1 and L2 are the same or different from each other and are each independently directly bonded; Substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group,

Ra, Rb and Rc are the same or different from each other and are each independently 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,

m and n are the same or different from each other and are each independently an integer from 0 to 4,

a is an integer from 0 to 5,

b is an integer from 0 to 2,

c is an integer from 0 to 7,

When m, n and a to c are 2 or more, the substituents in parentheses are the same or different from each other,

The Ar1 is represented by the following formula A,

[Formula A]

In Formula A,

Y is O; or S;,

X1 is CR11 or N; X2 is CR12 or N; X3 is CR13 or N; X4 is CR14 or N,

Two of X1 to X4 are N,

One of R11 to R14 is connected to L1 of Formula 1 above,

Substituents other than those connected to L1 of Formula 1 among R11 to R14; and R6 are each independently hydrogen; heavy hydrogen; halogen; 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 C1 to C60 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; Substituted or unsubstituted phosphine oxide group; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group, or two or more groups adjacent to each other are combined with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring,

d is an integer from 0 to 4, and when d is 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 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, an exemplary embodiment of the present application provides an organic light-emitting device in which the organic material layer containing the heterocyclic compound of Formula 1 further includes a heterocyclic compound represented by the following Formula 2.

[Formula 2]

In Formula 2,

Z is O; or S,

R1' to R8' are the same or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; 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 C1 to C60 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; Substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other are combined with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring,

One of R1' to R8' is a substituted or unsubstituted C2 to C60 heteroaryl group containing N.

In addition, another embodiment of the present application includes a heterocyclic compound represented by Formula 1; and a heterocyclic compound represented by Formula 2 above.

The compounds described in this specification can be used as organic layer materials for organic light-emitting devices. The above compounds can serve as hole injection materials, hole transport materials, light-emitting materials, electron transport materials, and electron injection materials in organic light-emitting devices. In particular, the compound can be used as a light-emitting layer material for an organic light-emitting device.

Specifically, the compound may be used alone as a light-emitting material, or as a host material or dopant material of a light-emitting layer. At this time, the compound represented by Formula 1 can be used as a bipolar host and represents n-type or p-type depending on the nature of the substituent. When the compound represented by Formula 1 is used in the organic layer, the driving voltage of the device can be lowered, the light efficiency can be improved, and the lifespan characteristics of the device can be improved due to the thermal stability of the compound.

In particular, the heterocyclic compound represented by Formula 1 and the heterocyclic compound represented by Formula 2 can be simultaneously used as a material for the light-emitting layer of an organic light-emitting device. In this case, the driving voltage of the device can be lowered, light efficiency can be improved, and the lifespan characteristics of the device can be particularly improved due to the thermal stability of the compound.

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

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; Cyano group; C1 to C60 alkyl group; C2 to C60 alkenyl group; C2 to C60 alkynyl group; C3 to C60 cycloalkyl group; C2 to C60 heterocycloalkyl group; Aryl group of C6 to C60; C2 to C60 heteroaryl group; silyl group; Phosphine oxide group; and one or more substituents selected from the group consisting of amine groups, or two or more substituents selected from the above-exemplified substituents are substituted or unsubstituted with a connected substituent.

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 /T1×100 = 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, the 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, cyclopentylmethyl group, cyclohexylmethyl group, octyl group, n-octyl group, tert -Octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, 2,2-dimethylheptyl group, 1-ethyl-propyl group, 1,1-dimethyl-propyl group , isohexyl group, 2-methylpentyl group, 4-methylhexyl group, 5-methylhexyl group, etc., but is not limited thereto.

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

In the present specification, the cycloalkyl group includes a monocyclic or polycyclic 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 includes S, O, Se, N, or Si as a hetero atom, includes a monocyclic or polycyclic ring having 2 to 60 carbon atoms, and may be further substituted by 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 pyridyl group, pyrrolyl group, pyrimidyl group, pyridazinyl group, furanyl group, thiophene group, imidazolyl group, pyrazolyl group, oxazolyl group, isoxazolyl group, and thiazolyl group. group, isothiazolyl group, triazolyl group, furazanyl group, oxadiazolyl group, thiadiazolyl group, dithiazolyl group, tetrazolyl group, pyranyl group, thiopyranyl group, diazinyl group, oxazinyl group. , thiazinyl group, deoxynyl group, triazinyl group, tetrazinyl group, quinolyl group, isoquinolyl group, quinazolinyl group, isoquinazolinyl group, quinozolyryl group, naphthyridyl group, acridinyl group, phenanthridide Nyl group, imidazopyridinyl group, diazanaphthalenyl group, triazindene group, indolyl group, indolizinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiophene group, benzofuran group , dibenzothiophene group, dibenzofuran group, carbazolyl group, benzocarbazolyl group, dibenzocarbazolyl group, phenazinyl group, dibenzosilol group, spirobi (dibenzosilol), dihydrophenazinyl group, Phenoxazinyl group, phenanthridyl group, imidazopyridinyl group, thienyl group, indolo[2,3-a]carbazolyl group, indolo[2,3-b]carbazolyl group, indolinyl group, 10, 11-dihydro-dibenzo[b,f]azepine group, 9,10-dihydroacridinyl group, phenanthrazinyl group, phenothiathiazinyl group, phthalazinyl group, naphthylidinyl group, phenanthrolinyl group, Benzo[c][1,2,5]thiadiazolyl group, 2,3-dihydrobenzo[b]thiophene, 2,3-dihydrobenzofuran, 5,10-dihydrodibenzo[b,e ][1,4]azacylinyl, pyrazolo[1,5-c]quinazolinyl group, pyrido[1,2-b]indazolyl group, pyrido[1,2-a]imidazo[1, Examples include, but are not limited to, 2-e]indolinyl group and 5,11-dihydroindeno[1,2-b]carbazolyl group.

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(R101)(R102)(R103), and R101 to R103 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)(R104)(R105), and R104 and R105 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, the phosphine oxide group includes, but is not limited to, dimethylphosphine oxide, diphenylphosphine oxide, and dinaphthylphosphine oxide.

In the present specification, the amine group is represented by -N(R106)(R107), R106 and R107 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.

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. That is, in one embodiment of the present application, hydrogen; Alternatively, it may indicate that deuterium can be substituted for each other.

In one embodiment of the present application, the repetition number of 0 means direct binding.

An exemplary embodiment of the present specification provides a heterocyclic compound of Formula 1 above.

[Formula 1]

In Formula 1,

R1 to R5 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; 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 C1 to C60 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; Substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other are combined with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring,

X is O; S; NRa or CRbRc,

L1 and L2 are the same or different from each other and are each independently directly bonded; Substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group,

Ra, Rb and Rc are the same or different from each other and are each independently 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,

m and n are the same or different from each other and are each independently an integer from 0 to 4,

a is an integer from 0 to 5,

b is an integer from 0 to 2,

c is an integer from 0 to 7,

When m, n and a to c are 2 or more, the substituents in parentheses are the same or different from each other,

The Ar1 is represented by the following formula A,

[Formula A]

In Formula A,

Y is O; or S;,

X1 is CR11 or N; X2 is CR12 or N; X3 is CR13 or N; X4 is CR14 or N,

Two of X1 to X4 are N,

One of R11 to R14 is connected to L1 of Formula 1 above,

Substituents other than those connected to L1 of Formula 1 among R11 to R14; and R6 are each independently hydrogen; heavy hydrogen; halogen; 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 C1 to C60 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; Substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other are combined with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring,

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

In an exemplary embodiment of the present application, Formula 1 may be expressed as Formula 3 or Formula 4 below.

[Formula 3]

[Formula 4]

In Formula 3 and Formula 4,

The definition of the substituent is the same as that in Formula 1 above.

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

[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

In Formulas 3-1 to 3-3,

The definition of the substituent is the same as that in Formula 3 above.

In an exemplary embodiment of the present application, Formula 4 may be represented by any one of the following Formulas 4-1 to 4-3.

[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

In Formulas 4-1 to 4-3,

The definition of the substituent is the same as that in Formula 4 above.

In the present invention, the compound represented by Formula 1 has benzocarbazole as the basic skeleton, and the substituent of -(L1)m-Ar1, which is an electron withdrawing group, is bonded to the basic skeleton, making the entire molecule bipolar. Because it has properties, it has the ability to increase the bonding force between holes and electrons.

In particular, the compound of Formula 1 of the present invention has a core structure in which a carbazole group is condensed with a naphthyl group having high hole mobility, and has higher stability and mobility for holes and electron mobility than a simple carbazole core. By introducing -(L1)m-Ar1 with a high value as a substituent, the flow of holes and electrons can be achieved more smoothly.

Accordingly, the number of excitons contributing to light emission within the light emitting layer is increased, thereby improving the luminous efficiency and driving voltage of the device, and improving the durability and stability of the device, thereby effectively increasing the lifespan of the device. In addition, in the case of the benzo[b]carbazole core in which the naphthyl group, which is the core structure, is applied in a linear structure as shown in Chemical Formula 4 (particularly, Chemical Formula 4-2) of the present invention, steric hindrance is reduced, structural stability is achieved, and high thermal resistance is achieved. It has stability. This effect shows the effect of increasing the lifespan through efficiency and high stability when driving the device.

For reference, as shown in Formula 3, in the case of the benzo[a]carbazole core, efficiency increases when driving the device by using steric hindrance with the -(L1)m-Ar1 functional group, which is an EWG group, and driving characteristics are improved. It shows the effect.

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

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,

The definition of each substituent is the same as that in Formula 1 above,

means the position connected to L2 of Formula 1 above.

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-3.

[Formula A-1]

[Formula A-2]

[Formula A-3]

In the above formulas A-1 to A-3,

One of R11 to R14 is connected to L1 of Formula 1 above,

The definitions of the remaining substituents are the same as those in Formula 1 above.

In an exemplary embodiment of the present application, R1 to R5 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; 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 C1 to C60 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; Substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other are combined with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted heterocycle.

In another embodiment, R1 to R5 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C6 to C60 aryl group; Substituted or unsubstituted C2 to C60 heteroaryl group; Substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group.

In another embodiment, R1 to R5 are the same as 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; Substituted or unsubstituted C2 to C40 heteroaryl group; Substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group.

In another embodiment, R1 to R5 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; C1 to C40 alkyl group; Aryl group of C6 to C40; and a C2 to C40 heteroaryl group.

In another embodiment, R1 to R5 are the same as or different from each other, and are each independently hydrogen; or deuterium;

In one embodiment of the present application, X is O; S; NRa or CRbRc.

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

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

In one embodiment of the present application, X is NRa.

In one embodiment of the present application, X is CRbRc.

In an exemplary embodiment of the present application, L1 and L2 are the same or different from each other and are each independently directly bonded; Substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group.

In another embodiment, L1 and L2 are the same or different from each other and are each independently directly bonded; Substituted or unsubstituted C6 to C40 arylene group; Or a substituted or unsubstituted C2 to C40 heteroarylene group.

In another embodiment, L1 and L2 are the same or different from each other and are each independently directly bonded; Substituted or unsubstituted C6 to C20 arylene group; Or a substituted or unsubstituted C2 to C20 heteroarylene group.

In another embodiment, L1 and L2 are the same or different from each other and are each independently directly bonded; Or it is a substituted or unsubstituted C6 to C20 arylene group.

In another embodiment, L1 and L2 are the same or different from each other and are each independently directly bonded; Or it is a C6 to C20 arylene group substituted or unsubstituted with deuterium.

In another embodiment, L1 and L2 are the same or different from each other and are each independently directly bonded; Or it is a monocyclic C6 to C10 arylene group substituted or unsubstituted with deuterium.

In another embodiment, L1 and L2 are the same or different from each other and are each independently directly bonded; Or it is a phenylene group substituted or unsubstituted with deuterium.

In an exemplary embodiment of the present application, Ra, Rb, and Rc are the same or different from each other, and are each independently 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.

In another embodiment, Ra, Rb, and Rc are the same or different from each other, and are each independently a 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 another embodiment, Ra, Rb, and Rc are the same or different from each other, and are each independently a 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 another embodiment, Ra, Rb, and Rc 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 naphthyl group; Substituted or unsubstituted dibenzofuran group; Or it may be a substituted or unsubstituted dibenzothiophene group.

In another embodiment, Ra, Rb, and Rc are the same or different from each other, and are each independently a phenyl group unsubstituted or substituted with deuterium; Biphenyl group substituted or unsubstituted with deuterium; Naphthyl group substituted or unsubstituted with deuterium; Dibenzofuran group substituted or unsubstituted with deuterium; Alternatively, it may be a dibenzothiophene group substituted or unsubstituted with deuterium.

In an exemplary embodiment of the present application, X1 is CR11 or N; X1 is CR12 or N; X3 is CR13 or N; X4 is CR14 or N, and two of X1 to X4 are N.

In an exemplary embodiment of the present application, X1 is N; X2 is N; X3 is CR13; X4 is CR14, and R13 may be connected to L1 of Formula 1 above.

In an exemplary embodiment of the present application, X1 is N; X2 is N; X3 is CR13; X4 is CR14, and R14 may be connected to L1 of Formula 1 above.

In an exemplary embodiment of the present application, X1 is N; X3 is N; X2 is CR12; X4 is CR14, and R14 may be connected to L1 of Formula 1 above.

In an exemplary embodiment of the present application, X1 is N; X3 is N; X2 is CR12; X4 is CR14, and R12 may be connected to L1 of Formula 1 above.

In an exemplary embodiment of the present application, X1 is N; X4 is N; X2 is CR12; X3 is CR13, and R12 may be connected to L1 of Formula 1 above.

In an exemplary embodiment of the present application, X1 is N; X4 is N; X2 is CR12; X3 is CR13, and R13 may be connected to L1 of Formula 1 above.

In an exemplary embodiment of the present application, X2 is N; X3 is N; X1 is CR11; X4 is CR14, and R11 may be connected to L1 of Formula 1 above.

In an exemplary embodiment of the present application, X2 is N; X3 is N; X1 is CR11; X4 is CR14, and R14 may be connected to L1 of Formula 1 above.

In an exemplary embodiment of the present application, X2 is N; X4 is N; X1 is CR11; X3 is CR13, and R11 may be connected to L1 of Formula 1 above.

In an exemplary embodiment of the present application, X2 is N; X4 is N; X1 is CR11; X3 is CR13, and R13 may be connected to L1 of Formula 1 above.

In an exemplary embodiment of the present application, X3 is N; X4 is N; X1 is CR11; X2 is CR12, and R11 may be connected to L1 of Formula 1 above.

In an exemplary embodiment of the present application, X3 is N; X4 is N; X1 is CR11; X2 is CR12, and R12 may be connected to L1 of Formula 1 above.

In an exemplary embodiment of the present application, a substituent other than that connected to L1 of Formula 1 among R11 to R14; and R6 are each independently hydrogen; heavy hydrogen; halogen; 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 C1 to C60 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; Substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other may be combined with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring.

In another exemplary embodiment, a substituent other than that connected to L1 of Formula 1 among R11 to R14; and R6 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C1 to C60 alkyl group; Substituted or unsubstituted C6 to C60 aryl group; Substituted or unsubstituted C2 to C60 heteroaryl group; Substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group.

In another exemplary embodiment, a substituent other than that connected to L1 of Formula 1 among R11 to R14; and R6 are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C6 to C60 aryl group; and a substituted or unsubstituted C2 to C60 heteroaryl group.

In another exemplary embodiment, a substituent other than that connected to L1 of Formula 1 among R11 to R14; and R6 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C6 to C40 aryl group; and a substituted or unsubstituted C2 to C40 heteroaryl group.

In another exemplary embodiment, a substituent other than that connected to L1 of Formula 1 among R11 to R14; and R6 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C6 to C20 aryl group; and a substituted or unsubstituted C2 to C20 heteroaryl group.

In another exemplary embodiment, a substituent other than that connected to L1 of Formula 1 among R11 to R14; and R6 are each independently hydrogen; heavy hydrogen; C6 to C20 aryl group substituted or unsubstituted with deuterium; and a C2 to C20 heteroaryl group substituted or unsubstituted with deuterium.

In another exemplary embodiment, a substituent other than that connected to L1 of Formula 1 among R11 to R14; and R6 are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted naphthyl group; Substituted or unsubstituted dibenzofuran group; Or it may be a substituted or unsubstituted dibenzothiophene group.

In another exemplary embodiment, a substituent other than that connected to L1 of Formula 1 among R11 to R14; and R6 are each independently hydrogen; heavy hydrogen; A phenyl group substituted or unsubstituted with deuterium; Biphenyl group substituted or unsubstituted with deuterium; Naphthyl group substituted or unsubstituted with deuterium; Dibenzofuran group substituted or unsubstituted with deuterium; Alternatively, it may be a dibenzothiophene group substituted or unsubstituted with deuterium.

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

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

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, the conditions required for each organic material layer are met by introducing substituents mainly used in hole injection layer materials, hole transport materials, light emitting layer materials, electron transport layer materials, and charge generation layer materials used in the manufacture of organic light-emitting devices into the core structure. You can synthesize the desired substance.

In addition, by introducing various substituents into the structure of Formula 1, it is possible to finely control the energy band gap, while improving the properties at the interface between organic materials and diversifying the uses of the material.

Meanwhile, the compound has a high glass transition temperature (Tg) and has excellent thermal stability. This increase in thermal stability is an important factor in providing driving stability to the device.

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 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 according to 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 according to 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 according to 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 according to Formula 1 may be used as a light-emitting layer material of the red organic light-emitting device.

Specific details about the heterocyclic compound represented by Formula 1 are the same as 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 the organic light-emitting device according to an exemplary embodiment of the present application, the organic material layer containing the heterocyclic compound of Formula 1 further includes a heterocyclic compound represented by the following Formula 2.

[Formula 2]

In Formula 2,

Z is O; or S,

R1' to R8' are the same or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; 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 C1 to C60 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; Substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other are combined with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring,

One of R1' to R8' is a substituted or unsubstituted C2 to C60 heteroaryl group containing N.

In an exemplary embodiment of the present application, Formula 2 may be represented by any one of the following Formulas 2-1 to 2-3.

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

In Formulas 2-1 to 2-3,

Z is the same as defined in Formula 2 above,

R11' to R19' are the same or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; 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 C1 to C60 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; Substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group,

One of R11' to R18' is a substituted or unsubstituted C2 to C60 heteroaryl group containing N.

In an exemplary embodiment of the present application, R11' to R19' are the same or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; 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 C1 to C60 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; Substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group.

In another embodiment, R11' to R19' are the same or different from each other, and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted C6 to C60 aryl group; Substituted or unsubstituted C2 to C60 heteroaryl group; Substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group.

In another embodiment, R11' to R19' are the same or different from each other, and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C6 to C40 aryl group; Substituted or unsubstituted C2 to C40 heteroaryl group; Substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group.

In another embodiment, R11' to R19' are the same or different from each other, and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted C6 to C20 aryl group; Substituted or unsubstituted C2 to C20 heteroaryl group; Substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group.

In another embodiment, R11' to R19' are the same or different from each other, and are each independently hydrogen; heavy hydrogen; A C6 to C20 aryl group substituted or unsubstituted with one or more substituents selected from the group consisting of a C6 to C20 aryl group and a substituted or unsubstituted amine group; and a substituted or unsubstituted amine group substituted or unsubstituted with one or more substituents selected from the group consisting of a C6 to C20 aryl group and a C2 to C20 heteroaryl group.

In an exemplary embodiment of the present application, one of R1' to R8' is a substituted or unsubstituted C2 to C60 heteroaryl group containing N.

In an exemplary embodiment of the present application, one of R1' to R8' is a substituted or unsubstituted C2 to C40 heteroaryl group containing N.

In an exemplary embodiment of the present application, one of R1' to R8' is a substituted or unsubstituted C2 to C20 heteroaryl group containing N.

In an exemplary embodiment of the present application, one of R1' to R8' is from the group consisting of a C6 to C20 aryl group containing N, a substituted or unsubstituted phosphine oxide group, and a substituted or unsubstituted heteroaryl group. It is a C2 to C20 heteroaryl group substituted or unsubstituted with one or more selected substituents.

In an exemplary embodiment of the present application, one of R1' to R8' is from the group consisting of a C6 to C20 aryl group containing N, a substituted or unsubstituted phosphine oxide group, and a substituted or unsubstituted heteroaryl group. It is a triazine group substituted or unsubstituted with one or more selected substituents.

In an exemplary embodiment of the present application, one of R1' to R8' is a substituted or unsubstituted triazine group.

In an exemplary embodiment of the present application, one of R11' to R18' is a substituted or unsubstituted C2 to C60 heteroaryl group containing N, and in this case, the definition is the same as one of R1' to R8'. do.

A compound of Formula 1 above; And when the compound of Formula 2 is included in the organic material layer of the organic light-emitting device, it shows better efficiency and lifespan effects. This result can be expected to indicate that an exciplex phenomenon occurs when two compounds are included at the same time.

The exciplex phenomenon is a phenomenon in which energy equivalent to the HOMO level of the donor (p-host) and the LUMO level of the acceptor (n-host) is released through electron exchange between two molecules. When an exciplex phenomenon occurs between two molecules, Reverse Intersystem Crossing (RISC) occurs, which can increase the internal quantum efficiency of fluorescence up to 100%. 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 driving voltage can be lowered, thereby helping to improve lifespan.

In an exemplary embodiment of the present application, the heterocyclic compound represented by Formula 2 may be any one selected from the following compounds.

In addition, another embodiment of the present application includes a heterocyclic compound represented by Formula 1; and a heterocyclic compound represented by Formula 2 above.

Specific details about the heterocyclic compound represented by the formula (1) and the heterocyclic compound represented by the formula (2) are the same as described above.

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 from 5:1 to 1:1, and from 1:2 to 2:1, but is not limited thereto.

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

In an exemplary embodiment of the present application, the organic layer includes a heterocyclic compound represented by Formula 1; and a heterocyclic compound represented by Formula 2 above, and can be used together with a phosphorescent dopant.

In an exemplary embodiment of the present application, the organic layer includes a heterocyclic compound represented by Formula 1; and a heterocyclic compound represented by Formula 2 above, and can be used together with an iridium-based dopant.

As the phosphorescent dopant material, those known in the art can be used.

For example, phosphorescent dopant materials represented by LL'MX', LL'L"M, LMX'X", L2MX', and L3M can be used, but the scope of the present invention is not limited by these examples.

Here, L, L', L", X' and X" are different bidentate ligands, and M is a metal that forms an octahedral complex.

M can be iridium, platinum, osmium, etc.

L is an anionic bidentate ligand coordinated to M with the iridium-based dopant by sp2 carbon and a hetero atom, and X may function to trap electrons or holes. Non-limiting examples of L include 2-(1-naphthyl)benzoxazole, (2-phenylbenzoxazole), (2-phenylbenzothiazole), (2-phenylbenzothiazole), (7,8 -Benzoquinoline), (thiophenyl pyrizine), phenylpyridine, benzothiophenyl pyridine, 3-methoxy-2-phenylpyridine, thiophenyl pyridine, tolyl pyridine, etc. Non-limiting examples of X' and

More specific examples are shown below, but are not limited to these examples.

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

In an exemplary embodiment of the present application, the content of the dopant may be 1% to 15%, preferably 3% to 10%, and more preferably 5% to 10%, based on the entire light emitting layer.

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 includes an electron blocking layer or a hole blocking layer, and the electron blocking layer or the hole blocking layer may include the heterocyclic compound.

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

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

Figure 3 illustrates 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. However, the scope of the present application is not limited by this laminated structure, and if necessary, the remaining layers except the light-emitting layer may be omitted, and other necessary functional layers may be added.

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 is formed by pre-mixing the heterocyclic compound of Formula 1 and the heterocyclic compound of Formula 2 using a thermal vacuum deposition method. A method for manufacturing a phosphorus organic light emitting device is provided.

The pre-mixed means mixing the materials first and mixing them in one park before depositing the heterocyclic compound of Formula 1 and the heterocyclic compound of Formula 2 on the organic material layer.

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

The organic material layer containing Formula 1 may additionally include other materials as needed.

Formula 1 above; And the organic material layer simultaneously containing Formula 2 may further include other materials as needed.

In the organic light emitting device according to an exemplary embodiment of the present application, materials other than the compounds of Formula 1 and Formula 2 are illustrated below, but these are for illustrative purposes only and are not intended to limit the scope of the present application. It can be replaced by materials known in the art.

As the anode material, materials with a relatively large work function can be used, 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 light emitting materials, 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 the host material of 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.

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.

<Manufacturing example>

<Preparation Example 1> Preparation of compound 1-1

1) Preparation of compound 1-1-1

2-bromo-5H-benzo[b]carbazole; A 5.0g (16.9mmol), 9-phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxabororan-2-yl)-9H-carbazole (9- phenyl-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole); Dissolve 6.2g (16.9mnol) of B, 1.0g (0.8mmol) of Pd(PPh ₃ ) ₄ , and 7.0g (50.7mmol) of K ₂ CO ₃ in 50mL/20mL of 1,4-dioxane/H ₂ O and reflux for 4 hours. did. After the reaction was completed, the filtrate was filtered under reduced pressure at room temperature and the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hex=1:3), and 6.8g (88%) of 1-1-1 was obtained.

2) Preparation of compound 1-1

Compound 1-1-1 6.8g (14.9mmol), 2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine (2-chloro-4-phenylbenzo[4,5] thieno[3,2-d]pyrimidine) 4.4g (14.9mmol), CuI 2.8g (14.9mmol), trans-1,2-diaminocyclohexane 1.7g (14.9mmol), K ₃ PO ₄ 6.3g (29.8mmol) It was dissolved in 50 mL of 1,4-dioxane and refluxed for 24 hours. After the reaction was completed, it was filtered under reduced pressure at room temperature, and the solvent was removed from the filtrate using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hex=1:3), and 8.3g of target compound 1-1 was obtained (yield 78%).

In Preparation Example 1, intermediate A of Table 1 below was used instead of 2-bromo-5H-benzo[b]carbazole (A), and 9-phenyl-3 -(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole (9-phenyl-3-(4,4,5,5- Instead of tetramethyl-1,3,2-dioxaborolan-2-yl)-9H-carbazole) (B), use intermediate B of Table 1 below, and use 2-chloro-4-phenylbenzo[4,5]thieno[3 ,2-d]pyrimidine (2-chloro-4-phenylbenzo[4,5]thieno[3,2-d]pyrimidine) (C), except that intermediate C of Table 1 below was used, and Preparation Example 1 above The following target compound was synthesized in the same manner as above.

<Preparation Example 2> Preparation of compound 1-34

1) Preparation of compound 1-34

4-([1,1'-biphenyl]-4-yl)-2-(2-(9-phenyl-9H-carbazol-3-yl)-5H-benzo[b]carbazol-5-yl )benzo[4,5]thieno[3,2-d]pyrimidine (4-([1,1'-biphenyl]-4-yl)-2-(2-(9-phenyl-9H-carbazol- 3-yl)-5H-benzo[b]carbazol-5-yl)benzo[4,5]thieno[3,2-d]pyrimidine); Compound A (3g, 3.8mmol) and trifluoromethanesulfonic acid (2.8g, 18.9mmol) were dissolved in benzene-d6 (20mL) and refluxed for 8 hours. After the reaction was completed, it was neutralized using an aqueous potassium phosphate solution, filtered under reduced pressure, and the solvent was removed from the filtrate using a rotary evaporator. The reaction product was purified by column chromatography (EA:Hex=1:3), and 2.8g of target compound 1-34 was obtained (89% yield).

The target compound was synthesized in the same manner as in Preparation Example 2, using Intermediate A of Table 2 below instead of Compound A in Preparation Example 2.

<Preparation Example 3> Preparation of compound 5-1

1) Preparation of compound 5-1-1

2,4-dichloro-6-phenyl-1,3,5-triazine 5.0g (22.1mmol), dibenzo[b,d ]furan-1-ylboronic acid (dibenzo[b,d]furan-1-ylboronic acid) 4.7g (22.1mmol), Pd(PPh ₃ ) ₄ 1.3g (1.1mmol), K ₂ CO ₃ 9.2g (66.3mmol) ) was dissolved in 1,4-dioxane/H ₂ O 50mL/20mL and refluxed for 3 hours. After the reaction was completed, the filtrate was filtered under reduced pressure at room temperature and the solvent was removed using a rotary evaporator. The reaction product was purified by column chromatography (DCM:Hex=1:3) and 6.0g (76%) of 5-1-1 was obtained.

2) Preparation of compound 5-1

Compound 5-1-1 6.0g (16.8mmol), naphthalen-2-ylboronic acid 2.9g (16.8mmol), Pd(PPh ₃ ) ₄ 1.0g (0.8mmol), K ₂ CO ₃ 7.0g (50.4mmol) was dissolved in 1,4-dioxane/H ₂ O 50mL/20mL and refluxed for 3 hours. After the reaction is complete, it is filtered under reduced pressure at room temperature. DCB was dissolved, silica purified, and then recrystallized using DCB to obtain 6.7g (89%) of target compound 5-1.

In Preparation Example 3, instead of 2,4-dichloro-6-phenyl-1,3,5-triazine (2,4-dichloro-6-phenyl-1,3,5-triazine) (A), of Table 3 below Intermediate A was used, and intermediate B of Table 3 below was used instead of dibenzo[b,d]furan-1-ylboronic acid (B), and naphthalene-2 The target compound below was synthesized in the same manner as in Preparation Example 3, except that intermediate C of Table 3 below was used instead of naphthalen-2-ylboronic acid (C).

<Preparation Example 4> Preparation of compound 5-27

1) Preparation of compound 5-27-1

In the preparation of compound 5-1-1 of Preparation Example 3, 2,4-dichloro-6-phenyl-1,3,5-triazine (2,4-dichloro-6-phenyl-1,3,5-triazine ) Instead, Intermediate A of Table 4 below was used, and Intermediate B of Table 4 below was used instead of dibenzo[b,d]furan-1-ylboronic acid. and prepared in the same manner to obtain 8.1 g (91%) of compound 5-27-1.

2) Preparation of compound 5-27

Compound 5-27-1 8.1g (13.8mmol), phenylboronic acid 1.7g (13.8mmol), Pd ₂ dba ₃ 0.6g (0.7mmol), Xphos 0.7g (1.4mmol), K2CO3 5.7g ( 41.4 mmol) was dissolved in 80 mL of Xylene and refluxed for 5 hours. After the reaction is complete, it is filtered under reduced pressure at room temperature. DCB was dissolved, silica was purified, and then recrystallized using DCB to obtain 6.8g (79%) of target compound 5-27.

Instead of 5.0 g (15.2 mmol) (A) of 2-(1-chlorodibenzo[b,d]furan-3-yl)-4,4,5,5-tetramethyl-1,3,2-dioxaborolane in Preparation Example 4 Use intermediate A in Table 4 below, use intermediate B in Table 4 instead of 2-chloro-4,6-di(naphthalen-2-yl)-1,3,5-triazine (B), and use phenylboronic acid. The target compound below was synthesized in the same manner as in Preparation Example 4, except that Intermediate C of Table 4 below was used instead of (C).

In addition to the compounds described in Preparation Examples 1 to 4, the remaining compounds of Formula 1 and Formula 2 were also prepared in the same manner as described in the Preparation Examples above.

Tables 5 and 6 below show 1H NMR data and FD-MS data of the synthesized compounds, and through the following data, it can be confirmed that the desired compound was synthesized.

compound number ^1H NMR (CDCl ₃ , 400Mz) 1-1 δ = 7.98~8.18(m, 9H), 7.79(d, 2H), 7.77(s, 2H), 7.40~7.67(m, 16H), 7.29(t, 1H) 1-2 δ = 8.30(d, 2H), 7.98~8.18(m, 9H), 7.85(d, 2H), 7.77(s, 2H), 7.40~7.67(m, 18H), 7.29(t, 1H) 1-5 δ = 8.34(s, 1H), 7.97~8.16(m, 13H), 7.77(s, 2H), 7.40~7.67(m, 15H), 7.29(t, 1H) 1-7 δ = 8.18(d, 2H), 8.16(d, 2H), 7.98~8.12(5H), 7.79(d, 4H), 7.77(s, 2H), 7.63~7.68(m, 5H), 7.41~7.56( m, 13H), 7.29(t, 1H) 1-15 δ = 7.98~8.18(m, 9H), 7.89(d, 1H), 7.77(s, 2H), 7.29~7.74(m, 20H) 1-19 δ = 8.45(d, 1H), 7.93~8.16(m, 11H), 7.82(d, 1H), 7.77(s, 2H), 7.45~7.67(m, 15H), 7.40(s, 1H), 7.29( t, 1H) 1-20 δ = 8.46(d, 1H), 7.98~8.18(m, 11H), 7.80~8.72(m, 2H), 7.77(s, 2H), 7.45~7.67(m, 14H), 7.40(s, 1H), 7.29(t, 1H) 1-24 δ = 7.98~8.18(m, 9H), 7.88(d, 1H), 7.80(s, 1H), 7.79(d, 2H), 7.77(s, 2H), 7.63~7.67(m, 5H), 7.28~ 7.55(m, 12H) 1-50 δ = 8.15~8.16(d, 3H), 7.98~8.05(m, 3H), 7.77~7.79(m, 4H), 7.26~7.66(m, 21H), 7.09~7.11(m, 4H) 1-56 δ = 8.30(d, 2H), 8.16~8.18(m, 3H), 7.98~8.05(m, 3H), 7.89(d, 1H), 7.85(d, 2H), 7.77(s, 1H), 7.62~ 7.67(m, 5H), 7.32~7.55(m, 12H) 1-59 δ = 8.34(s, 1H), 8.16~8.18(d, 3H), 7.92~8.01(m, 8H), 7.32~7.76(m, 15H) 1-67 δ =8.45(d, 1H), 8.41(d, 1H), 8.16~8.20(m, 4H), 7.98~8.05(m, 4H), 7.79(d, 2H), 7.77(s, 1H), 7.40~ 7.59(m, 12H) 1-78 δ = 8.45(d, 1H), 8.30(d, 2H), 8.12~8.18(m, 5H), 8.00(d, 2H), 7.98(d, 1H), 7.85(d, 2H), 7.77(s, 2H), 7.41~7.67(m, 18H), 7.29(t, 1H) 1-80 δ = 8.35(d, 1H), 8.12~8.16(m, 5H), 7.98~8.00(m, 3H), 7.79(d, 4H), 7.77(s, 2H), 7.63~7.68(m, 5H), 7.41~7.53(m, 13H), 7.29(t, 1H) 1-85 δ = 8.49(d, 1H), 8.45(d, 1H), 8.10~8.16(m, 5H), 8.00(d, 1H), 7.98(d, 1H), 7.79(d, 2H), 7.77(s, 1H), 7.40~7.68(m, 17H), 7.29(t, 1H) 1-87 δ =8.45(d, 1H), 8.16~8.18(d, 3H), 7.89~8.01(m, 4H), 7.79(d, 2H), 7.77(s, 1H), 7.64~7.75(m, 5H), 7.50~7.55(m, 5H), 7.32~7.41(m, 4H), 1-88 δ = 8.46(d, 2H), 8.9(d, 2H), 8.16~8.17(m, 4H), 7.94~8.00(m, 3H), 7.85(d, 2H), 7.82d(d, 1H), 7.77 (s, 1H), 7.67(d, 2H), 7.39~7.56(m, 12H) 1-90 δ = 8.30(d, 2H), 7.98~8.18(m, 9H), 7.85(d, 2H), 7.77(s, 2H), 7.39~7.67(m, 18H), 7.30(t, 1H) 1-93 δ =7.98~8.18(m, 9H), 7.78~7.79(m, 3H), 7.77(s, 2H), 7.63~7.68(m, 4H), 7.41~7.55(m, 13H), 7.29(t, 1H) ), 7.19(d, 2H) 1-99 δ = 8.18(d, 1H), 8.16(d, 2H), 7.89~8.05(m, 5H), 7.67~7.79(m, 8H), 7.32~7.55(m, 9H) 1-100 δ = 8.45(d, 1H), 8.30(d, 2H), 8.16~8.18(d, 3H), 7.94~8.05(m, 5H), 7.83~7.85(m, 3H), 7.77(s, 1H), 7.67(t, 2H), 7.39~7.52(m, 12) 1-111 δ = 8.18(d, 1H), 8.16(d, 2H), 7.95~8.06(m, 5H), 7.66~7.79(m, 8H), 7.32~7.55(m, 9H) 1-145 δ = 8.51(d, 2H), 8.30(d, 3H), 7.98~8.16(m, 6H), 7.85(d, 2H), 7.42~7.67(m, 19H), 7.29~7.31(m, 2H) 1-149 δ = 7.98~8.16(m, 6H), 7.90(d, 1H), 7.79(d, 3H), 7.41~7.66(m, 19H), 7.29(t, 1H) 2-3 δ = 8.18(d, 2H), 8.12~15(m, 3H), 8.00(d, 2H), 7.77(d, 2H), 7.32~7.68(m, 25H) 2-15 δ = 8.18(d, 2H), 8.16(d, 2H), 8.12(d, 1H), 8.00(d, 2H), 7.89(d, 1H), 7.77(d, 2H), 7.28~7.67(m, 22H) 2-18 δ = 8.18(d, 2H), 8.16(d, 2H), 8.12(d, 1H), 8.00(d, 2H), 7.86~7.89(d, 2H), 7.77(d, 2H), 7.29~7.70( m, 21H) 2-20 δ = 8.45(d, 1H), 8.12~8.19(m, 5H), 7.98~8.01(m, 4H), 7.80~7.86(m, 2H), 7.78(d, 2H), 7.33~7.68(m, 18H) ) 2-44 δ = 8.49(d, 1H), 8.34(s, 1H), 8.10~8.18(m, 5H), 7.87~8.00(m, 5H), 7.77(s, 1H), 7.29~7.70(m, 19H) 2-49 δ = 8.18(d, 1H), 8.16(d, 2H), 8.06(s, 1H), 8.00(d, 1H), 7.79~7.87(m, 4H), 7.77(s, 1H), 7.26~7.67( m, 21H), 7.11(d, 4H) 2-52 δ = 8.18(d, 1H), 8.16(d, 2H), 8.00(d, 1H), 7.67~7.87(m, 8H), 7.77(s, 1H), 7.26~7.55(m, 18H), 7.11( d, 4H) 2-66 δ = 8.45(d, 1H), 7.98~8.18(m, 8H), 7.79(d, 2H), 7.77(s, 1H), 7.60~7.67(m, H), 7.32~7.55(m, 9H) 2-73 δ = 8.45(d, 1H), 8.41(d, 1H), 8.34(s, 1H), 8.16~8.20(m, 4H), 7.87~8.01(m, 6H), 7.52~7.77(m, 11H), 7.40(s, 1H), 7.38d(1, H), 7.32(d, 1H) 2-77 δ = 8.12~8.18(m, 5H), 8.00(d, 2H), 7.89(d, 1H), 7.79(d, 2H), 7.77(s, 2H), 7.32~7.67(m, 18H) 2-82 δ = 8.12~8.18(m, 5H), 8.00(d, 2H), 7.89(d, 1H), 7.76~7.79(m, 6H), 7.29~7.66(m, 20H) 2-88 δ = 8.45(d, 1H), 8.30(d, 2H), 8.16~8.18(m, 3H), 7.82~7.98(m, 7H), 7.77(s, 1H), 7.66~7.67(m, 3H), 7.37~7.56(m, 12H) 2-98 δ = 8.30(d, 2H), 8.10~8.16(m, 5H), 8.00(d, 1H), 7.85~7.90(m, 3H), 7.77(s, 1H), 7.28~7.70(m, 22H) 2-99 δ = 8.18(d, 1H), 8.16(d, 2H), 7.89~8.00(m, 3H), 7.66~7.79(m, 10H), 7.55(s, 1H), 7.51(d, 2H), 7.32~ 7.51(m, 6H) 2-100 δ = 8.45(d, 1H), 8.30(d, 2H), 8.18(d, 1H), 8.16(d, 2H), 7.94~8.00(m, 3H), 7.77~7.85(m, 4H), 7.66~ 7.70(m, 5H), 7.32~7.56(m, 11H) 2-111 δ = 8.16~8.18(m, 3H), 7.89~8.00(m, 3H), 7.66~7.79(m, 10H), 7.55(s, 1H), 7.51(d, 2H), 7.32~7.42(m, 6H) ) 2-123 δ = 8.28(d, 2H), 8.16~8.18(m, 3H), 7.89~8.01(m, 4H), 7.66~7.78(m, 7H), 7.55(s, 1H), 7.51(d, 2H), 7.33~7.41(m, 6H) 3-5 δ = 8.51(d, 1H), 8.34(s, 1H), 7.92~8.16(m, 13H), 7.77(s, 2H), 7.45~7.67(m, 14H), 7.29(t, 1H) 3-15 δ = 8.51(d, 1H), 7.98~8.18(m, 9H), 7.89(d, 1H), 7.77(s, 2H), 7.75(d, 1H), 7.32~7.67(m, 18H) 3-17 δ = 8.51(d, 1H), 7.89~8.17(m, 11H), 7.77(s, 2H), 7.75(d, 1H), 7.29~7.68(m, 17H) 3-19 δ = 8.51(d, 1H), 8.45(d, 1H), 7.94~8.19(m, 11H), 7.82(d, 1H), 7.77(s, 2H), 7.45~7.67(m, 15H), 7.29( t, 1H) 3-20 δ = 8.52(d, 1H), 8.45(d, 1H), 7.98~8.18(m, 11H), 7.86(d, 1H), 7.80(d, 1H), 7.77(s, 2H), 7.46~7.67( m, 14H), 7.29(t, 1H) 3-24 δ = 8.50(d, 1H), 7.98~8.18(m, 9H), 7.89(d, 1H), 7.80(s, 1H), 7.79(d, 2H), 7.77(s, 2H), 7.32~7.68( m, 16H) 3-27 δ = 8.51(d, 1H), 8.45(d, 1H), 7.97~8.19(m, 11H), 7.79(d, 2H), 7.77(s, 2H), 7.41~7.67(m, 14H), 7.29( t, 1H) 3-49 δ = 8.51(d, 1H), 7.98~8.18(m, 7H), 7.87(d, 1H), 7.79(d, 2H), 7.77(s, 1H), 7.26~7.68(m, 19H), 7.00~ 7.03(m, 4H) 3-64 δ = 8.51(d, 1H), 7.99~8.18(m, 6H), 7.77~7.88(m, 6H), 7.66~7.67(m, 3H), 7.38~7.52(m, 9H), 7.25~7.26(d) , 4H) 3-67 δ = 8.51(d, 1H), 8.45(d, 1H), 8.41(d, 1H), 7.98~8.18(m, 8H), 7.79(d, 2H), 7.77(s, 1H), 7.41~7.67( m, 11H) 3-70 δ = 8.51(d, 1H), 8.45(d, 1H), 8.41(d, 1H), 8.30(d, 2H), 7.97~8.20(m, 8H), 7.85(d, 2H), 7.77(s, 1H), 7.67)(d, 2H), 7.51~7.58(m, 11H) 3-77 δ = 8.51(d, 1H), 8.45(d, 1H), 8.12~8.18(m, 5H), 7.98~8.00(m, 3H), 7.79(d, 2H), 7.77(s, 2H), 7.41~ 7.66(m, 15H), 7.29(t, 1H) 3-83 δ = 8.51(d, 1H), 8.45(d, 1H), 8.12~8.18(m, 5H), 7.89~8.00(m, 5H), 7.79(d, 2H), 7.77(s, 2H), 7.28~ 7.68(m, 16H) 3-87 δ = 8.51(d, 1H), 8.45(d, 1H), 8.12~8.17(m, 3H), 7.89~8.00(m, 4H), 7.41~7.75(m, 16H) 3-88 δ = 8.51(d, 1H), 8.45(d, 2H), 8.30(d, 2H), 8.12~8.17(m, 3H), 7.94~8.01(m, 4H), 7.85(d, 2H), 7.82( d, 1H), 7.77(s, 1H), 7.67(t, 2H), 7.41~7.56(m, 11H) 3-92 δ = 8.51(d, 1H), 7.98~8.18(m, 9H), 7.79(d, 4H), 7.77(s, 2H), 7.41~7.68(m, 17H), 7.29(t, 1H) 3-94 δ = 8.51(d, 1H), 7.98~8.18(m, 9H), 7.79(d, 2H), 7.77(s, 2H), 7.42~7.67(m, 19H), 7.29(t, 1H) 3-99 δ = 8.52(d, 1H), 7.89~8.17(m, 8H), 7.79(d, 2H), 7.77(s, 1H), 7.32~7.68(m, 13H) 3-100 δ = 8.51(d, 1H), 8.45(d, 1H), 8.30(d, 2H), 7.94~8.16(m, 8H), 7.85(d, 2H), 7.82(d, 1H), 7.77(s, 1H), 7.67(t, 2H), 7.41~7.56(m, 11H) 3-141 δ = 8.52(d, 1H), 8.49(d, 2H), 7.98~6.16(m, 7H), 7.79(d, 2H), 7.41~7.68(m, 17H), 7.29(t, 1H) 4-8 δ = 8.51(d, 1H), 8.09~8.18(m, 6H), 8.00(d, 2H), 7.79(d, 2H), 7.77(s, 2H), 7.32~7.70(m, 21H) 4-15 δ = 8.51(d, 1H), 8.12~8.18(m, 5H), 8.00(d, 2H), 7.89(d, 1H), 7.79(d, 2H), 7.77(s, 2H), 7.29~7.70( m, 19H) 4-17 δ = 8.51(d, 1H), 8.12~8.18(m, 5H), 7.89~8.00(m, 4H), 7.29~7.77(m, 22H) 4-19 δ = 8.51(d, 1H), 8.45(d, 1H), 8.12~8.18(m, 5H), 7.94~8.00(m, 4H), 7.32~7.82(m, 21H) 4-22 δ = 8.51(d, 1H), 8.42~8.44(m, 2H), 8.12~8.18(m, 5H), 8.00(d, 2H), 7.98(d, 1H), 7.29~7.810(m, 21H) 4-23 δ = 8.51(d, 1H), 8.12~8.18(m, 5H), 8.00(d, 2H), 7.89(d, 1H), 7.29~7.79(m, 23H) 4-28 δ = 8.51(d, 1H), 8.45(d, 1H), 8.12~8.18(m, 5H), 7.94~8.00(m, 5H), 7.30~7.80(m, 20H) 4-49 δ = 8.51(d, 1H), 8.00~8.19(m, 5H), 7.01~7.87(m, 29H) 4-53 δ = 8.52(d, 1H), 8.18(d, 1H), 8.16(d, 1H), 8.12(d, 1H), 8.00(d, 1H), 7.88(d, 1H), 7.33~7.79(m, 19H) 4-65 δ = 8.51(d, 1H), 8.45(d, 1H), 8.18(d, 1H), 8.16(d, 1H), 8.12(d, 1H), 7.94~8.00(m, 3H), 7.70~7.79( m, 4H), 7.32~7.67(m, 13H) 4-80 δ = 8.50(d, 1H), 8.12~8.18(m, 5H), 8.00(d, 2H), 7.89(d, 1H), 7.79(d, 4H), 7.77(s, 2H), 7.29~7.66( m, 19H) 4-81 δ = 8.51(d, 1H), 8.12~8.18(m, 5H), 8.00(d, 2H), 7.89(d, 1H), 7.79(d, 3H), 7.77(s, 2H), 7.29~7.66( m, 18H), 7.19(d, 2H) 4-87 δ = 8.51(d, 1H), 8.12~8.18(m, 3H), 7.89~8.00(m, 4H), 7.51~7.79(m, 12H), 7.32~7.42(m, 5H) 4-88 δ = 8.51(d, 1H), 8.45(d, 1H), 8.30(d, 2H), 8.12~8.18(m, 3H), 7.77~8.01(m, 8H), 7.66~7.67(m, 3H), 7.32~7.57(m, 11H) 4-89 δ = 8.51(d, 1H), 8.12~8.18(m, 5H), 8.00(d, 2H), 7.70~7.79(m, 4H), 7.29~7.66(m, 18H) 4-99 δ = 8.51(d, 1H), 8.12~8.17(m, 3H), 7.89~8.00(m, 3H), 7.52~7.80(m, 13H), 7.32~7.42(m, 5H) 4-112 δ = 8.51(d, 1H), 8.45(d, 1H), 8.30(d, 2H), 8.12~8.18(m, 3H), 7.94~8.02(m, 3H), 7.77~7.85(m, 4H), 7.67~7.70(m, 4H), 7.32~7.57(m, 11H) 5-1 δ = 9.09(s, 1H), 8.49(d, 1H), 8.28(d, 2H), 7.89~8.01(m, 4H), 7.75(d, 1H), 7.33~7.67(m, 10H) 5-3 δ = 9.09(s, 1H), 8.49(d, 1H), 7.85~8.01(m, 6H), 7.76(d, 1H), 7.24~7.65(m, 14H) 5-24 δ = 9.10(s, 1H), 8.49(d, 1H), 8.28(d, 2H), 7.92~8.01(m, 7H), 7.73(d, 1H), 7.75(d, 2H), 7.41~7.63( m, 11H), 7.25(d, 4H) 5-27 δ = 9.09(s, 2H), 8.49(d, 2H), 8.16(d, 2H), 8.0(d, 4H), 7.92(d, 2H), 7.79(d, 2H), 7.40~7.68(m, 13H) 5-35 δ = 8.28(d, 4H), 8.16(d, 1H), 8.14(d, 1H), 7..81~8.00(m, 5H), 7.41~7.65(m, 14H), 7.25(d, 4H) 5-38 δ = 9.09(s, 1H), 8.55(d, 1H), 8.49(d, 1H), 8.28(d, 2H), 8.18(d, 1H), 7.90~7.99(m, 7H), 7.73~7.75( d, 2H), 7.71(s, 1H), 7.52~7.64(m, 10H), 7.41(t, 1H) 5-45 δ = 8.55(d, 1H), 8.28(d, 4H), 8.16(d, 2H), 7.94(d, 1H), 7.89(d, 1H), 7.66~7.69(m, 5H), 7.25~7.56( m, 12H) 5-54 δ = 8.28(d, 4H), 7.89(d, 1H), 7.75(d, 1H), 7.62~7.66(m, 4H), 7.32~7.56(m, 18H), 6.69(d, 2H), 6.39( d, 1H), 6.33(d, 1H) 5-74 δ = 8.28(d, 4H), 8.16(d, 2H), 7.67~7.88(m, 6H), 7.40~7.52(m, 12H), 7.20(t, 2H), 6.81(t, 1H), 6.63( d, 2H), 6.39(d, 1H) 5-78 δ = 9.09(s, 2H), 8.49(d, 2H), 8.45(d, 1H), 7.92~8.04(m, 8H), 7.77(s, 1H), 7.41~7.60(m, 11H) 5-79 δ = 8.29(d, 4H), 8.16(d, 2H), 7.88~7.99(m, 6H), 7.41~7.73(m, 13H) 7.25(d, 4H)

compound FD-Mass compound FD-Mass 1-1 m/z=718.87 (C50H30N4S, 718.22) 3-20 m/z=825.01 (C56H32N4S2, 824.21) 1-2 m/z=794.96 (C56H34N4S, 794.25) 3-24 m/z=808.94 (C56H32N4OS, 808.23) 1-5 m/z=768.92 (C54H32N4S, 768.23) 3-27 m/z=825.01 (C56H32N4S2, 824.21) 1-7 m/z=794.96 (C56H34N4S, 794.25) 3-49 m/z=793.97 (C57H35N3S, 793.26) 1-15 m/z=808.94 (C56H32N4OS, 808.23) 3-64 m/z=719.85 (C50H29N3OS, 719.20) 1-19 m/z=825.01 (C56H32N4S2, 824.21) 3-67 m/z=659.82 (C44H25N3S2, 659.15) 1-20 m/z=825.01 (C56H32N4S2, 824.21) 3-70 m/z=735.92 (C50H29N3S2, 735.18) 1-24 m/z=808.94 (C56H32N4OS, 808.23) 3-77 m/z=718.87 (C50H30N4S, 718.22) 1-34 m/z=829.17 (C56D34N4S, 828.46) 3-83 m/z=808.94 (C56H32N4OS, 808.23) 1-50 m/z=793.97 (C57H35N3S, 793.26) 3-87 m/z=643.75 (C44H25N3OS, 643.17) 1-56 m/z=719.85 (C50H29N3OS, 719.20) 3-88 m/z=735.92 (C50H29N3S2, 735.18) 1-59 m/z=693.81 (C48H27N3OS, 693.19) 3-92 m/z=794.96 (C56H34N4S, 794.25) 1-67 m/z=659.82 (C44H25N3S2, 659.15) 3-94 m/z=794.96 (C56H34N4S, 794.25) 1-78 m/z=794.96 (C56H34N4S, 794.25) 3-99 m/z=643.75 (C44H25N3OS, 643.17) 1-80 m/z=794.96 (C56H34N4S, 794.25) 3-100 m/z=735.92 (C50H29N3S2, 735.18) 1-85 m/z=718.87 (C50H30N4S, 718.22) 3-132 m/z=749.05 (C50D30N4S, 748.41) 1-87 m/z=643.75 (C44H25N3OS, 643.17) 3-141 m/z=718.87 (C50H30N4S, 718.22) 1-88 m/z=735.92 (C50H29N3S2, 735.18) 4-8 m/z=778.90 (C56H34N4O, 778.27) 1-90 m/z=794.96 (C56H34N4S, 794.25) 4-15 m/z=792.88 (C56H32N4O2, 792.25) 1-93 m/z=794.96 (C56H34N4S, 794.25) 4-17 m/z=792.88 (C56H32N4O2, 792.25) 1-99 m/z=643.75 (C44H25N3OS, 643.17) 4-19 m/z=808.94 (C56H32N4OS, 808.23) 1-100 m/z=735.92 (C50H29N3S2, 735.18) 4-22 m/z=808.94 (C56H32N4OS, 808.23) 1-111 m/z=643.75 (C44H25N3OS, 643.17) 4-23 m/z=792.88 (C56H32N4O2, 792.25) 1-145 m/z=794.96 (C56H34N4S, 794.25) 4-28 m/z=808.94 (C56H32N4OS, 808.23) 1-149 m/z=718.87 (C50H30N4S, 718.22) 4-49 m/z=777.91 (C57H35N3O, 777.28) 1-157 m/z=749.05 (C50D30N4S, 748.41) 4-53 m/z=627.69 (C44H25N3O2, 627.19) 1-160 m/z=727.92 (C50H21D9N4S, 727.28) 4-65 m/z=643.75 (C44H25N3OS, 643.17) 2-3 m/z=778.90 (C56H34N4O, 778.27) 4-80 m/z=778.90 (C56H34N4O, 778.27) 2-15 m/z=792.88 (C56H32N4O2, 792.25) 4-81 m/z=778.90 (C56H34N4O, 778.27) 2-18 m/z=792.88 (C56H32N4O2, 792.25) 4-87 m/z=627.69 (C44H25N3O2, 627.19) 2-20 m/z=808.94 (C56H32N4OS, 808.23) 4-88 m/z=719.85 (C50H29N3OS, 719.20) 2-31 m/z=732.98 (C50D30N4O, 732.43) 4-89 m/z=702.80 (C50H30N4O, 702.24) 2-44 m/z=752.86 (C50H32N4O, 752.26) 4-99 m/z=627.69 (C44H25N3O2, 627.19) 2-49 m/z=777.91 (C57H35N3O, 777.28) 4-108 m/z=732.98 (C50D30N4O, 732.43) 2-52 m/z=777.91 (C57H35N3O, 777.28) 4-112 m/z=719.85 (C50H29N3OS, 719.20) 2-66 m/z=643.75 (C44H25N3OS, 643.17) 5-1 m/z=449.50 (C31H19N3O, 449.15) 2-73 m/z=643.75 (C44H25N3OS, 643.17) 5-3 m/z=525.60 (C37H23N3O, 525.18) 2-77 m/z=702.80 (C50H30N4O, 702.24) 5-4 m/z=548.74 (C37D23N3O, 548.33) 2-82 m/z=778.90 (C56H34N4O, 778.27) 5-8 m/z=600.81 (C41D25N3O, 600.36) 2-88 m/z=719.85 (C50H29N3OS, 719.20) 5-14 m/z=669.93 (C46H3D28N3O, 669.42) 2-98 m/z=778.90 (C56H34N4O, 778.27) 5-18 m/z=680.93 (C47D29N3O, 680.41) 2-99 m/z=627.69 (C44H25N3O2, 627.19) 5-24 m/z=651.75 (C47H29N3O, 651.23) 2-100 m/z=719.85 (C50H29N3OS, 719.20) 5-27 m/z=625.72 (C45H27N3O, 625.22) 2-108 m/z=732.98 (C50D30N4O, 732.43) 5-35 m/z=651.75 (C47H29N3O, 651.23) 2-111 m/z=627.69 (C44H25N3O2, 627.19) 5-38 m/z=625.72 (C45H27N3O, 625.22) 2-123 m/z=627.69 (C44H25N3O2, 627.19) 5-45 m/z=614.69 (C43H26N4O, 614.21) 3-5 m/z=768.92 (C54H32N4S, 768.23) 5-54 m/z=732.83 (C51H32N4O2, 732.25) 3-15 m/z=808.94 (C56H32N4OS, 808.23) 5-74 m/z=666.77 (C47H30N4O, 666.24 3-17 m/z=808.94 (C56H32N4OS, 808.23) 5-78 m/z=591.72 (C41H25N3S, 591.18) 3-19 m/z=825.01 (C56H32N4S2, 824.21) 5-79 m/z=667.82 (C47H29N3S, 667.21)

<Experimental Example 1> - Fabrication of organic light emitting device

(1) Fabrication of organic light emitting devices

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

As a hole injection layer, which is a common layer on the ITO transparent electrode (anode), 4,4',4''-tris[2-naphthyl(phenyl)amino] triphenylamine (4,4',4''-Tris[ 2-naphthyl(phenyl)amino] triphenylamine: 2-TNATA) was deposited, and N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl) was deposited as a hole transport layer. )-4,4'-diamine (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine: NPB) was deposited.

After forming the hole injection layer and the hole transport layer in this way, a light-emitting layer was thermally vacuum deposited thereon as follows. The light-emitting layer was deposited with a compound listed in Table 7 as a red host, and (piq)2(Ir)(acac) was used as a red phosphorescent dopant to dope the host with 3 wt% of (piq)2(Ir)(acac). It was deposited to a thickness of 400Å.

Afterwards, Bathophenanthroline (Bphen) was deposited to a thickness of 30Å as a hole blocking layer, and tris(8-hydroxyquinolinato)aluminium (Alq3) was deposited on top of it as an electron transport layer. It was deposited to a thickness of 250Å.

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. An organic light emitting device was manufactured.

Meanwhile, all organic compounds required for the production of organic light-emitting devices were purified by vacuum sublimation under 10 ^-6 to 10 ^-8 torr for each material and used in the production of organic light-emitting devices.

(2) Driving voltage and luminous efficiency of organic light-emitting devices

The electroluminescence (EL) characteristics of the organic light-emitting device manufactured as described above were measured using the M7000 from MacScience, and the standard luminance was measured to be 6,000 cd using the lifespan measurement equipment (M6000) manufactured by MacScience using the measurement results. When /m ² , T90 was measured. The results of measuring the driving voltage, luminous efficiency, color coordinate (CIE), and lifespan of the organic light-emitting device manufactured according to the present invention are shown in Table 7 below.

compound threshold voltage
(V _on ) driving voltage
(V _op ) Luminous efficiency
(cd/A) Color coordinates
(x, y) life span
(T ₉₀ ) Comparative Example 1 Ref. One 6.4 7.02 10.44 (0.686, 0.314) 52 Comparative Example 2 Ref. 2 6.51 7.22 10.12 (0.684, 0316) 59 Comparative Example 3 Ref. 3 6.38 7.14 11.81 (0.685, 0.315) 69 Comparative Example 4 Ref. 4 6.29 6.86 13.2 (0.683, 0.317) 68 Comparative Example 5 Ref. 5 6.24 6.74 14.26 (0.685, 0315) 78 Comparative Example 6 Ref. 6 6.28 6.94 13.83 (0.683, 0.317) 80 Comparative Example 7 Ref. 7 6.15 6.79 14.73 (0.683, 0.317) 88 Comparative Example 8 Ref. 8 6.23 6.63 15.87 (0.684, 0316) 75 Comparative Example 9 Ref. 9 6.15 6.78 14.73 (0.685, 0.315) 91 Comparative Example 10 Ref. 10 6.18 6.83 16.12 (0.683, 0.317) 82 Comparative Example 11 Ref. 11 6.21 6.69 15.73 (0.685, 0315) 99 Comparative Example 12 Ref. 12 6.17 6.73 16.87 (0.683, 0.317) 87 Comparative Example 13 Ref. 13 6.27 6.90 15.92 (0.683, 0.317) 79 Comparative Example 14 Ref. 14 6.34 6.72 14.88 (0.685, 0315) 68 Comparative Example 15 Ref. 15 6.40 6.83 15.27 (0.683, 0.317) 81 Example 1 1-1 5.4 6.19 21.18 (0.684, 0.316) 158 Example 2 1-2 5.62 6.24 22.41 (0.685, 0.315) 178 Example 3 1-5 5.57 6.14 22.48 (0.685, 0.315) 181 Example 4 1-7 5.56 6.09 21.92 (0.684, 0.316) 155 Example 5 1-15 5.51 6.24 22.27 (0.684, 0.316) 140 Example 6 1-20 5.61 6.33 23.21 (0.684, 0.316) 138 Example 7 1-24 5.43 6.17 23.27 (0.684, 0.316) 135 Example 8 1-34 5.41 6.22 22.82 (0.679, 0.321) 201 Example 9 1-50 5.49 6.32 22.54 (0.683, 0.317) 173 Example 10 1-56 5.59 6.24 22.94 (0.683, 0.317) 153 Example 11 1-67 5.48 6.21 21.84 (0.683, 0.317) 161 Example 12 1-80 5.45 6.19 22.13 (0.683, 0.317) 152 Example 13 1-87 5.57 6.11 23.24 (0.684, 0.316) 143 Example 14 1-88 5.46 6.28 21.17 (0.683, 0.317) 164 Example 15 1-90 5.41 6.22 22.17 (0.683, 0.317) 144 Example 16 1-93 5.52 6.31 23.77 (0.685, 0.315) 135 Example 17 1-96 5.48 6.27 22.24 (0.682, 0.317) 171 Example 18 1-99 5.42 6.15 21.54 (0.682, 0.317) 151 Example 19 1-100 5.58 6.33 23.27 (0.682, 0.318) 124 Example 20 1-145 5.51 6.24 22.12 (0.682, 0.318) 148 Example 21 1-149 5.60 6.18 22.98 (0.684, 0.316) 131 Example 22 1-157 5.54 6.24 23.11 (0.683, 0.317) 197 Example 23 1-160 5.48 6.31 23.24 (0.682, 0.318) 124 Example 24 2-3 5.69 6.22 22.12 (0.681, 0.319) 134 Example 25 2-15 5.52 6.17 21.75 (0.681, 0.319) 144 Example 26 2-18 5.71 6.34 23.21 (0.681, 0.319) 171 Example 27 2-20 5.69 6.18 24.18 (0.684, 0.316) 138 Example 28 2-31 5.59 6.28 23.87 (0.681, 0.319) 219 Example 29 2-44 5.62 6.38 22.81 (0.681, 0.319) 157 Example 30 2-49 5.58 6.41 23.45 (0.681, 0.319) 182 Example 31 2-66 5.71 6.29 20.81 (0.681, 0.319) 167 Example 32 2-73 5.68 6.33 23.15 (0.681, 0.319) 184 Example 33 2-88 5.73 6.35 23.00 (0.681, 0.319) 175 Example 34 2-98 5.66 6.29 24.83 (0.684, 0.316) 145 Example 35 2-100 5.75 6.41 21.75 (0.681, 0.319) 146 Example 36 2-108 5.61 6.21 22.71 (0.681, 0.319) 199 Example 37 2-111 5.81 6.24 22.85 (0.681, 0.319) 164 Example 38 2-123 5.73 6.50 22.79 (0.681, 0.319) 157 Example 39 3-5 5.68 6.23 23.45 (0.681, 0.319) 132 Example 40 3-17 5.78 6.71 22.19 (0.682, 0.318) 157 Example 41 3-20 5.71 6.45 23.04 (0.681, 0.319) 141 Example 42 3-27 5.69 6.23 22.75 (0.681, 0.319) 122 Example 43 3-49 5.64 6.36 22.91 (0.682, 0.318) 147 Example 44 3-64 5.67 6.32 22.99 (0.681, 0.319) 143 Example 45 3-67 5.51 6.24 22.58 (0.682, 0.318) 151 Example 46 3-77 5.62 6.33 22.34 (0.681, 0.319) 144 Example 47 3-87 5.68 6.47 23.18 (0.681, 0.319) 133 Example 48 3-88 5.63 6.30 23.53 (0.682, 0.318) 151 Example 49 3-92 5.34 6.63 21.91 (0.682, 0.318) 162 Example 50 3-99 5.68 6.18 22.54 (0.681, 0.319) 148 Example 51 3-100 5.57 6.42 22.81 (0.681, 0.319) 150 Example 52 3-132 5.74 6.27 23.08 (0.684, 0.316) 221 Example 53 3-141 5.69 6.37 23.12 (0.684, 0.316) 144 Example 54 4-8 5.74 6.31 24.3 (0.684, 0.316) 133 Example 55 4-15 5.51 6.45 22.18 (0.684, 0.316) 119 Example 56 4-19 5.68 6.89 23.35 (0.684, 0.316) 127 Example 57 4-23 5.73 6.35 22.91 (0.684, 0.316) 140 Example 58 4-49 5.85 6.61 23.0 (0.685, 0.315) 125 Example 59 4-53 5.69 6.33 22.71 (0.681, 0.319) 145 Example 60 4-65 5.71 6.34 22.40 (0.685, 0.315) 103 Example 61 4-80 5.66 6.43 24.11 (0.684, 0.316) 131 Example 62 4-87 5.70 6.22 23.61 (0.684, 0.316) 127 Example 63 4-88 5.63 6.46 22.53 (0.681, 0.319) 130 Example 64 4-89 5.68 6.28 23.82 (0.684, 0.316) 141 Example 65 4-99 5.59 6.39 22.71 (0.685, 0.315) 128 Example 66 4-108 5.72 6.31 23.24 (0.683, 0.317) 137 Example 67 4-112 5.78 6.19 21.48 (0.684, 0.316) 153

From the results in Table 7, the organic light-emitting devices of Examples 1 to 32, which used the compound having the bipolar characteristic of the present invention as the light-emitting layer of the organic light-emitting device, had a lower driving voltage than the organic light-emitting devices of Comparative Examples 1 to 12. It was confirmed that this was low, and the luminous efficiency and lifespan were significantly improved. The compound of the present invention can lower the driving voltage at which electrons and holes are injected through a donor with good hole transport ability and an acceptor with good electron transport ability, and can improve efficiency and lifespan through the formation of an effective recombination zone (RZ). there is.

It was confirmed that the organic light emitting devices of Examples 2, 11, 19, 27, 39, and 59 of Table 7 had significantly improved luminous efficiency and device life compared to the organic light emitting devices of Comparative Examples 1, 2, 13, and 15. . The compound of the present invention can easily control the HOMO and LUMO energy levels by introducing various substituents into the core portion, thereby enabling effective electron and hole transfer. Due to the above effect, RZ formation can be easily controlled, and through this, exciton generation efficiency is increased, thereby improving luminous efficiency and device lifespan when driving the device.

The organic light-emitting devices of Examples 1, 3, 7, 13, 28, 33, 40, 42, 47, 54, 57, and 60 in Table 7 were added to the organic light-emitting devices of Comparative Examples 8, 9, 10, 11, and 12. Compared to this, it was confirmed that the luminous efficiency and device lifespan were significantly improved. By applying a naphthyl group with high hole mobility to the carbazole core, stability and mobility for holes can be increased, and by introducing -(L1)m-Ar1 with high electron stability and mobility, hole and mobility Electron flow can occur well.

In addition, benzo[b]carbazole, which uses a naphthyl group in a linear structure, shows high stability and efficiency when driving the device through structural stability. And in the case of benzo[a]carbazoleco, the light emission and driving of the device can be improved due to steric hindrance with -(L1)m-Ar1.

The organic light-emitting devices of Examples 4, 8, 10, 21, 31, 41, 46, and 55 of Table 7 showed significantly improved luminous efficiency and device lifespan compared to the organic light-emitting devices of Comparative Examples 4, 5, 6, and 14. I was able to confirm. Higher electron mobility is achieved by applying a three-ring pyrimidine or pyrazine functional group with S or O rather than an aryl or two-ring quinazoline or quinoxaline functional group, which are functional groups used to increase electron mobility (i.e., -(L1)m-Ar1). It forms an effective flow of electrons through its stability and mobility, and this allows the entire molecule to exhibit stronger bipolar characteristics. The bipolar phenomenon increases the stability and mobility of electrons and holes within one molecule, thereby effectively forming RZ.

As can be seen from the above device evaluation, it was confirmed that when the compound corresponding to the above invention was used as a light-emitting layer of an organic light-emitting device, it showed an excellent increase in lifespan characteristics compared to a compound not substituted with deuterium. When hydrogen is replaced with deuterium, the mass increases by two times. At this time, it has a lower vibrational energy than hydrogen, thereby lowering the energy of the molecule and stabilizing it. Therefore, since the bond dissociation energy is greater for the carbon-deuterium bond than for the carbon-hydrogen bond, the molecular structure can be considered more stable when substituted with deuterium, which is believed to affect lifespan.

<Experimental Example 2> - Production of organic light emitting device

(1) Manufacturing of organic light emitting devices

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

As a hole injection layer, which is a common layer on the ITO transparent electrode (anode), 4,4',4''-tris[2-naphthyl(phenyl)amino] triphenylamine (4,4',4''-Tris[ 2-naphthyl(phenyl)amino] triphenylamine: 2-TNATA) was deposited, and N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl) was deposited as a hole transport layer. )-4,4'-diamine (N,N'-di(1-naphthyl)-N,N'-diphenyl-(1,1'-biphenyl)-4,4'-diamine: NPB) was deposited.

After forming the hole injection layer and the hole transport layer in this way, a light-emitting layer was thermally vacuum deposited thereon as follows. The light-emitting layer was deposited from one source with two compounds listed in Table 8 below as a red host, and (piq)2(Ir)(acac) was used as a red phosphorescent dopant to the host. was doped with 3 wt% and deposited to a thickness of 400 Å.

Afterwards, Bathophenanthroline (Bphen) was deposited to a thickness of 30Å as a hole blocking layer, and tris(8-hydroxyquinolinato)aluminium (Alq3) was deposited on top of it as an electron transport layer. It was deposited to a thickness of 250Å.

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. An organic light emitting device was manufactured.

Meanwhile, all organic compounds required for the production of organic light-emitting devices were purified by vacuum sublimation under 10 ^-6 to 10 ^-8 torr for each material and used in the production of organic light-emitting devices.

(2) Driving voltage and luminous efficiency of organic light-emitting devices

The electroluminescence (EL) characteristics of the organic light-emitting device manufactured as described above were measured using the M7000 from MacScience, and the standard luminance was measured to be 6,000 cd using the lifespan measurement equipment (M6000) manufactured by MacScience using the measurement results. When /m ² , T90 was measured. Table 8 shows the results of measuring the driving voltage, luminous efficiency, color coordinate (CIE), and lifespan of the organic light-emitting device manufactured according to the present invention. (The ratio of P and N refers to the weight ratio)

compound
(P:N) ratio
(P:N) threshold voltage
(V _on ) driving voltage
(V _op ) efficiency
(cd/A) Color coordinates
(x, y) life span
(T ₉₀ ) Comparative Example 16 Ref. 1:5-1 1:1 5.32 6.37 20.71 (0.683, 0.315) 184 Comparative Example 17 Ref. 3:5-3 1:1 5.11 6.20 21.91 (0.682, 0.316) 191 Comparative Example 18 Ref. 4:5-1 1:1 5.20 6.13 20.33 (0.683, 0.315) 182 Comparative Example 19 Ref. 6:5-3 1:1 5.13 6.18 21.99 (0.680, 0.317) 185 Comparative Example 20 Ref. 8:5-24 1:1 5.26 6.21 22.81 (0.681, 0.317) 203 Comparative Example 21 Ref. 11:5-35 1:1 5.20 6.12 23.03 (0.681, 0.318) 198 Comparative Example 22 Ref. 13:5-8 1:1 5.17 6.21 23.88 (0.681, 0.317) 224 Comparative Example 23 Ref. 3:5-45 1:1 5.18 6.17 21.81 (0.681, 0.317) 208 Comparative Example 24 Ref. 4:5-24 1:1 5.34 6.02 22.14 (0.681, 0.318) 198 Comparative Example 25 Ref. 6:5-35 1:1 5.23 6.02 22.08 (0.681, 0.318) 193 Comparative Example 26 Ref. 8:5-35 1:1 5.20 6.12 23.03 (0.681, 0.318) 188 Comparative Example 27 Ref. 11:5-45 1:1 5.18 6.17 24.81 (0.681, 0.317) 213 Comparative Example 28 Ref. 15:5-78 1:1 5.21 6.24 24.27 (0.681, 0.317) 207 Example 68 1-2:5-3 3:1 4.59 5.12 32.02 (0.681, 0.318) 402 Example 34 2:1 4.47 4.99 33.1 (0.681, 0.318) 398 Example 35 1:1 4.27 4.88 31.5 (0.683, 0.316) 330 Example 36 1:2 4.14 4.36 35.16 (0.681, 0.316) 442 Example 37 1:3 3.98 4.17 32.43 (0.680, 0.318) 484 Example 38 1-87:5-45 3:1 4.59 4.88 33.02 (0.681, 0.318) 413 Example 39 2:1 4.37 4.69 36.8 (0.681, 0.318) 421 Example 40 1:1 4.21 4.67 32.4 (0.683, 0.316) 322 Example 41 1:2 4.04 4.26 39.16 (0.681, 0.316) 452 Example 42 1:3 3.88 4.08 36.43 (0.680, 0.318) 464 Example 43 1-2:5-1 1:1 4.38 4.98 30.5 (0.683, 0.316) 310 Example 44 1-7:5-27 1:1 4.17 4.58 31.5 (0.681, 0.319) 332 Example 45 1-34:5-35 1:1 4.25 4.61 32.1 (0.684, 0.316) 421 Example 46 1-87:5-38 1:1 4.17 4.77 32.8 (0.684, 0.316) 341 Example 47 1-149:5-1 1:1 4.27 4.79 31.9 (0.684, 0.316) 328 Example 48 2-20:5-24 1:1 4.29 4.81 33.5 (0.681, 0.319) 310 Example 49 2-98:5-8 1:1 4.35 4.77 32.4 (0.685, 0.315) 399 Example 50 3-49:5-24 1:1 4.11 4.89 32.2 (0.684, 0.316) 338 Example 52 3-132:5-1 1:1 4.20 4.81 30.9 (0.683, 0.317) 316 Example 53 4-8:5-35 1:1 4.34 4.78 32.6 (0.684, 0.316) 301 Example 54 4-89:5-24 1:1 4.14 4.91 33.4 (0.684, 0.316) 385 Example 55 1-7:5-27 1:1 4.25 4.85 31.1 (0.681, 0.319) 361 Example 56 1-157:5-35 1:1 4.24 4.81 34.1 (0.681, 0.319) 471 Example 57 1-160:5-38 1:1 4.31 4.90 32.8 (0.682, 0.318) 378 Example 58 2-31:5-45 1:1 4.19 4.85 32.2 (0.681, 0.319) 421 Example 59 3-5:5-54 1:1 4.28 4.98 33.8 (0.684, 0.316) 389 Example 60 4-53:5-74 1:1 4.39 4.87 31.1 (0.684, 0.316) 381 Example 61 4-108:5-24 1:1 4.11 4.97 33.9 (0.684, 0.316) 490 Example 62 1-56:5-35 1:1 4.26 4.75 30.9 (0.681, 0.319) 386 Example 63 1-67:5-54 1:1 4.35 4.80 32.4 (0.684, 0.316) 377

From the results in Table 8, when the compound of the present invention is used as a bipolar host and deposited by mixing with an N host, the driving voltage, luminous efficiency, and lifespan are superior to those of an organic light-emitting device containing a host compound composed of a conventional single compound. This improvement was confirmed.

The heterocyclic compound of Formula 1 of the present invention is a bipolar host with good hole and electron transport ability and is used as a P type host, and the compound of Formula 2 is used as an N type host to effectively balance the charge in the device. In addition, it can be expected that the exiplex phenomenon of the bipolar P type host + N type host compound will appear.

The exciplex phenomenon is a phenomenon in which energy of the size of the donor's HOMO and the acceptor's LUMO is released through electron exchange between two molecules. An exciplex phenomenon occurs between two molecules, resulting in Reverse Intersystem Crossing (RISC), which can increase the internal quantum efficiency of fluorescence to 100% and facilitate electronic transfer from the host to the dopant.

Through this, when the two molecules are combined in an appropriate ratio, effective RZ can be formed and can help improve the driving voltage, emission efficiency, and lifespan when driving the device.

In addition, the light-emitting host composed of multiple types of compounds of the present invention was deposited by pre-mixing the compounds, forming a single deposition source, and using a thermal vacuum deposition method. At this time, since multiple depositions are not performed, the uniformity and characteristics of the thin film can be improved, the process process can be simplified, costs can be reduced, and organic light-emitting devices with improved driving voltage, luminous efficiency, and lifespan can be formed. there is.

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 (15)

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

In Formula 1,
R1 to R5 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; 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 C1 to C60 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; Substituted or unsubstituted phosphine oxide group; and two or more groups selected from the group consisting of a substituted or unsubstituted amine group, or two or more groups adjacent to each other are combined with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring,
X is O; S; NRa or CRbRc,
L1 and L2 are the same or different from each other and are each independently directly bonded; Substituted or unsubstituted C6 to C60 arylene group; Or a substituted or unsubstituted C2 to C60 heteroarylene group,
Ra, Rb and Rc are the same or different from each other and are each independently 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,
m and n are the same or different from each other and are each independently an integer from 0 to 4,
a is an integer from 0 to 5,
b is an integer from 0 to 2,
c is an integer from 0 to 7,
When m, n and a to c are 2 or more, the substituents in parentheses are the same or different from each other,
The Ar1 is represented by the following formula A,
[Formula A]

In Formula A,
Y is O; or S;,
X1 is CR11 or N; X2 is CR12 or N; X3 is CR13 or N; X4 is CR14 or N,
Two of X1 to X4 are N,
One of R11 to R14 is connected to L1 of Formula 1 above,
Substituents other than those connected to L1 of Formula 1 among R11 to R14; and R6 are each independently hydrogen; heavy hydrogen; halogen; 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 C1 to C60 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; Substituted or unsubstituted phosphine oxide group; And two or more groups selected from the group consisting of a substituted or unsubstituted amine group, or two or more groups adjacent to each other are combined with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring,
d is an integer from 0 to 4, and when d is 2 or more, the substituents in parentheses are the same or different from each other. The method according to claim 1, wherein the formula 1 is a heterocyclic compound represented by the following formula 3 or formula 4:
[Formula 3]

[Formula 4]

In Formula 3 and Formula 4,
The definition of the substituent is the same as that in Formula 1 above. The method according to claim 2, wherein Formula 3 is a heterocyclic compound represented by any one of the following Formulas 3-1 to 3-3:
[Formula 3-1]

[Formula 3-2]

[Formula 3-3]

In Formulas 3-1 to 3-3,
The definition of the substituent is the same as that in Formula 3 above. The method according to claim 2, wherein the formula 4 is a heterocyclic compound represented by any one of the following formulas 4-1 to 4-3:
[Formula 4-1]

[Formula 4-2]

[Formula 4-3]

In Formulas 4-1 to 4-3,
The definition of the substituent is the same as that in Formula 4 above. The method of claim 1, wherein the formula 1 is a heterocyclic compound represented by any one of the following formulas 1-1 to 1-4:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Formulas 1-1 to 1-4,
The definition of each substituent is the same as that in Formula 1 above,
means the position connected to L2 of Formula 1 above. The method according to claim 1, wherein the formula A is a heterocyclic compound represented by any one of the following formulas A-1 to A-3:
[Formula A-1]

[Formula A-2]

[Formula A-3]

In the above formulas A-1 to A-3,
One of R11 to R14 is connected to L1 of Formula 1 above,
The definitions of the remaining substituents are the same as those in Formula 1 above. 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 includes the heterocyclic compound according to any one of claims 1 to 7. Phosphorus organic light emitting device. The organic light-emitting device of claim 8, wherein the organic material layer containing the heterocyclic compound further includes a heterocyclic compound represented by the following formula (2):
[Formula 2]

In Formula 2,
Z is O; or S,
R1' to R8' are the same or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; 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 C1 to C60 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; Substituted or unsubstituted phosphine oxide group; and a substituted or unsubstituted amine group, or two or more groups adjacent to each other are combined with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring,
One of R1' to R8' is a substituted or unsubstituted C2 to C60 heteroaryl group containing N. The organic light-emitting device of claim 9, wherein the heterocyclic compound represented by Formula 2 is represented by any one of the following compounds:



The organic light-emitting device of claim 8, wherein the organic material layer includes a light-emitting layer, and the light-emitting layer includes the heterocyclic compound. The organic light-emitting device of claim 8, wherein the organic material layer includes a light-emitting layer, the light-emitting layer includes a host material, and the host material includes the heterocyclic compound. The method according to claim 8, wherein the organic light emitting device comprises a light emitting layer, a hole injection layer, and a hole transport layer. An organic light emitting device further comprising one or two layers selected from the group consisting of an electron injection layer, an electron transport layer, an electron blocking layer, and a hole blocking layer. A heterocyclic compound according to any one of claims 1 to 7; and a composition for an organic material layer of an organic light-emitting device comprising a heterocyclic compound represented by the following formula (2):
[Formula 2]

In Formula 2,
Z is O; or S,
R1' to R8' are the same or different from each other, and are each independently hydrogen; heavy hydrogen; halogen; 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 C1 to C60 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; Substituted or unsubstituted phosphine oxide group; and two or more groups selected from the group consisting of a substituted or unsubstituted amine group, or two or more groups adjacent to each other are combined with each other to form a substituted or unsubstituted aliphatic or aromatic hydrocarbon ring or a substituted or unsubstituted hetero ring,
One of R1' to R8' is a substituted or unsubstituted C2 to C60 heteroaryl group containing N. The composition for an organic material layer of an organic light-emitting device according to claim 14, wherein the weight ratio of the heterocyclic compound to the heterocyclic compound represented by Formula 2 in the composition is 1:10 to 10:1.