KR102605828B1 - Hetero-cyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

This specification relates to heterocyclic compounds and organic light-emitting devices containing the same.

Description

Heterocyclic compound and organic light-emitting device containing the same {HETERO-CYCLIC COMPOUND AND ORGANIC LIGHT EMITTING DEVICE COMPRISING THE SAME}

This specification relates to heterocyclic compounds and organic light-emitting devices containing the same.

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

Most of the materials used in organic light-emitting devices are pure organic materials or complexes of organic materials and metals. Depending on the application, hole injection materials, hole transport materials, light-emitting materials, electron transport materials, electron injection materials, etc. It can be divided into: Here, organic materials with p-type properties, that is, organic materials that are easily oxidized and have an electrochemically stable state upon oxidation, are mainly used as hole injection materials or hole transport materials. Meanwhile, organic materials with n-type properties, that is, organic materials that are easily reduced and have an electrochemically stable state upon reduction, are mainly used as electron injection materials or electron transport materials. The emitting layer material is preferably a material that has both p-type and n-type properties, that is, a material that is stable in both oxidation and reduction states, and excitons are formed when holes and electrons recombine in the emitting layer. A material with high luminous efficiency that converts light into light is desirable.

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

Korean Patent Publication No. 2016-132822

The present specification provides heterocyclic compounds and organic light-emitting devices containing the same.

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

[Formula 1]

In Formula 1,

Z is O or S,

R1 and R2 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

R3 to R6 are each independently hydrogen or combined with each other to form a hydrocarbon ring,

L is a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,

a is an integer from 1 to 3, and when a is 2 or more, 2 or more Ls are the same or different from each other,

b is an integer from 1 to 4, and if b is 2 or more, the structures in parentheses are the same or different,

Ar1 is any one selected from the group consisting of:

In the above structure,

is the part connected to L,

c is an integer from 1 to 5, and when c is 2 or more, 2 or more G15 are the same or different from each other,

d is an integer from 1 to 4, and when d is 2 or more, 2 or more G16 are the same or different from each other,

X1 to X4 are the same or different from each other and are each independently N or CR10, provided that at least two of X1 to

R10 and G1 to G16 are the same or different from each other and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or it is a substituted or unsubstituted heterocyclic group.

Another embodiment of the present specification includes a first electrode; a second electrode provided opposite to the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layers includes the heterocyclic compound.

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

1 to 4 illustrate an organic light emitting device according to an exemplary embodiment of the present specification.

Hereinafter, this specification will be described in more detail.

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

[Formula 1]

In Formula 1,

Z is O or S,

R1 and R2 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,

R3 to R6 are each independently hydrogen or combined with each other to form a hydrocarbon ring,

L is a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted divalent heterocyclic group,

a is an integer from 1 to 3, and when a is 2 or more, 2 or more Ls are the same or different from each other,

b is an integer from 1 to 4, and if b is 2 or more, the structures in parentheses are the same or different,

Ar1 is any one selected from the group consisting of:

In the above structure,

is the part connected to L,

c is an integer from 1 to 5, and when c is 2 or more, 2 or more G15 are the same or different from each other,

d is an integer from 1 to 4, and when d is 2 or more, 2 or more G16 are the same or different from each other,

X1 to X4 are the same or different from each other and are each independently N or CR10, provided that at least two of X1 to

R10 and G1 to G16 are the same or different from each other and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or it is a substituted or unsubstituted heterocyclic group.

The compound represented by Formula 1 of the present invention is polarized by including only one substituent in a xanthene group, thioxanthene group, benzoxanthene group, or benzothioxanthene group where Z is O or S. Accordingly, the dipole moment is improved and the lifespan is improved.

In addition, the compound represented by Formula 1 of the present invention includes a polycyclic aryl group as R1 and R2; Alternatively, polarization is improved by including a heterocyclic group. In addition, the compound improves electron transfer characteristics by substituting Ar1 on one side of the xanthene group, thereby improving the efficiency of the organic light-emitting device.

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, when a member is said to be located “on” another member, this includes not only the case where a member is in contact with another member, but also the case where another member exists between the two members.

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

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.

As used herein, the term “substituted or unsubstituted” refers to deuterium; halogen group; Cyano group (-CN); ester group; imide group; Amine group; Alkoxy group; Alkyl group; Cycloalkyl group; Aryl group; and a heterocyclic group, or is substituted with a substituent in which two or more of the above-exemplified substituents are linked, or does not have any substituent. For example, “a substituent group in which two or more substituents are connected” may be a biphenyl group. That is, the biphenyl group may be an aryl group, or it may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the alkyl group may be straight chain or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples include methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl. , isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, etc., but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 50 carbon atoms, for example, 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto.

If the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable to have 10 to 30 carbon atoms. Specifically, the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthrene group, triphenylene group, pyrene group, phenalenyl group, perylenyl group, chrysenyl group, fluorenyl group, fluoranthene group, etc. It is not limited to this.

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

When the fluorenyl group is substituted, , , and It can be etc. However, it is not limited to this.

In the present specification, the description of the aryl group described above may be referred to, except that the arylene group is divalent.

In the present specification, the heterocyclic group includes one or more non-carbon atoms and heteroatoms. Specifically, the heterocyclic group may include one or more atoms selected from the group consisting of O, N, S, and P. The number of carbon atoms is not particularly limited, but is preferably 1 to 50 carbon atoms, and more preferably 2 to 30 carbon atoms, and the heterocyclic group may be monocyclic or polycyclic. The heterocyclic group may be an aromatic ring, an aliphatic ring, or a condensed ring thereof. Examples of the heterocyclic group include thiophene group, furanyl group, pyrrole group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, Triazolyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolyl group, quinazolyl group, quinoxalyl group, phthalazinyl group, pyrido pyrimidyl group, pyrido pyrazinyl group, pyrazino pyrazinyl group, isoquinolyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, Examples include, but are not limited to, phenanthroline, isoxazolyl, thiadiazolyl, phenothiazinyl, and dibenzofuranyl.

In the present specification, the description of the heterocyclic group described above may be referred to, except that the divalent heterocyclic group is divalent.

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

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, and specifically includes cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but are limited thereto. That is not the case.

In the present specification, the hydrocarbon ring may be an aromatic, aliphatic, or a condensed ring of aromatic and aliphatic, and may be selected from examples of the cycloalkyl group or aryl group.

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 30 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n. -Hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, etc., but is not limited thereto.

In this specification, the amine group is -NH ₂ ; Alkylamine group; N-alkylarylamine group; Arylamine group; N-arylheteroarylamine group; It may be selected from the group consisting of N-alkylheteroarylamine group and heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 0 to 30. Specific examples of amine groups include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, and 9-methyl-anthracenylamine group. , diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, N-phenylbiphenylamine group, N-phenylnaphthylamine group, N-bi Phenylnaphthylamine group, N-naphthylfluorenylamine group, N-phenylphenanthrenylamine group, N-biphenylphenanthrenylamine group, N-phenylfluorenylamine group, N-phenylterphenylamine group, N-phenanthrenylfluorenylamine group, N-biphenylfluorenylamine group, etc., but is not limited thereto.

In the present specification, N-alkylarylamine group refers to an amine group in which the N of the amine group is substituted with an alkyl group and an aryl group.

In the present specification, N-arylheteroarylamine group refers to an amine group in which an aryl group and a heteroaryl group are substituted at the N of the amine group.

In the present specification, N-alkylheteroarylamine group refers to an amine group in which the N of the amine group is substituted with an alkyl group and a heteroaryl group.

In this specification, the alkyl groups in the alkylamine group, N-arylalkylamine group, and N-alkylheteroarylamine group are the same as the examples of the alkyl groups described above.

In one embodiment of the present specification, L is a direct bond; A substituted or unsubstituted arylene group having 6 to 30 carbon atoms; Or it is a substituted or unsubstituted divalent heterocyclic group having 2 to 30 carbon atoms.

In one embodiment of the present specification, L is a direct bond; A substituted or unsubstituted monocyclic arylene group having 6 to 30 carbon atoms; A substituted or unsubstituted polycyclic arylene group having 10 to 30 carbon atoms; Or it is a substituted or unsubstituted divalent heterocyclic group having 2 to 30 carbon atoms.

In one embodiment of the present specification, L is a direct bond; A substituted or unsubstituted monocyclic arylene group having 6 to 30 carbon atoms; A substituted or unsubstituted polycyclic arylene group having 10 to 30 carbon atoms; Or it is a substituted or unsubstituted divalent N-containing heterocyclic group having 2 to 30 carbon atoms.

In one embodiment of the present specification, L is a direct bond; Substituted or unsubstituted phenylene group; Substituted or unsubstituted biphenylene group; Substituted or unsubstituted naphthylene group; Or it is a substituted or unsubstituted divalent pyridine group.

In one embodiment of the present specification, L is a direct bond; An arylene group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, cyano group, alkyl group, and aryl group; or direct combination; It is a divalent heterocyclic group substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, cyano group, alkyl group, and aryl group.

In one embodiment of the present specification, L is a direct bond; An arylene group having 6 to 30 carbon atoms substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, cyano group, alkyl group, and aryl group; or a divalent heterocyclic group having 2 to 30 carbon atoms substituted or unsubstituted with one or more substituents selected from the group consisting of deuterium, cyano group, alkyl group, and aryl group.

In one embodiment of the present specification, L is a direct bond; A phenylene group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, cyano group, alkyl group, and aryl group; A biphenylene group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, cyano group, alkyl group, and aryl group; A naphthylene group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, cyano group, alkyl group, and aryl group; or a divalent pyridine group unsubstituted or substituted with one or more substituents selected from the group consisting of deuterium, cyano group, alkyl group, and aryl group.

In one embodiment of the present specification, L is a direct bond; Arylene group substituted or unsubstituted with deuterium, cyano group, alkyl group, or aryl group; It is a divalent heterocyclic group substituted or unsubstituted with deuterium, cyano group, alkyl group, or aryl group.

In one embodiment of the present specification, L is a direct bond; A phenylene group substituted or unsubstituted with deuterium, cyano group, alkyl group, or aryl group; Biphenylene group substituted or unsubstituted with deuterium, cyano group, alkyl group, or aryl group; Naphthylene group substituted or unsubstituted with deuterium, cyano group, alkyl group, or aryl group; or a divalent pyridine group substituted or unsubstituted with deuterium, cyano group, alkyl group, or aryl group.

In one embodiment of the present specification, L is a direct bond; A phenylene group substituted or unsubstituted with a cyano group or an alkyl group; Biphenylene group substituted or unsubstituted with a cyano group or an alkyl group; Naphthylene group substituted or unsubstituted with a cyano group or an alkyl group; Or it is a divalent pyridine group substituted or unsubstituted with a cyano group or an alkyl group.

In one embodiment of the present specification, L is a direct bond; phenylene group; A biphenylene group substituted or unsubstituted with a cyano group; naphthylene group; Or it is a divalent pyridine group.

In an exemplary embodiment of the present specification, R1 and R2 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or it is a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

In an exemplary embodiment of the present specification, R1 and R2 are the same as or different from each other, and are each independently a substituted or unsubstituted monocyclic aryl group having 6 to 30 carbon atoms; A substituted or unsubstituted polycyclic aryl group having 10 to 30 carbon atoms; Or it is a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

In an exemplary embodiment of the present specification, R1 and R2 are the same as or different from each other, and are each independently a substituted or unsubstituted monocyclic aryl group having 6 to 30 carbon atoms; A substituted or unsubstituted polycyclic aryl group having 10 to 30 carbon atoms; Or it is a substituted or unsubstituted N-containing heterocyclic group having 2 to 30 carbon atoms.

In an exemplary embodiment of the present specification, R1 and R2 are the same as or different from each other, and are each independently a monocyclic aryl group having 6 to 30 carbon atoms; A polycyclic aryl group having 10 to 30 carbon atoms; Or it is an N-containing heterocyclic group having 2 to 30 carbon atoms.

In an exemplary embodiment of the present specification, R1 and R2 are the same as or different from each other, and are each independently a substituted or unsubstituted phenyl group; Substituted or unsubstituted naphthyl group; Or a substituted or unsubstituted pyridine group.

In an exemplary embodiment of the present specification, R1 and R2 are the same as or different from each other, and are each independently a phenyl group; naphthyl group; Or it is a pyridine group.

In one embodiment of the present specification, Ar1 is any one of the following structures.

In the above structure,

is the part connected to L,

c is an integer from 1 to 5, and when c is 2 or more, 2 or more G15 are the same or different from each other,

d is an integer from 1 to 4, and when d is 2 or more, 2 or more G16 are the same or different from each other,

X1 to X4 are the same or different from each other and are each independently N or CR10, provided that at least two of X1 to

R10 and G1 to G16 are the same or different from each other and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or it is a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, Ar1 is any one of the following structures.

In the above structure, c, d, X1 to X4 and G1 to G16 are the same as described above.

In an exemplary embodiment of the present specification, two of X1 to X4 are N, the other two are CR10, and R10 is hydrogen; heavy hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or it is a substituted or unsubstituted heterocyclic group.

In an exemplary embodiment of the present specification, two of X1 to X4 are N, the other two are CR10, and R10 is hydrogen.

In an exemplary embodiment of the present specification, X2 and X3 are N, X1 and X4 are CR10, and R10 is hydrogen; heavy hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or it is a substituted or unsubstituted heterocyclic group.

In an exemplary embodiment of the present specification, X2 and X3 are N, X1 and X4 are CR10, and R10 is hydrogen.

In an exemplary embodiment of the present specification, G1 to G16 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or it is a substituted or unsubstituted heterocyclic group.

In an exemplary embodiment of the present specification, G1 to G16 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or it is a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

In an exemplary embodiment of the present specification, G1 to G16 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; Or it is a substituted or unsubstituted aryl group.

In an exemplary embodiment of the present specification, G1 to G16 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; Or it is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, G1 to G16 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; Or, it is an aryl group unsubstituted or substituted with deuterium, cyano group, alkyl group, aryl group, or heterocyclic group.

In an exemplary embodiment of the present specification, G1 to G16 are the same as or different from each other, and are each independently hydrogen; heavy hydrogen; Substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Substituted or unsubstituted naphthyl group; Substituted or unsubstituted fluoranthene group; Substituted or unsubstituted dibenzothiophene group; Or a substituted or unsubstituted dibenzofuran group.

In an exemplary embodiment of the present specification, G1 to G16 are the same as or different from each other, and are each independently hydrogen; Or a substituted or unsubstituted phenyl group.

In an exemplary embodiment of the present specification, G1 to G16 are the same as or different from each other, and are each independently hydrogen; Or it is a phenyl group substituted or unsubstituted with a cyano group or a pyridine group.

In one embodiment of the present specification, b is an integer of 1 to 3.

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

In one embodiment of the present specification, Formula 1 is 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,

Z, R1, R2, a, L and Ar1 are the same as defined in Formula 1 above.

In one embodiment of the present specification, Formula 1 is represented by Formula 1-1.

In an exemplary embodiment of the present specification, Formula 1 is represented by Formula 1-2.

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

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

In an exemplary embodiment of the present specification, Formula 1 is represented by any one of the following Formulas 1-5 to 1-7.

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

In Formulas 1-5 to 1-7,

Z, R1 to R6, L, a, b, and Ar1 are the same as defined in Formula 1 above.

In one embodiment of the present specification, Formula 1 is represented by Formula 1-5.

In one embodiment of the present specification, Formula 1 is represented by Formula 1-6.

In one embodiment of the present specification, Formula 1 is represented by Formula 1-7.

In an exemplary embodiment of the present specification, the heterocyclic compound of Formula 1 has any one of the following structures.

The core structure of Chemical Formula 1 according to an embodiment of the present specification can be prepared as shown in the following reaction scheme, substituents can be combined by methods known in the art, and the type, position, or number of substituents are known in the art. It may be changed according to known technology.

<Reaction formula>

In the above reaction formula,

Z, L, a, R1 to R6, Ar1 and b are the same as defined in Formula 1,

A is Cl or Br.

An exemplary embodiment of the present specification includes a first electrode; a second electrode provided opposite to the first electrode; and an organic light-emitting device including one or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include the heterocyclic compound described above.

The organic light-emitting device of the present specification is manufactured using manufacturing methods and materials known in the art, except that at least one layer of the organic material layer contains the heterocyclic compound of the present specification, that is, the heterocyclic compound represented by Formula 1 above. can be manufactured.

For example, the organic light emitting device of the present specification can be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, a metal or a conductive metal oxide or an alloy thereof is deposited on the substrate using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. It can be manufactured by forming a first electrode, forming an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, and an electron transport layer thereon, and then depositing a material that can be used as a second electrode thereon. In addition to this method, an organic light-emitting device can be made by sequentially depositing the second electrode material, the organic material layer, and the first electrode material on the substrate. In addition, the heterocyclic compound represented by Formula 1 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, doctor blading, inkjet printing, screen printing, spraying, roll coating, etc., but is not limited to these.

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

The organic material layer may have a multi-layer structure including a hole injection layer, a hole transport layer, a layer that simultaneously performs hole injection and hole transport, an electron suppression layer, a light emitting layer and an electron transport layer, an electron injection layer, and a layer that performs both electron injection and electron transport. However, it is not limited to this and may have a single-layer structure. In addition, the organic material layer uses a variety of polymer materials to form a smaller number of layers by using a solvent process rather than a deposition method, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer. It can be manufactured in layers.

In one embodiment of the present specification, the organic material layer includes an electron injection layer, an electron transport layer, or a layer that simultaneously performs electron injection and electron transport, and the electron injection layer, the electron transport layer, or a layer that performs electron injection and electron transport simultaneously Includes the above heterocyclic compounds.

In one embodiment of the present specification, the organic material layer includes a hole blocking layer, and the hole blocking layer includes the heterocyclic compound.

According to an exemplary embodiment of the present specification, the organic material layer may further include one or more layers selected from the group consisting of a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, and an electron injection layer.

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

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

For example, the structure of the organic light emitting device of this specification may have the same structure as shown in FIGS. 1 to 4, but is not limited thereto.

Figure 1 illustrates the structure of an organic light-emitting device 10 in which a first electrode 2, a light-emitting layer 3, and a second electrode 4 are sequentially stacked on a substrate 1. 1 is an exemplary structure of an organic light-emitting device according to an exemplary embodiment of the present specification, and may further include another organic material layer.

2 shows a first electrode 2, a hole injection layer 5, a hole transport layer 6, a light emitting layer 3, an electron transport layer 7, an electron injection layer 8, and a second electrode ( 4) The structure of this sequentially stacked organic light emitting device is illustrated. 2 is an exemplary structure according to an embodiment of the present specification, and may further include another organic material layer.

In Figure 3, the first electrode 2, the hole injection layer 5, the first hole transport layer 6-1, the second hole transport layer 6-2, the light emitting layer 3, the electron injection and The structure of an organic light emitting device in which the transport layer 9 and the second electrode 4 are sequentially stacked is illustrated. 3 is an exemplary structure according to an embodiment of the present specification, and may further include another organic material layer.

4 shows a first electrode 2, a hole injection layer 5, a first hole transport layer 6-1, a second hole transport layer 6-2, a light emitting layer 3, and a hole blocking layer on the substrate 1. (10). The structure of an organic light emitting device in which the electron injection and transport layer 9 and the second electrode 4 are sequentially stacked is illustrated. 4 is an exemplary structure according to an embodiment of the present specification, and may further include another organic material layer.

Specifically, the organic light emitting device may have a stacked structure, for example, as shown below, in addition to the structure specified in the drawings, but is not limited thereto.

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

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

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

(4) Anode/hole transport layer/light emitting layer/electron transport layer/cathode

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

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

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

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

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

(10) Anode/hole transport layer/electron suppression layer/light emitting layer/electron transport layer/cathode

(11) Anode/hole transport layer/electron suppression layer/light emitting layer/electron transport layer/electron injection layer/cathode

(12) Anode/hole injection layer/hole transport layer/electron suppression layer/light emitting layer/electron transport layer/cathode

(13) Anode/hole injection layer/hole transport layer/electron suppression layer/light-emitting layer/electron transport layer/electron injection layer/cathode

(14) Anode/hole transport layer/light emitting layer/hole suppression layer/electron transport layer/cathode

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

(16) Anode/hole injection layer/hole transport layer/light emitting layer/hole suppression layer/electron transport layer/cathode

(17) Anode/hole injection layer/hole transport layer/light-emitting layer/hole suppression layer/electron transport layer/electron injection layer/cathode

(18) Anode/hole injection layer/hole transport layer/electron suppression layer/light-emitting layer/hole suppression layer/electron transport layer/electron injection layer/cathode

In one embodiment of the present specification, the hole transport layer may have a multilayer structure. For example, it may be composed of a first hole transport layer and a second hole transport layer containing different materials.

The anode is an electrode that injects holes, and the anode material is generally preferably a material with a large work function to facilitate hole injection into the organic layer. Specific examples of anode materials that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, and gold, or alloys thereof; Metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide (IZO); Combinations of metals and oxides such as ZnO:Al or SnO ₂ :Sb; and conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited to these. .

The cathode is an electrode that injects electrons, and the cathode material is preferably a material with a low work function to facilitate electron injection into the organic layer. Specific examples of cathode materials include metals such as magnesium, calcium, sodium, potassium, titanium, indium, yttrium, lithium, gadolinium, aluminum, silver, tin and lead, or alloys thereof; There are multi-layer structure materials such as LiF/Al or LiO2/Al, but they are not limited to these.

The hole injection layer is a layer that serves to facilitate the injection of holes from the anode to the light emitting layer, and the hole injection material is a material that can well inject holes from the anode at a low voltage. HOMO (highest occupied) of the hole injection material It is preferable that the molecular orbital is between the work function of the anode material and the HOMO of the surrounding organic layer. Examples of hole injection materials include metal porphyrine, oligothiophene, arylamine-based organic substances, hexanitrilehexaazatriphenylene-based organic substances, quinacridone-based organic substances, and perylene-based organic substances. Organic materials, carbazole-based organic materials, fluorene-based organic materials, anthraquinone, and polyaniline- and polythiophene-based conductive polymers, etc., but are not limited to these. Specifically, the hole injection material may be a compound containing substituted or unsubstituted carbazole and substituted or unsubstituted fluorene, but is not limited thereto.

In one embodiment of the present specification, the thickness of the hole injection layer may be 1 nm to 150 nm. If the thickness of the hole injection layer is 1 nm or more, there is an advantage in preventing the hole injection characteristics from deteriorating, and if it is 150 nm or less, the thickness of the hole injection layer is so thick that the driving voltage is increased to improve the movement of holes. There is an advantage to preventing this.

The hole transport layer may play a role in facilitating the transport of holes. The hole transport material is a material that can transport holes from the anode or hole injection layer and transfer them to the light emitting layer, and a material with high mobility for holes is suitable. Examples of hole transport materials include arylamine-based organic materials, carbazole-based organic materials, quinoxaline-based organic materials, fluorene-based organic materials, conductive polymers, and block copolymers with both conjugated and non-conjugated portions. It is not limited to only. Specifically, the hole transport material includes quinoxazoline-based compounds and arylamine-based compounds, but is not limited thereto.

An additional hole buffer layer may be provided between the hole injection layer and the hole transport layer, and may include hole injection or transport materials known in the art.

An electron blocking layer may be provided between the hole transport layer and the light emitting layer. The electron blocking layer may be made of the above-mentioned compounds or materials known in the art.

The light-emitting layer may emit red, green, or blue light and may be made of a phosphorescent material or a fluorescent material. The light-emitting material is a material that can emit light in the visible range by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and is preferably a material with good quantum efficiency for fluorescence or phosphorescence. Specific examples include 8-hydroxy-quinoline aluminum complex (Alq ₃ ), carbazole-based compounds, dimerized styryl compounds, BAlq, 10-hydroxybenzoquinoline-metal compounds, benzoxazole-based compounds, and benzoxazole. Thiazole-based compounds, benzimidazole-based compounds, poly(p-phenylenevinylene) (PPV)-based polymers, spiro compounds, polyfluorene, and rubrene, but are not limited to these. no.

In one embodiment of the present specification, the light emitting layer includes a host and a dopant. The host may include the above-mentioned compounds, condensed aromatic ring derivatives, and heterocycle-containing compounds. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, and fluoranthene compounds, and heterocycle-containing compounds include carbazole derivatives, dibenzofuran derivatives, and ladder-type compounds. These include, but are not limited to, furan compounds and pyrimidine derivatives.

The dopants include PIQIr(acac)(bis(1-phenylsoquinoline)acetylacetonate iridium), PQIr(acac)(bis(1-phenylquinoline)acetylacetonate iridium), PQIr(tris(1-phenylquinoline)iridium), and PtOEP(octaethylporphyrin platinum). The same phosphorescent material or a fluorescent material such as Alq ₃ (tris(8-hydroxyquinolino)aluminum) may be used, but it is not limited to this. If the light-emitting layer emits green light, a phosphor such as Ir(ppy) ₃ (fac tris(2-phenylpyridine)iridium) or a fluorescent material such as Alq3 (tris(8-hydroxyquinolino)aluminum) can be used as the light-emitting dopant. However, it is not limited to this. If the light-emitting layer emits blue light, the light-emitting dopants include (4,6-F ₂ ppy) ₂ Irpic, spiro-DPVBi, spiro-6P, distylbenzene (DSB), distrylarylene (DSA), and PFO-based polymers. , PPV-based, pyrene-based, and arylamine-based compounds may be used, but are not limited to these.

In one embodiment of the present specification, a hole blocking layer may be provided between the electron transport layer and the light emitting layer, and materials known in the art may be used for the hole blocking layer.

The electron transport layer may play a role in facilitating the transport of electrons. The electron transport material is a material that can easily inject electrons from the cathode and transfer them to the light-emitting layer, and a material with high mobility for electrons is suitable. Specific examples include, but are not limited to, an Al complex of 8-hydroxyquinoline, a complex containing Alq ₃ , organic radical compounds, anthracene-based compounds, imidazole-based compounds, and hydroxyflavone-metal complexes. The thickness of the electron transport layer may be 1 nm to 50 nm. If the thickness of the electron transport layer is 1 nm or more, there is an advantage in preventing the electron transport characteristics from deteriorating, and if it is 50 nm or less, the thickness of the electron transport layer is too thick to prevent the driving voltage from increasing to improve the movement of electrons. There are benefits to this.

The electron injection layer may serve to facilitate injection of electrons. The electron injection material has the ability to transport electrons, has an excellent electron injection effect from the cathode, a light emitting layer or a light emitting material, prevents movement of excitons generated in the light emitting layer to the hole injection layer, and also has an excellent electron injection effect from the cathode to the light emitting layer or light emitting material. , Compounds with excellent thin film forming ability are preferred. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, anthracene, and imidazole. etc. and their derivatives; metal complex compounds; Nitrogen-containing 5-membered ring derivatives; and lithium quinolate (LiQ), but is not limited thereto.

In one embodiment of the present specification, the organic material layer containing the heterocyclic compound of Formula 1 is an electron injection layer, an electron transport layer, or a layer that performs electron injection and electron transport at the same time, and the electron injection layer, the electron transport layer, or the electron injection and The layer that simultaneously transports electrons further includes a metal complex.

In an exemplary embodiment of the present specification, examples of the metal complex include Al complex of 8-hydroxyquinoline (Alq ₃ ), LiQ, and metal complex compounds, but are not limited thereto.

Examples of the metal complex compounds include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, Tris(2-methyl-8-hydroxyquinolinato)aluminum, Tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato)beryllium, bis(10-hydroxybenzo[h]quinolinato)zinc, bis(2-methyl-8-quinolinato)chlorogallium, bis(2-methyl-8-quinolinato)( o-cresolato) gallium, bis(2-methyl-8-quinolinato)(1-naphtolato) aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato) gallium, etc. It is not limited to this.

In one embodiment of the present specification, the heterocyclic compound of Formula 1 and the metal complex may be included in the electron injection layer, the electron transport layer, or the layer that simultaneously performs electron injection and electron transport at a mass ratio of 0.5:1.5 to 1.5:0.5. .

The hole blocking layer is a layer that prevents holes from reaching the cathode, and can generally be formed under the same conditions as the hole injection layer. Specifically, it includes oxadiazole derivatives, triazole derivatives, phenanthroline derivatives, BCP, and aluminum complexes, but is not limited thereto.

An exemplary embodiment of the present specification includes a compound represented by Formula 1; and a metal complex.

The description of the metal complex included in the composition is the same as that described above for the electron injection layer, the electron transport layer, or the layer that performs both electron injection and electron transport.

In one embodiment of the present specification, the heterocyclic compound of Formula 1 and the metal complex in the composition may be included in a mass ratio of 0.5:1.5 to 1.5:0.5.

The organic light emitting device according to the present invention may be a front emitting type, a back emitting type, or a double-sided emitting type depending on the material used.

Hereinafter, in order to explain the present specification in detail, examples will be given in detail. However, the embodiments according to the present specification may be modified into various other forms, and the scope of the present specification is not to be construed as being limited to the embodiments described in detail below. The embodiments of this specification are provided to more completely explain the present specification to those with average knowledge in the art.

Manufacturing example 1-1: Preparation of compound E1

In a nitrogen atmosphere, E1-A (20 g, 43.4 mmol) and E1-B (10.5 g, 43.4 mmol) were added to 400 mL of tetrahydrofuran, stirred, and refluxed. Afterwards, potassium carbonate (18 g, 130.3 mmol) was dissolved in 18 mL of water, stirred sufficiently, and then tetrakistriphenyl-phosphinopalladium (1.5 g, 1.3 mmol) was added. After reacting for 2 hours, the mixture was cooled to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again dissolved in 468 mL of 20 times chloroform, washed twice with water, the organic layer was separated, anhydrous magnesium sulfate was added, stirred, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized with chloroform and ethyl acetate to prepare white solid compound E1 (18g, 77%, MS: [M+H]+ = 539).

Manufacturing example 1-2: Preparation of compound E2

Compound E2 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was used according to the above reaction scheme.

MS: [M+H] ⁺ = 589

Manufacturing example 1-3: Preparation of compound E3

Compound E3 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared according to the above reaction scheme.

MS: [M+H] ⁺ = 691

Manufacturing example 1-4: Preparation of compound E4

Compound E4 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared according to the above reaction scheme.

MS: [M+H] ⁺ = 639

Manufacturing example 1-5: Preparation of compound E5

Compound E5 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was used according to the above reaction scheme.

MS: [M+H] ⁺ = 641

Manufacturing example 1-6: Preparation of compound E6

Compound E6 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was used according to the above reaction formula.

MS: [M+H] ⁺ = 528

Manufacturing example 1-7: Preparation of compound E7

Compound E7 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared according to the above reaction scheme.

MS: [M+H] ⁺ = 566

Manufacturing example 1-8: Preparation of compound E8

Compound E8 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared according to the above reaction scheme.

MS: [M+H] ⁺ = 616

Manufacturing example 1-9: Preparation of compound E9

Compound E9 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared according to the above reaction scheme.

MS: [M+H] ⁺ = 614

Manufacturing example 1-10: Preparation of compound E10

Compound E10 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was used according to the above reaction scheme.

MS: [M+H] ⁺ = 616

Manufacturing example 1-11: Preparation of compound E11

Compound E11 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was used according to the above reaction scheme.

MS: [M+H] ⁺ = 589

Manufacturing example 1-12: Preparation of compound E12

Compound E12 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was used according to the above reaction scheme.

MS: [M+H] ⁺ = 563

Manufacturing example 1-13: Preparation of compound E13

Compound E13 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared according to the above reaction scheme.

MS: [M+H] ⁺ = 630

Manufacturing example 1-14: Preparation of compound E14

Compound E14 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was used according to the above reaction scheme.

MS: [M+H] ⁺ = 707

Manufacturing example 1-15: Preparation of compound E15

Compound E15 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared according to the above reaction scheme.

MS: [M+H] ⁺ = 733

Example 1-1.

A glass substrate coated with a thin film of ITO (indium tin oxide) with a thickness of 1000 Å was placed in distilled water with a detergent dissolved in it and washed with ultrasonic waves. At this time, a detergent from Fischer Co. was used, and distilled water filtered secondarily using a filter from Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, it was ultrasonic washed with solvents of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Additionally, the substrate was cleaned for 5 minutes using oxygen plasma and then transported to a vacuum evaporator.

On the ITO transparent electrode prepared in this way, the following HI-A compound was thermally vacuum deposited to a thickness of 600 Å to form a hole injection layer. On the hole injection layer, 50Å of the following HAT compound and 60Å of the following HT-A compound were sequentially vacuum deposited to form a first hole transport layer and a second hole transport layer.

Next, the following BH compound and BD compound were vacuum deposited on the second hole transport layer with a film thickness of 20 nm at a weight ratio of 25:1 to form a light emitting layer.

On the emitting layer, compound E1 prepared in Preparation Example 1-1 and the following LiQ compound were vacuum deposited at a weight ratio of 1:1 to form an electron injection and transport layer with a thickness of 350 Å. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 10 Å and aluminum to a thickness of 1000 Å on the electron injection and transport layer.

In the above process, the deposition rate of organic materials was maintained at 0.4 Å/sec to 0.9 Å/sec, the deposition rate of lithium fluoride of the cathode was maintained at 0.3 Å/sec, and aluminum was maintained at 2 Å/sec, and the vacuum level during deposition was An organic light emitting device was manufactured by maintaining 1×10 ^-7 torr to 5×10 ^-5 torr.

Example 1-2 to 1-15.

An organic light emitting device was manufactured in the same manner as in Example 1-1, except that compounds E2 to E15 shown in Table 1 below were used instead of compound E1 in Example 1-1.

Comparative example 1-1 to 1-13.

An organic light emitting device was manufactured in the same manner as in Example 1-1, except that compounds ET-A to ET-M shown in Table 1 below were used instead of compound E1 in Example 1-1.

For the organic light emitting devices manufactured in Examples 1-1 to 1-15 and Comparative Examples 1-1 to 1-13, the driving voltage and luminous efficiency were measured at a current density of 10 mA/cm ² and at a current density of 20 mA/cm ² The time (T90) for the current density to reach 90% of the initial luminance was measured. The results are shown in Table 1 below.

division compound Voltage
(V
@10 mA/cm ² ) efficiency
(cd/A
@10 mA/cm ² ) Color coordinates
(x, y) Lifespan (h)
T90 at
20 mA/cm ² ) Example 1-1 E1 4.44 4.85 (0.140, 0.092) 155 Example 1-2 E2 4.53 4.75 (0.140, 0.093) 175 Example 1-3 E3 4.48 5.00 (0.140, 0.093) 141 Example 1-4 E4 4.48 4.85 (0.141, 0.092) 159 Examples 1-5 E5 4.57 4.97 (0.140, 0.092) 143 Example 1-6 E6 4.57 4.66 (0.140, 0.093) 133 Example 1-7 E7 4.48 4.82 (0.140, 0.093) 161 Examples 1-8 E8 4.49 4.80 (0.141, 0.092) 180 Example 1-9 E9 4.66 4.61 (0.140, 0.092) 205 Examples 1-10 E10 4.48 4.95 (0.140, 0.093) 149 Example 1-11 E11 4.44 4.92 (0.140, 0.093) 154 Examples 1-12 E12 4.57 4.60 (0.140, 0.092) 125 Example 1-13 E13 4.71 4.66 (0.140, 0.093) 194 Example 1-14 E14 4.53 5.05 (0.140, 0.093) 138 Example 1-15 E15 4.53 4.92 (0.140, 0.092) 147 Comparative Example 1-1 ET-A 4.97 3.40 (0.140, 0.093) 110 Comparative Example 1-2 ET-B 5.21 3.14 (0.141, 0.092) 109 Comparative Example 1-3 ET-C 5.02 3.50 (0.140, 0.092) 100 Comparative Example 1-4 ET-D 5.02 3.49 (0.140, 0.093) 37 Comparative Example 1-5 ET-E 5.12 3.42 (0.140, 0.093) 44 Comparative Example 1-6 ET-F 5.07 3.60 (0.141, 0.092) 37 Comparative Example 1-7 ET-G 5.07 3.49 (0.140, 0.092) 41 Comparative Example 1-8 ET-H 4.58 4.42 (0.140, 0.093) 36 Comparative Example 1-9 ET-I 4.76 4.24 (0.140, 0.093) 41 Comparative Example 1-10 ET-J 4.57 4.55 (0.141, 0.092) 30 Comparative Example 1-11 ET-K 4.52 4.53 (0.141, 0.092) 31 Comparative Example 1-12 ET-L 4.67 4.42 (0.141, 0.092) 33 Comparative Example 1-13 ET-M 5.42 3.07 (0.141, 0.092) 86

As shown in Table 1, the compound represented by Formula 1 according to the present specification can be used in an organic material layer that simultaneously injects and transports electrons of an organic light-emitting device.

Comparing Examples 1-1 to 1-15 of Table 1 and Comparative Examples 1-1 and 1-3, in the organic light-emitting device using the heterocyclic compound of Formula 1 according to the present specification, the quinazoline group is substituted at a different position. It was confirmed that it showed significantly superior characteristics in terms of efficiency than the organic light emitting device using the compound applied.

Comparing Examples 1-1 to 1-15 of Table 1 and Comparative Examples 1-2 and 1-13, the organic light-emitting device using the heterocyclic compound of Formula 1 according to the present specification has substituents on both sides of the xanthene group. It was confirmed that it showed significantly better characteristics in terms of efficiency and lifespan than the organic light-emitting device using a compound containing.

Comparing Examples 1-1 to 1-15 and Comparative Examples 1-4 to 1-7 in Table 1, the organic light-emitting device using the heterocyclic compound of Formula 1 according to the present specification has a substituent with a different structure as Ar1. It was confirmed that it showed significantly superior characteristics in terms of efficiency and lifespan compared to organic light-emitting devices using substituted compounds.

Comparing Examples 1-1 to 1-15 and Comparative Examples 1-8 to 1-12 of Table 1, the organic light-emitting device using the heterocyclic compound of Formula 1 according to the present specification has R1 and R2 bonded to each other. It was confirmed that the organic light-emitting device exhibited significantly superior characteristics in terms of lifespan than an organic light-emitting device using a compound that formed an aromatic ring or substituted (L) _a -Ar1 on a fluorene group.

Example 2-1.

A glass substrate coated with a thin film of ITO (indium tin oxide) with a thickness of 1000 Å was placed in distilled water with a detergent dissolved in it and washed with ultrasonic waves. At this time, a detergent from Fischer Co. was used, and distilled water filtered secondarily using a filter from Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, it was ultrasonic washed with solvents of isopropyl alcohol, acetone, and methanol, dried, and then transported to a plasma cleaner. Additionally, the substrate was cleaned for 5 minutes using oxygen plasma and then transported to a vacuum evaporator.

On the ITO transparent electrode prepared in this way, the following HI-A compound was thermally vacuum deposited to a thickness of 600 Å to form a hole injection layer. On the hole injection layer, 50Å of the following HAT compound and 60Å of the following HT-A compound were sequentially vacuum deposited to form a first hole transport layer and a second hole transport layer.

Next, the following BH compound and BD compound were vacuum deposited on the second hole transport layer with a film thickness of 20 nm at a weight ratio of 25:1 to form a light emitting layer.

On the emitting layer, compound E1 prepared in Preparation Example 1-1 was vacuum deposited to a thickness of 50 Å to form a hole blocking layer, and ET-N and the following LiQ compound were vacuum deposited at a weight ratio of 1:1 to a thickness of 300 Å. An electron injection and transport layer was formed. A cathode was formed by sequentially depositing lithium fluoride (LiF) to a thickness of 10 Å and aluminum to a thickness of 1000 Å on the electron injection and transport layer.

In the above process, the deposition rate of organic matter was maintained at 0.4 Å/sec to 0.9 Å/sec, the deposition rate of lithium fluoride of the cathode was maintained at 0.3 Å/sec, and aluminum was maintained at 2 Å/sec, and the vacuum level during deposition was An organic light emitting device was manufactured by maintaining 1×10 ^-7 torr to 5×10 ^-5 torr.

Example 2-2 to 2-13.

An organic light-emitting device was manufactured in the same manner as in Example 2-1, except that compounds E2 to E8, E10 to E12, E14, and E15 shown in Table 2 below were used instead of compound E1 in Example 2-1. Manufactured.

Comparative example 2-1 to 2-11.

The same method as Example 2-1, except that compounds ET-A to ET-H and ET-J to ET-L shown in Table 2 below were used instead of compound E1 of Example 2-1, respectively. An organic light emitting device was manufactured.

For the organic light-emitting devices manufactured in Examples 2-1 to 2-13 and Comparative Examples 2-1 to 2-11, the driving voltage and luminous efficiency were measured at a current density of 10 mA/cm ² and at a current density of 20 mA/cm ² The time (T90) for the current density to reach 90% of the initial luminance was measured. The results are shown in Table 2 below.

division compound Voltage
(V
@10 mA/cm ² ) efficiency
(cd/A
@10 mA/cm ² ) Color coordinates
(x, y) Lifespan (h)
T90 at
20 mA/cm ² ) Example 2-1 E1 4.35 5.09 (0.140, 0.092) 126 Example 2-2 E2 4.44 4.99 (0.140, 0.093) 138 Example 2-3 E3 4.26 5.25 (0.140, 0.093) 114 Example 2-4 E4 4.39 5.09 (0.141, 0.092) 128 Example 2-5 E5 4.26 5.22 (0.140, 0.092) 108 Example 2-6 E6 4.48 4.89 (0.140, 0.093) 108 Example 2-7 E7 4.31 5.12 (0.140, 0.093) 122 Example 2-8 E8 4.40 5.04 (0.141, 0.092) 146 Example 2-9 E10 4.31 5.19 (0.140, 0.093) 121 Example 2-10 E11 4.14 5.17 (0.140, 0.093) 117 Example 2-11 E12 4.48 5.00 (0.140, 0.092) 95 Example 2-12 E14 4.31 5.30 (0.140, 0.093) 112 Example 2-13 E15 4.22 5.27 (0.140, 0.092) 103 Comparative Example 2-1 ET-A 4.87 3.56 (0.140, 0.093) 89 Comparative Example 2-2 ET-B 5.10 3.29 (0.141, 0.092) 61 Comparative Example 2-3 ET-C 4.78 3.67 (0.140, 0.092) 81 Comparative Example 2-4 ET-D 4.92 3.67 (0.140, 0.093) 30 Comparative Example 2-5 ET-E 5.02 3.59 (0.140, 0.093) 36 Comparative Example 2-6 ET-F 4.82 3.78 (0.141, 0.092) 30 Comparative Example 2-7 ET-G 4.97 3.67 (0.140, 0.092) 33 Comparative Example 2-8 ET-H 4.49 4.64 (0.140, 0.093) 29 Comparative Example 2-9 ET-J 4.39 4.78 (0.141, 0.092) 24 Comparative Example 2-10 ET-K 4.22 4.75 (0.141, 0.092) 23 Comparative Example 2-11 ET-L 4.57 4.64 (0.141, 0.092) 27

As shown in Table 2, the compound represented by Chemical Formula 1 according to the present specification can be used in an organic material layer that blocks holes in an organic light-emitting device.

Comparing Examples 2-1 to 2-13 of Table 2 and Comparative Examples 2-1 and 2-3, in the organic light-emitting device using the heterocyclic compound of Formula 1 according to the present specification, the quinazoline group is substituted at a different position. It was confirmed that the organic light-emitting device showed significantly superior characteristics in terms of efficiency than the organic light-emitting device using the compound applied.

Comparing Examples 2-1 to 2-13 of Table 2 and Comparative Example 2-2, the organic light-emitting device using the heterocyclic compound of Formula 1 according to the present specification is a compound in which both sides of the xanthene group contain substituents. It was confirmed that it showed significantly better characteristics in terms of efficiency and lifespan than the organic light-emitting device to which it was applied.

Comparing Examples 2-1 to 2-13 and Comparative Examples 2-4 to 2-7 in Table 2, the organic light-emitting device using the heterocyclic compound of Formula 1 according to the present specification has a substituent with a different structure as Ar1. It was confirmed that it showed significantly better properties in terms of efficiency and lifespan than organic light-emitting devices using substituted compounds.

Comparing Examples 2-1 to 2-13 and Comparative Examples 2-8 to 2-11 in Table 2, the organic light-emitting device using the heterocyclic compound of Formula 1 according to the present specification has R1 and R2 bonded to each other. It was confirmed that the organic light-emitting device exhibited significantly superior characteristics in terms of lifespan than an organic light-emitting device using a compound that formed an aromatic ring or substituted (L) _a -Ar1 on a fluorene group.

1: substrate
2: first electrode
3: Light-emitting layer
4: second electrode
5: Hole injection layer
6: Hole transport layer
6-1: First hole transport layer
6-2: Second hole transport layer
7: Electron transport layer
8: Electron injection layer
9: Electron injection and transport layer
10: Hole blocking layer

Claims (10)

Heterocyclic compound of formula 1:
[Formula 1]

In Formula 1,
Z is O or S,
R1 and R2 are the same or different from each other, and are each independently an aryl group having 6 to 30 carbon atoms; Or a pyridine group,
R3 to R6 are each independently hydrogen or combined with each other to form a hydrocarbon ring,
L is a direct bond; Arylene group substituted or unsubstituted with a cyano group; Or a divalent pyridine group,
a is an integer from 1 to 3, and when a is 2 or more, 2 or more Ls are the same or different from each other,
b is 1,
Ar1 is any one selected from the group consisting of:

In the above structure,
is the part connected to L,
c is an integer from 1 to 5, and when c is 2 or more, 2 or more G15 are the same or different from each other,
d is an integer from 1 to 4, and when d is 2 or more, 2 or more G16 are the same or different from each other,
X1 to X4 are the same or different from each other and are each independently N or CR10, provided that at least two of X1 to
R10 and G1 to G16 are the same or different from each other and are each independently hydrogen; It is an aryl group substituted or unsubstituted with one or more types selected from the group consisting of a cyano group and a pyridine group. In claim 1,
The L is a direct bond; phenylene group; A biphenylene group substituted or unsubstituted with a cyano group; naphthylene group; Or a heterocyclic compound that is a divalent pyridine group. In claim 1,
R1 and R2 are the same as or different from each other, and are each independently a phenyl group; naphthyl group; Or a heterocyclic compound that is a pyridine group. delete The method according to claim 1, wherein the formula 1 is a heterocyclic compound represented by any one of the following formulas 1-5 to 1-7:
[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

In Formulas 1-5 to 1-7,
Z, R1 to R6, L, a, b, and Ar1 are the same as defined in Formula 1 above. The method according to claim 1, wherein the heterocyclic compound of Formula 1 is a heterocyclic compound having any one of the following structures:

first electrode; a second electrode provided opposite the first electrode; And an organic light-emitting device comprising one or more organic material layers provided between the first electrode and the second electrode, wherein one or more layers of the organic material layers include the heterocyclic compound of any one of claims 1 to 3 and claims 5 to 6. An organic light-emitting device. The method of claim 7, wherein the organic material layer includes an electron injection layer, an electron transport layer, or a layer that simultaneously performs electron injection and electron transport, and the electron injection layer, the electron transport layer, or a layer that performs both electron injection and electron transport is the heterocyclic compound. An organic light-emitting device comprising a. The organic light emitting device according to claim 8, wherein the electron injection layer, the electron transport layer, or the layer that simultaneously performs electron injection and electron transport further includes a metal complex. In claim 7,
An organic light-emitting device wherein the organic material layer includes a hole blocking layer, and the hole blocking layer includes the heterocyclic compound.