KR102560362B1 - Hetero-cyclic compound and organic light emitting device comprising the same - Google Patents

Abstract

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

Description

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

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

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

Most of the materials used in organic light emitting devices are pure organic materials or complex compounds in which organic materials and metals are complexed, and may be classified into hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, etc. depending on the use. Here, as the hole injection material or the hole transport material, an organic material having a p-type property, that is, an organic material that is easily oxidized and has an electrochemically stable state when oxidized is mainly used. On the other hand, as an electron injection material or electron transport material, an organic material having an n-type property, that is, an organic material that is easily reduced and has an electrochemically stable state upon reduction is mainly used. As the material for the light emitting layer, a material having both p-type and n-type properties, that is, a material having a stable form in both oxidation and reduction states is preferable, and a material with high luminous efficiency that converts excitons into light when formed by recombination of holes and electrons in the light emitting layer is preferable.

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

Korean Patent Publication No. 2016-132822

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

An exemplary embodiment of the present specification provides a heterocyclic compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

Z is O or S;

R1 and R2 are the same as or different from each other, are substituted or unsubstituted alkyl groups, or combine with each other to form an aliphatic ring;

L is a direct bond; or a substituted or unsubstituted arylene group;

a is an integer from 1 to 3, and when a is 2 or more, 2 or more L's are the same as or different from each other;

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

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 G17s are the same as or different from each other;

delete

X1 to X4 are the same as or different from each other, and are each independently N or CR3, provided that at least two of X1 to X4 are N,

R3, G1 to G15 and G17 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

delete

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

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

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

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

The present specification provides a heterocyclic compound represented by Formula 1 below.

[Formula 1]

In Formula 1,

Z is O or S;

R1 and R2 are the same as or different from each other, are substituted or unsubstituted alkyl groups, or combine with each other to form an aliphatic ring;

L is a direct bond; or a substituted or unsubstituted arylene group;

a is an integer from 1 to 3, and when a is 2 or more, 2 or more L's are the same as or different from each other;

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

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 G17s are the same as or different from each other;

delete

X1 to X4 are the same as or different from each other, and are each independently N or CR3, provided that at least two of X1 to X4 are N,

R3, G1 to G15 and G17 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

delete

In the organic light emitting device, when the dipole moment of the organic material is increased, the lifespan of the device is improved.

In the compound represented by Formula 1 of the present invention, polarization is achieved by including only one substituent of a xanthen group or thioxanthen group in which Z is O or S, and thus the dipole moment is improved and the lifetime is improved. In addition, including an alkyl group as R1 and R2 increases the polarization effect between the xanthen group and the substituent (Ar1), and includes an Ar1 structure as the substituent to improve electron transfer characteristics, thereby improving the efficiency of the organic light emitting device.

In the present specification, when a certain component is said to "include", it means that it may further include other components without excluding other components unless otherwise stated.

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 the present specification are described below, but are not limited thereto.

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

In this specification, the term "substituted or unsubstituted" means deuterium; halogen group; Cyano group (-CN); ester group; imide group; amine group; alkoxy group; an alkyl group; cycloalkyl group; aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a heterocyclic group, or is substituted with a substituent in which two or more substituents from among the above exemplified substituents are connected, or does not have any substituents. For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent in which two phenyl groups are connected.

In the present specification, the alkyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. 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-dimethylheptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, etc. It is not limited to this.

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, a terphenyl group, and the like, but is not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it is 10-30 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, and the like, but is not limited thereto.

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

When the fluorenyl group is substituted, , , and etc. However, it is not limited thereto.

In the present specification, the description of the above-described aryl group can be cited except that the arylene group is divalent.

In the present specification, the heterocyclic group includes at least one atom or heteroatom other than carbon, and specifically, the heteroatom may include at least one atom selected from the group consisting of O, N, S, and P. The number of carbon atoms is not particularly limited, but preferably has 1 to 50 carbon atoms, 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 a thiophene group, a furanyl group, a pyrrole group, an imidazolyl group, a thiazolyl group, an oxazolyl group, an oxadiazolyl group, a pyridyl group, a bipyridyl group, a pyrimidyl group, a triazinyl group, a triazolyl group, an acridyl group, a pyridazinyl group, a pyrazinyl group, a quinolyl group, a quinazolyl group, a quinoxalyl group, a phthalazinyl group, and a pyrido Pyrimidyl, pyridopyrazinyl, pyrazinopyrazinyl, isoquinolyl, indolyl, carbazolyl, benzoxazolyl, benzimidazolyl, benzothiazolyl, benzocarbazolyl, benzothiophene, dibenzothiophene, benzofuranyl, phenanthroline, isoxazolyl, thiadiazolyl group, a phenothiazinyl group and a dibenzofuranyl group, but are not limited thereto.

In the present 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, specifically 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, adamantane, etc., but are not limited thereto.

In the present specification, the aliphatic ring may be selected from examples of the cycloalkyl group.

In the present specification, the alkoxy group may be straight chain, branched chain or cyclic chain. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specifically, it may be 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, and the like, but is not limited thereto.

In the present specification, the amine group is -NH ₂ ; Alkylamine group; N-alkyl arylamine group; Arylamine group; N-arylheteroarylamine group; It may be selected from the group consisting of an N-alkylheteroarylamine group and a heteroarylamine group, and the number of carbon atoms is not particularly limited, but is preferably 0 to 30. Specific examples of the amine group include a methylamine group, a dimethylamine group, an ethylamine group, a diethylamine group, a phenylamine group, a naphthylamine group, a biphenylamine group, an anthracenylamine group, and a 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 are not limited thereto.

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

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

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

In the present specification, the alkyl group of the alkylamine group, the N-arylalkylamine group, and the N-alkylheteroarylamine group is the same as the above-mentioned alkyl group.

In one embodiment of the present specification, a is 1 or 2.

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

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

In one embodiment of the present specification, L is a direct bond; Or an arylene group unsubstituted or substituted with one or more substituents selected from the group consisting of heavy hydrogen, a cyano group, an alkyl group and an aryl group.

In one embodiment of the present specification, L is a direct bond; Or an arylene group having 6 to 30 carbon atoms 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; A phenylene group unsubstituted or substituted with one or more substituents selected from the group consisting of heavy hydrogen, a cyano group, an alkyl group and an aryl group; A biphenylene group unsubstituted or substituted with one or more substituents selected from the group consisting of heavy hydrogen, a cyano group, an alkyl group and an aryl group; Or 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.

In one embodiment of the present specification, L is a direct bond; Or an arylene group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group or an aryl group.

In one embodiment of the present specification, L is a direct bond; A phenylene group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group or an aryl group; Biphenylene group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group or an aryl group; Or a naphthylene group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group or an aryl group.

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

In one embodiment of the present specification, R1 and R2 are the same as or different from each other, and each independently is a substituted or unsubstituted alkyl group, or is bonded to each other to form an aliphatic ring.

In one embodiment of the present specification, R1 and R2 are the same as or different from each other, and each independently represents a substituted or unsubstituted alkyl group having 1 to 30 carbon atoms.

In one embodiment of the present specification, R1 and R2 are the same as or different from each other, and each independently represents a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

In one embodiment of the present specification, R1 and R2 are the same as or different from each other, and each independently represents a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms.

In one embodiment of the present specification, R1 and R2 are the same as or different from each other, and each independently represents an alkyl group having 1 to 10 carbon atoms.

In one embodiment of the present specification, R1 and R2 are the same as or different from each other, and each independently represents an alkyl group having 1 to 5 carbon atoms.

In one embodiment of the present specification, R1 and R2 are the same as or different from each other, and each independently represents a methyl group, an ethyl group, a propyl group, or a butyl group.

In one embodiment of the present specification, R1 and R2 are each a methyl group or an ethyl group.

In one embodiment of the present specification, the R1 and R2 combine with each other to form an aliphatic ring.

In one embodiment of the present specification, R1 and R2 combine with each other to form a 3- to 20-membered aliphatic ring or adamantane.

In one embodiment of the present specification, R1 and R2 combine with each other to form a 3- to 10-membered aliphatic ring or adamantane.

In one embodiment of the present specification, R1 and R2 combine with each other to form a 6-membered ring or adamantane.

In one embodiment of the present specification, R1 and R2 are each a methyl group or an ethyl group, or bonded to each other to form a 6-membered ring or adamantane.

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 G17s are the same as or different from each other;

delete

X1 to X4 are the same as or different from each other, and are each independently N or CR3, provided that at least two of X1 to X4 are N,

delete

R3, G1 to G15 and G17 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

delete

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

In the above structure, c, X1 to X4, G1 to G15 and G17 are the same as described above.

In one embodiment of the present specification, two of X1 to X4 are N, the other two are CR3, R3 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, two of X1 to X4 are N, the other two are CR3, and R3 is hydrogen.

In one embodiment of the present specification, X2 and X3 are N, X1 and X4 are CR3, R3 is hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, X2 and X3 are N, X1 and X4 are CR3, and R3 is hydrogen.

delete

delete

delete

delete

delete

delete

In one embodiment of the present specification, G1 to G15 and G17 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, G1 to G15 and G17 are the same as or different from each other, and 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 a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

In one embodiment of the present specification, G1 to G15 and G17 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group, an aryl group, or a heterocyclic group; or a heterocyclic group having 2 to 30 carbon atoms unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group, an aryl group or a heterocyclic group.

In one embodiment of the present specification, G1 to G15 and G17 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; A substituted or unsubstituted naphthyl group; A substituted or unsubstituted fluoranthene group; A substituted or unsubstituted dibenzothiophene group; Or a substituted or unsubstituted dibenzofuran group, wherein the substituted or unsubstituted deuterium; cyano group; an alkyl group; It means that it is substituted or unsubstituted with any one or two or more linked substituents selected from the group consisting of an aryl group and a heterocyclic group.

In one embodiment of the present specification, G1 to G15 and G17 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A phenyl group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group, an aryl group, an alkoxy group, or a heterocyclic group; a biphenyl group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group, an aryl group, an alkoxy group, or a heterocyclic group; a naphthyl group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group, an aryl group, an alkoxy group, or a heterocyclic group; a fluoranthene group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group, an aryl group, an alkoxy group, or a heterocyclic group; dibenzothiophene group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group, an aryl group, an alkoxy group, or a heterocyclic group; or a dibenzofuran group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group, an aryl group, an alkoxy group, or a heterocyclic group.

In one embodiment of the present specification, G1 to G15 and G17 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A phenyl group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an N-containing heterocyclic group; Biphenyl group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an N-containing heterocyclic group; a naphthyl group unsubstituted or substituted with a heavy hydrogen, cyano group, alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, or N-containing heterocyclic group; A fluoranthene group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an N-containing heterocyclic group; a dibenzothiophene group unsubstituted or substituted with a heavy hydrogen, cyano group, alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, or N-containing heterocyclic group; or a dibenzofuran group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or an N-containing heterocyclic group.

In one embodiment of the present specification, G1 to G15 and G17 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A phenyl group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group, a pyridine group, an alkoxy group, or a naphthyl group; a biphenyl group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group, a pyridine group, an alkoxy group, or a naphthyl group; a naphthyl group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group, a pyridine group, an alkoxy group, or a naphthyl group; a fluoranthene group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group, a pyridine group, an alkoxy group, or a naphthyl group; dibenzothiophene group unsubstituted or substituted with heavy hydrogen, cyano group, heavy hydrogen, cyano group, alkyl group, pyridine group, alkoxy group or naphthyl group; or a dibenzofuran group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group, a pyridine group, an alkoxy group, or a naphthyl group.

In one embodiment of the present specification, G1 to G15 and G17 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A phenyl group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group, a pyridine group, an alkoxy group, or a naphthyl group; a biphenyl group unsubstituted or substituted with a cyano group; naphthyl group; Fluoranthene group; Dibenzothiophene group; or a dibenzofuran group.

In one embodiment of the present specification, b is an integer from 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 Formulas 1-1 to 1-4 below.

[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 one 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, Chemical Formula 1 is represented by Chemical Formulas 1-4.

In one embodiment of the present specification, b is 2.

In one embodiment of the present specification, Formula 1 is represented by any one of Formulas 1-5 to 1-10 below.

[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

In Formulas 1-5 to 1-10,

Z, R1 and R2 are the same as defined in Formula 1 above,

L1 and L2 are the same as or different from each other, and are each independently a direct bond; Or a substituted or unsubstituted arylene group,

a1 and a2 are each an integer from 1 to 3;

When a1 is 2 or more, 2 or more L1s are the same or different from each other,

When a2 is 2 or more, 2 or more L2s are the same or different,

Ar2 and Ar3 are the same as or different from each other, and are each independently any one selected from the group consisting of

In the above structure,

Is a part connected to L1 or L2,

c is an integer from 1 to 5, and when c is 2 or more, 2 or more G17s are the same as or different from each other;

delete

X1 to X4 are the same as or different from each other, and are each independently N or CR3, provided that at least two of X1 to X4 are N,

delete

R3, G1 to G15 and G17 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, the L1 and L2 are the same as or different from each other, and are each independently a direct bond; or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In one embodiment of the present specification, the L1 and L2 are the same as or different from each other, and are each independently a direct bond; A substituted or unsubstituted monocyclic arylene group having 6 to 30 carbon atoms; or a substituted or unsubstituted polycyclic arylene group having 10 to 30 carbon atoms.

In one embodiment of the present specification, the L1 and L2 are the same as or different from each other, and are each independently a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene group; Or a substituted or unsubstituted naphthylene group.

In one embodiment of the present specification, the L1 and L2 are the same as or different from each other, and are each independently a direct bond; Or an arylene group unsubstituted or substituted with one or more substituents selected from the group consisting of heavy hydrogen, a cyano group, an alkyl group and an aryl group.

In one embodiment of the present specification, the L1 and L2 are the same as or different from each other, and are each independently a direct bond; Or an arylene group having 6 to 30 carbon atoms 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, the L1 and L2 are the same as or different from each other, and are each independently a direct bond; A phenylene group unsubstituted or substituted with one or more substituents selected from the group consisting of heavy hydrogen, a cyano group, an alkyl group and an aryl group; A biphenylene group unsubstituted or substituted with one or more substituents selected from the group consisting of heavy hydrogen, a cyano group, an alkyl group and an aryl group; Or 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.

In one embodiment of the present specification, the L1 and L2 are the same as or different from each other, and are each independently a direct bond; Or an arylene group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group or an aryl group.

In one embodiment of the present specification, the L1 and L2 are the same as or different from each other, and are each independently a direct bond; A phenylene group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group or an aryl group; Biphenylene group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group or an aryl group; Or a naphthylene group unsubstituted or substituted with heavy hydrogen, a cyano group, an alkyl group or an aryl group.

In one embodiment of the present specification, the L1 and L2 are the same as or different from each other, and are each independently a direct bond; A phenylene group unsubstituted or substituted with a cyano group or an alkyl group; a biphenylene group unsubstituted or substituted with a cyano group or an alkyl group; or a naphthylene group unsubstituted or substituted with a cyano group or an alkyl group.

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

The core structure of Formula 1 according to an exemplary embodiment of the present specification may be prepared as in the following reaction scheme, substituents may be combined by a method known in the art, and the type, position or number of substituents may be changed according to techniques known in the art.

<reaction formula>

In the above reaction formula,

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

A is Cl or Br.

An exemplary embodiment of the present specification is a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one of the organic material layers includes the aforementioned heterocyclic compound.

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

For example, the organic light emitting device of the present specification may be manufactured by sequentially stacking a first electrode, an organic material layer, and a second electrode on a substrate. At this time, by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation, a metal or a conductive metal oxide or an alloy thereof is deposited on the substrate to form a first electrode, form 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 deposit a material that can be used as a second electrode thereon. In addition to this method, an organic light emitting device may be manufactured by sequentially depositing a second electrode material, an organic material layer, and a first electrode material on a substrate. In addition, the heterocyclic compound represented by Chemical Formula 1 may be formed as an organic material layer by a solution coating method as well as a vacuum deposition method when manufacturing an organic light emitting device. Here, the solution coating method 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 for simultaneously injecting and transporting holes, an electron suppressing layer, a light emitting layer and an electron transport layer, an electron injection layer, and a layer for simultaneously injecting and transporting electrons, but is not limited thereto and may have a single layer structure. In addition, the organic layer may be formed with a smaller number of layers by a solvent process, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer, rather than a deposition method, using various polymer materials.

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 injects and transports electrons, and the electron injection layer, the electron transport layer, or the layer that simultaneously injects and transports electrons includes the heterocyclic compound.

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 one 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 the present specification may have a structure as shown in FIGS. 1 to 4 , but is not limited thereto.

1 illustrates a 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, the first electrode 2, the hole injection layer 5, the hole transport layer 6, the light emitting layer 3, the electron transport layer 7, the electron injection layer 8, and the second electrode 4 are sequentially stacked on the substrate 1. The structure of the organic light emitting device is illustrated. 2 is an exemplary structure according to an exemplary embodiment of the present specification, and may further include another organic material layer.

3 illustrates a structure of an organic light emitting device in which 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, an electron injection and transport layer 9, and a second electrode 4 are sequentially stacked on a substrate 1. 3 is an exemplary structure according to an exemplary 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 10 on a substrate 1. A structure of an organic light emitting device in which an electron injection and transport layer 9 and a second electrode 4 are sequentially stacked is illustrated. 4 is an exemplary structure according to an exemplary embodiment of the present specification, and may further include another organic material layer.

Specifically, the organic light emitting device may have, for example, the following laminated structure in addition to the structure specified in the drawing, 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 blocking layer / electron transport layer / cathode

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

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

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

(18) anode/hole injection layer/hole transport layer/electron suppression layer/emission 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 including different materials.

The anode is an electrode for injecting holes, and a material having a high work function is preferable so that holes can be smoothly injected into the organic material layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, 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 thereto.

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

The hole injection layer is a layer that serves to smoothly inject holes from the anode to the light emitting layer, and the hole injection material is a material that can receive holes well from the anode at a low voltage. The highest occupied molecular orbital (HOMO) of the hole injection material is preferably between the work function of the anode material and the HOMO of the surrounding organic material layer. Examples of hole injection substances include porphyrine, olotiphyophen, arylamine -based organic substance, hexanitril hexatrylene -based organic matter, quinacridone -based organic substance, perylene organic matter Len's organic matter, Antracquinone, and polyaniline and polytinopene -based conductive polymers, etc., but are not limited to them. Specifically, as the hole injection material, a compound containing substituted or unsubstituted carbazole and substituted or unsubstituted fluorene may be used, but is not limited thereto.

In one embodiment of the present specification, the hole injection layer may have a thickness of 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 too thick to improve the movement of holes. There is an advantage in preventing the increase in driving voltage.

The hole transport layer may play a role of facilitating hole transport. As the hole transport material, a material capable of receiving holes transported from the anode or the hole injection layer and transferring them to the light emitting layer, and a material having high hole mobility is suitable. Examples of the hole transport material include, but are not limited to, arylamine-based organic materials, carbazole-based organic materials, quinoxaline-based organic materials, fluorene-based organic materials, conductive polymers, and block copolymers having both conjugated and non-conjugated portions. Specifically, examples of the hole transport material include quinoxazoline-based compounds and arylamine-based compounds, but are not limited thereto.

A hole buffer layer may be additionally provided between the hole injection layer and the hole transport layer, and may include a hole injection or transport material known in the art.

An electron blocking layer may be provided between the hole transport layer and the light emitting layer. For the electron suppression layer, the above compounds or materials known in the art may be used.

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

In one embodiment of the present specification, the light emitting layer includes a host and a dopant. The host may include the aforementioned 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, fluoranthene compounds, and the like, and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder-type furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

As the dopant, a phosphorescent material such as PIQIr (acac) (bis(1-phenylisoquinoline)acetylacetonateiridium), PQIr (acac) (bis(1-phenylquinoline)acetylacetonate iridium), PQIr (tris(1-phenylquinoline)iridium), PtOEP (octaethylporphyrin platinum), or a fluorescent material such as Alq ₃ (tris(8-hydroxyquinolino)aluminum) This may be used, but is not limited thereto. When the light emitting layer emits green light, a phosphorescent material such as Ir(ppy) ₃ (fac tris(2-phenylpyridine)iridium) or a fluorescent material such as Alq ₃ (tris(8-hydroxyquinolino)aluminum) may be used as the light emitting dopant, but is not limited thereto. When the light emitting layer emits blue light, (4,6-F ₂ ppy) ₂ Irpic, spiro-DPVBi, spiro-6P, distylbenzene (DSB), distryarylene (DSA), PFO-based polymers, PPV-based, pyrene-based, arylamine-based compounds, etc. may be used as the light-emitting dopant, but are not limited thereto.

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 serve to facilitate electron transport. As the electron transport material, a material capable of receiving electrons well from the cathode and transferring them to the light emitting layer, and a material having high electron mobility is suitable. Specific examples include Al complexes of 8-hydroxyquinoline, complexes containing Alq ₃ , organic radical compounds, anthracene-based compounds, imidazole-based compounds, and hydroxyflavone-metal complexes, but are not limited thereto. The electron transport layer may have a thickness of 1 nm to 50 nm. If the thickness of the electron transport layer is 1 nm or more, there is an advantage in preventing deterioration in electron transport properties, and if it is 50 nm or less, the thickness of the electron transport layer is too thick to improve the movement of electrons. There is an advantage in preventing the increase in driving voltage.

The electron injection layer may serve to smoothly inject electrons. As the electron injection material, a compound having the ability to transport electrons, having an excellent electron injection effect from the cathode, an excellent electron injection effect with respect to the light emitting layer or the light emitting material, preventing movement of excitons generated in the light emitting layer to the hole injection layer, and also having excellent thin film forming ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylene tetracarboxylic acid, fluorenylidene methane, anthron, anthracene, imidazole, etc. and their derivatives; metal complex compounds; Nitrogen-containing 5-membered ring derivatives; and lithium quinolate (LiQ), but are 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 simultaneously injects and transports electrons, and the electron injection layer, the electron transport layer, or the layer that simultaneously injects and transports electrons further includes a metal complex.

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

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis (8-hydroxyquinolinato) zinc, bis (8-hydroxyquinolinato) copper, bis (8-hydroxyquinolinato) manganese, tris (8-hydroxyquinolinato) aluminum, tris (2-methyl-8-hydroxyquinolinato) aluminum, tris (8-hydroxyquinolinato) gallium, bis (10-hydroxy Benzo[h]quinolinato)berylium, 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-na Ptolato) gallium, etc., but is not limited thereto.

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

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

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

Description of the metal complex included in the composition is the same as described above for the electron injection layer, the electron transport layer, or the electron injection and electron transport layer.

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 top emission type, a bottom emission type, or a double side emission type depending on the material used.

Hereinafter, examples will be described in detail in order to specifically describe the present specification. However, embodiments according to the present specification may be modified in many different forms, and the scope of the present specification is not construed as being limited to the embodiments described below. The embodiments herein are provided to more completely explain the present specification to those skilled in the art.

manufacturing example 1-1: Preparation of compound E1

In a nitrogen atmosphere, E1-A (20 g, 78.7 mmol) and E1-B (18.9 g, 78.7 mmol) were added to 400 mL of tetrahydrofuran, stirred and refluxed. Thereafter, potassium carbonate (32.6 g, 236.1 mmol) was dissolved in 33 mL of water, and after stirring sufficiently, tetrakistriphenyl-phosphinopalladium (2.7 g, 2.4 mmol) was added. After reacting for 2 hours, cooled to room temperature, separated the organic layer and the water layer, and then distilled the organic layer. This was put into 653 mL of 20 times chloroform again to dissolve, washed twice with water, separated the organic layer, stirred with anhydrous magnesium sulfate, filtered, and the filtrate was distilled under reduced pressure. The concentrated compound was recrystallized from chloroform and ethyl acetate to obtain a white solid compound E1 (22.5g, 69%, MS: [M+H]+ = 415).

delete

delete

delete

delete

delete

delete

delete

delete

manufacturing example 1-4: Preparation of compound E4

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

MS: [M+H] ⁺ = 515

manufacturing example 1-5: Preparation of compound E5

Compound E5 was prepared in the same manner as in Preparation Example 1-1, except for using each starting material as in the above reaction scheme.

MS: [M+H] ⁺ = 567

delete

delete

delete

delete

manufacturing example 1-7: Preparation of Compound E7

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

MS: [M+H] ⁺ = 615

manufacturing example 1-8: Preparation of compound E8

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

MS: [M+H] ⁺ = 505

manufacturing example 1-9: Preparation of compound E9

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

MS: [M+H] ⁺ = 520

manufacturing example 1-10: Preparation of compound E10

Compound E10 was prepared in the same manner as in Preparation Example 1-1, except for using each starting material as in the reaction scheme.

MS: [M+H] ⁺ = 632

delete

delete

delete

delete

manufacturing example 1-12: Preparation of compound E12

Compound E12 was prepared in the same manner as in Preparation Example 1-1, except for using each starting material as in the above reaction scheme.

MS: [M+H] ⁺ = 573

manufacturing example 1-13: Preparation of compound E13

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

MS: [M+H] ⁺ = 507

delete

delete

delete

Example 1-1.

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1000 Å was put in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product of Fischer Co. was used as a detergent, and distilled water filtered through a second filter of a product of Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with solvents such as isopropyl alcohol, acetone, and methanol, dried, and transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum deposition machine.

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

Subsequently, a light emitting layer was formed by vacuum depositing the following BH compound and BD compound at a weight ratio of 25:1 to a film thickness of 20 nm on the second hole transport layer.

On the light 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 negative electrode 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 the organic material was maintained at 0.4 Å/sec to 0.9 Å/sec, the deposition rate of lithium fluoride on the cathode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum level during deposition was maintained at 1×10 ⁻⁷ torr to 5×10 ⁻⁵ torr to manufacture an organic light emitting device.

Examples 1-4, 1-5, 1-7 to 1-10, 1-12 and 1-13.

An organic light emitting device was manufactured in the same manner as in Example 1-1, except that compounds E4, E5, E7 to E10, E12 and E13 described in Table 1 were used instead of Compound E1 of Example 1-1.

comparative example 1-1 to 1-14.

An organic light emitting device was manufactured in the same manner as in Example 1-1, except for using compounds ET-A to ET-N in Table 1 below instead of Compound E1 of Example 1-1.

For the organic light-emitting devices prepared in Examples 1-1, 1-4, 1-5, 1-7 to 1-10, 1-12, and 1-13 and Comparative Examples 1-1 to 1-14, the driving voltage and luminous efficiency were measured at a current density of 10 mA/cm ² , and the time (T90) at which the initial luminance reached 90% at a current density of 20 mA/cm ² 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) Life (h)
T90 at
20 mA/cm ² ) Example 1-1 E1 4.66 4.88 (0.140, 0.090) 162 Example 1-4 E4 4.57 4.95 (0.141, 0.090) 143 Example 1-5 E5 4.71 5.08 (0.140, 0.090) 142 Examples 1-7 E7 4.47 5.10 (0.140, 0.091) 136 Examples 1-8 E8 4.77 4.78 (0.140, 0.090) 162 Examples 1-9 E9 4.71 5.03 (0.140, 0.092) 157 Examples 1-10 E10 4.85 4.82 (0.140, 0.091) 137 Examples 1-12 E12 4.75 5.01 (0.140, 0.092) 111 Examples 1-13 E13 4.71 4.93 (0.140, 0.091) 118 Comparative Example 1-1 ET-A 4.71 4.39 (0.140, 0.092) 39 Comparative Example 1-2 ET-B 4.61 4.48 (0.140, 0.091) 35 Comparative Example 1-3 ET-C 4.66 4.44 (0.141, 0.090) 36 Comparative Example 1-4 ET-D 4.61 4.46 (0.140, 0.090) 34 Comparative Example 1-5 ET-E 5.08 3.35 (0.140, 0.092) 64 Comparative Example 1-6 ET-F 5.13 3.16 (0.140, 0.091) 67 Comparative Example 1-7 ET-G 4.83 3.37 (0.141, 0.090) 61 Comparative Example 1-8 ET-H 5.15 3.15 (0.140, 0.090) 73 Comparative Example 1-9 ET-I 5.08 3.32 (0.140, 0.092) 71 Comparative Example 1-10 ET-J 5.23 3.18 (0.140, 0.090) 64 Comparative Example 1-11 ET-K 4.98 3.12 (0.140, 0.092) 44 Comparative Example 1-12 ET-L 5.13 3.30 (0.140, 0.091) 45 Comparative Example 1-13 ET-M 5.08 3.25 (0.141, 0.090) 50 Comparative Example 1-14 ET-N 5.18 3.30 (0.141, 0.092) 54

As described in Table 1 above, the compound represented by Chemical Formula 1 according to the present specification may be used in an organic material layer that simultaneously injects and transports electrons in an organic light emitting device.

Comparing Examples 1-1, 1-4, 1-5, 1-7 to 1-10, 1-12, and 1-13 with Comparative Example 1-1 in Table 1, it can be seen that the organic light-emitting device to which the heterocyclic compound of Formula 1 according to the present specification is applied exhibits significantly better characteristics in terms of lifespan than the organic light-emitting device to which a compound in which R1 and R2 are bonded to each other to form an aromatic ring is applied.

Comparing Examples 1-1, 1-4, 1-5, 1-7 to 1-10, 1-12 and 1-13 and Comparative Examples 1-2 to 1-4 in Table 1, it can be seen that the organic light-emitting device to which the heterocyclic compound of Formula 1 according to the present specification is applied exhibits significantly better characteristics in terms of lifespan than the organic light-emitting device to which the compound in which the fluorene group is substituted is applied.

Comparing Examples 1-1, 1-4, 1-5, 1-7 to 1-10, 1-12 and 1-13 with Comparative Examples 1-5 and 1-7 in Table 1, it can be seen that the organic light emitting device to which the heterocyclic compound of Formula 1 according to the present specification is applied exhibits significantly better characteristics in terms of efficiency and lifespan than the organic light emitting device to which a compound containing a heterocyclic group is applied as the linker (L).

Comparing Examples 1-1, 1-4, 1-5, 1-7 to 1-10, 1-12, and 1-13 with Comparative Examples 1-8 and 1-9 in Table 1, it can be seen that the organic light-emitting device to which the heterocyclic compound of Formula 1 according to the present specification is applied exhibits significantly better characteristics in terms of efficiency and lifespan than the organic light-emitting device to which a compound containing both xanthen or thioxanthen substituents is applied.

Comparing Examples 1-1, 1-4, 1-5, 1-7 to 1-10, 1-12 and 1-13 with Comparative Examples 1-6 and 1-14 in Table 1, it can be seen that the organic light-emitting device to which the heterocyclic compound of Formula 1 according to the present specification is applied exhibits significantly better characteristics in terms of efficiency and lifetime than the organic light-emitting device to which the compound in which Z is N is applied.

Comparing Examples 1-1, 1-4, 1-5, 1-7 to 1-10, 1-12 and 1-13 with Comparative Examples 1-10 to 1-13 in Table 1, it can be seen that the organic light-emitting device to which the heterocyclic compound of Formula 1 according to the present specification is applied exhibits significantly better characteristics in terms of efficiency and lifespan than the organic light-emitting device to which the compound containing a benzoimidazole group unsubstituted or substituted with Ar1 is applied.

Example 2-1.

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1000 Å was put in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product of Fischer Co. was used as a detergent, and distilled water filtered through a second filter of a product of Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was performed twice with distilled water for 10 minutes. After washing with distilled water, ultrasonic cleaning was performed with solvents such as isopropyl alcohol, acetone, and methanol, dried, and transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transferred to a vacuum deposition machine.

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

Subsequently, a light emitting layer was formed by vacuum depositing the following BH compound and BD compound at a weight ratio of 25:1 to a film thickness of 20 nm on the second hole transport layer.

On the light 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-O 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 300 Å. A negative electrode 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 the organic material was maintained at 0.4 Å/sec to 0.9 Å/sec, the deposition rate of lithium fluoride on the cathode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum level during deposition was maintained at 1×10 ⁻⁷ torr to 5×10 ⁻⁵ torr to manufacture an organic light emitting device.

Examples 2-4, 2-5, 2-7 to 2-9, 2-11 and 2-12.

An organic light emitting device was manufactured in the same manner as in Example 2-1, except that compounds E4, E5, E7 to E9, E12 and E13 described in Table 2 were used instead of compound E1 of Example 2-1.

comparative example 2-1 to 2-14.

An organic light emitting diode was manufactured in the same manner as in Example 2-1, except for using compounds ET-A to ET-N in Table 2 below instead of Compound E1 of Example 2-1.

For the organic light-emitting devices prepared in Examples 2-1, 2-4, 2-5, 2-7 to 2-9, 2-11, and 2-12 and Comparative Examples 2-1 to 2-14, the driving voltage and luminous efficiency were measured at a current density of 10 mA/cm ² , and the time (T90) at which the initial luminance reached 90% at a current density of 20 mA/cm ² 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) Life (h)
T90 at
20 mA/cm ² ) Example 2-1 E1 4.60 5.02 (0.140, 0.090) 155 Example 2-4 E4 4.51 5.01 (0.141, 0.090) 139 Example 2-5 E5 4.51 5.22 (0.140, 0.090) 136 Examples 2-7 E7 4.42 5.25 (0.140, 0.091) 131 Example 2-8 E8 4.71 4.91 (0.140, 0.090) 155 Example 2-9 E9 4.65 5.17 (0.140, 0.092) 150 Examples 2-11 E12 4.60 5.15 (0.140, 0.092) 102 Examples 2-12 E13 4.65 5.07 (0.140, 0.091) 105 Comparative Example 2-1 ET-A 4.65 4.52 (0.140, 0.092) 37 Comparative Example 2-2 ET-B 4.55 4.47 (0.140, 0.091) 33 Comparative Example 2-3 ET-C 4.60 4.52 (0.141, 0.090) 34 Comparative Example 2-4 ET-D 4.55 4.51 (0.140, 0.090) 33 Comparative Example 2-5 ET-E 4.87 3.45 (0.140, 0.092) 61 Comparative Example 2-6 ET-F 5.07 3.25 (0.140, 0.091) 64 Comparative Example 2-7 ET-G 4.77 3.47 (0.141, 0.090) 59 Comparative Example 2-8 ET-H 5.08 3.24 (0.140, 0.090) 70 Comparative Example 2-9 ET-I 5.02 3.41 (0.140, 0.092) 68 Comparative Example 2-10 ET-J 5.02 3.34 (0.140, 0.090) 45 Comparative Example 2-11 ET-K 4.92 3.21 (0.140, 0.092) 42 Comparative Example 2-12 ET-L 4.97 3.40 (0.140, 0.091) 43 Comparative Example 2-13 ET-M 5.02 3.35 (0.141, 0.090) 48 Comparative Example 2-14 ET-N 5.12 3.40 (0.141, 0.092) 52

As described in Table 2, the compound represented by Formula 1 according to the present specification may be used in an organic material layer that may be used in a hole blocking layer of an organic light emitting device.

Comparing Examples 2-1, 2-4, 2-5, 2-7 to 2-9, 2-11, and 2-12 of Table 2 with Comparative Example 2-1, it was confirmed that the organic light-emitting device to which the heterocyclic compound of Formula 1 according to the present specification is applied exhibits significantly better characteristics in terms of lifespan than the organic light-emitting device to which a compound in which R1 and R2 are bonded to each other to form an aromatic ring is applied.

Comparing Examples 2-1, 2-4, 2-5, 2-7 to 2-9, 2-11 and 2-12 and Comparative Examples 2-2 to 2-4 in Table 2, it was confirmed that the organic light-emitting device to which the heterocyclic compound of Formula 1 according to the present specification was applied exhibited significantly better characteristics in terms of lifespan than the organic light-emitting device to which the compound in which the fluorene group was substituted was applied.

Comparing Examples 2-1, 2-4, 2-5, 2-7 to 2-9, 2-11 and 2-12 and Comparative Examples 2-5 and 2-7 in Table 2, it was confirmed that the organic light-emitting device to which the heterocyclic compound of Formula 1 according to the present specification is applied exhibits significantly better characteristics in terms of efficiency and lifespan than the organic light-emitting device to which a compound containing a heterocyclic group is applied as a linker (L).

Comparing Examples 2-1, 2-4, 2-5, 2-7 to 2-9, 2-11 and 2-12 and Comparative Examples 2-8 and 2-9 in Table 2, it was confirmed that the organic light-emitting device to which the heterocyclic compound of Formula 1 according to the present specification was applied exhibited significantly better characteristics in terms of efficiency and lifespan than the organic light-emitting device to which a compound containing both xanthene and thioxanthen containing substituents was applied.

Comparing Examples 2-1, 2-4, 2-5, 2-7 to 2-9, 2-11 and 2-12 and Comparative Examples 2-6 and 2-14 in Table 2, it was confirmed that the organic light emitting device to which the heterocyclic compound of Formula 1 according to the present specification is applied exhibits significantly better characteristics in terms of efficiency and lifespan than the organic light emitting device to which the compound in which Z is N is applied.

Comparing Examples 2-1, 2-4, 2-5, 2-7 to 2-9, 2-11 and 2-12 and Comparative Examples 2-10 to 2-13 in Table 2, it can be seen that the organic light-emitting device to which the heterocyclic compound of Formula 1 according to the present specification is applied exhibits significantly better characteristics in terms of efficiency and lifetime than the organic light-emitting device to which the compound containing a benzoimidazole group unsubstituted or substituted with Ar1 is applied.

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 (9)

Heterocyclic compounds of formula 1:
[Formula 1]

In Formula 1,
Z is O or S;
R1 and R2 are the same as or different from each other, are alkyl groups, or combine with each other to form a 6-membered ring;
L is a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene group; Or a substituted or unsubstituted naphthylene group,
a is an integer from 1 to 3, and when a is 2 or more, 2 or more L's are the same as or different from each other;
b is an integer from 1 to 4, and when b is 2 or more, the structures in parentheses are the same as or different from each other,
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 G17s are the same as or different from each other;
X1 to X4 are the same as or different from each other, and are each independently N or CR3, provided that at least two of X1 to X4 are N,
R3, G1 to G15 and G17 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
The substituted or unsubstituted deuterium; cyano group; an alkyl group; aryl group; And any one selected from the group consisting of a heterocyclic group, or means substituted or unsubstituted with a substituent linked to two or more. delete The method of claim 1,
Formula 1 is a heterocyclic compound of any one of 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. The method of claim 1,
Formula 1 is a heterocyclic compound of any one of Formulas 1-5 to 1-10:
[Formula 1-5]

[Formula 1-6]

[Formula 1-7]

[Formula 1-8]

[Formula 1-9]

[Formula 1-10]

In Formulas 1-5 to 1-10,
Z, R1 and R2 are the same as defined in Formula 1 above,
L1 and L2 are the same as or different from each other, and are each independently a direct bond; A substituted or unsubstituted phenylene group; A substituted or unsubstituted biphenylene group; Or a substituted or unsubstituted naphthylene group,
a1 and a2 are each an integer from 1 to 3;
When a1 is 2 or more, 2 or more L1s are the same or different from each other,
When a2 is 2 or more, 2 or more L2s are the same or different,
Ar2 and Ar3 are the same as or different from each other, and are each independently any one selected from the group consisting of

In the above structure,
Is a part connected to L1 or L2,
c is an integer from 1 to 5, and when c is 2 or more, 2 or more G17s are the same as or different from each other;
X1 to X4 are the same as or different from each other, and are each independently N or CR3, provided that at least two of X1 to X4 are N,
R3, G1 to G15 and G17 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group,
The substituted or unsubstituted deuterium; cyano group; an alkyl group; aryl group; And any one selected from the group consisting of a heterocyclic group, or means substituted or unsubstituted with a substituent linked to two or more. The method of claim 1,
The heterocyclic compound of Formula 1 is any one of the following structures:

a first electrode; a second electrode provided to face the first electrode; and one or more organic material layers provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer includes the heterocyclic compound according to any one of claims 1 and 3 to 5. An organic light emitting device. The organic light emitting device of claim 6, wherein the organic material layer includes an electron injection layer, an electron transport layer, or a layer that simultaneously injects and transports electrons, and the electron injection layer, the electron transport layer, or the layer that simultaneously injects and transports electrons includes the heterocyclic compound. The organic light emitting device of claim 7, wherein the electron injection layer, the electron transport layer, or the electron injection and electron transport layer further comprises a metal complex. The method of claim 6,
wherein the organic material layer includes a hole blocking layer, and the hole blocking layer includes the heterocyclic compound.