KR20210155035A - 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. The heterocyclic compound according to an exemplary embodiment of the present specification can be used as a material of an organic material layer of the organic light emitting device, and by using the same, it is possible to improve efficiency, lower driving voltage and/or improve lifespan characteristics in the organic light emitting device.

Description

Heterocyclic compound and organic light-emitting device comprising 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 combine in the organic thin film to form a pair, and then disappear and emit light. The organic thin film may be composed of a single layer or multiple layers, if necessary.

As materials used in organic light emitting devices, pure organic materials or complex compounds in which organic materials and metals are complexed account for most, and depending on the use, hole injection material, hole transport material, light emitting material, electron transport material, electron injection material can be divided into 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 during oxidation is mainly used. On the other hand, as an electron injection material or an 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 during reduction is mainly used. As the light emitting layer material, a material having both p-type properties and n-type properties, that is, a material having a stable form in both oxidation and reduction states is preferable, and excitons generated by recombination of holes and electrons in the light emitting layer are formed A material with high luminous efficiency that converts it into light when it is formed is preferable.

In order to improve the performance, lifespan or efficiency of an organic light emitting device, the development of a material for an organic thin film 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 the following formula (1).

[Formula 1]

In Formula 1,

b is an integer of 1 to 3, and when b is 2 or more, the structures in parentheses are the same as or different from each other,

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 alkyl group, or combine with each other to form an aliphatic ring;

L is a direct bond; monocyclic arylene group; or a bicyclic arylene group;

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

X1 to X3 are the same as or different from each other, and each independently represents CR3 or N, provided that at least two of X1 to X3 are N;

R3 is hydrogen; a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

G1 and G2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

Another embodiment of the present specification is a first electrode; a second electrode provided to face the first electrode; and at least one organic material layer provided between the first electrode and the second electrode, wherein at least one 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 for 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 lifespan characteristics in an organic light emitting device.

1 to 4 illustrate an organic light emitting diode 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 the following formula (1).

[Formula 1]

In Formula 1,

b is an integer of 1 to 3, and when b is 2 or more, the structures in parentheses are the same as or different from each other,

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 alkyl group, or combine with each other to form an aliphatic ring;

L is a direct bond; monocyclic arylene group; or a bicyclic arylene group;

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

X1 to X3 are the same as or different from each other, and each independently represents CR3 or N, provided that at least two of X1 to X3 are N;

R3 is hydrogen; a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,

G1 and G2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

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

The compound represented by Formula 1 of the present invention is polarized by including a substituent in only one of the xanthene group or thioxanthene group in which Z is O or S, thereby exhibiting an effect of improving the dipole moment. In addition, by including an alkyl group as R1 and R2, the polarization effect between the xanthene group and the substituent (triazine group or pyrimidine group) is increased, and the electron transfer property is improved by including triazine or pyrimidine as a substituent, thereby improving the efficiency of the organic light-emitting device This shows an improved effect.

In the present specification, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

In this specification, when a member is said to be located "on" another member, this includes not only a case in which a member is in contact with another member but also a case in which another member exists between the two members.

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

는 다른 치환기 또는 결합부에 결합되는 부위를 의미한다.In this specification,

is another substituent or means a site bonded to the bonding portion.

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 position at which the hydrogen atom is substituted, that is, a position where the substituent is substitutable, is substituted. , two or more substituents may be the same as or different from each other.

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; cyano group (-CN); ester group; imid; 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, is substituted with a substituent to which two or more of 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-dimethyl heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 4-methylhexyl, 5-methylhexyl, and the like.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 50 carbon atoms, such as 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 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 C10-30. Specifically, the polycyclic aryl group may be a naphthyl group, an anthracenyl group, a phenanthrene group, a triphenylene group, a pyrene group, a phenalenyl group, a perylenyl group, a chrysenyl group, a fluorenyl group, a fluoranthene group, etc. The present invention is not limited thereto.

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

,

,

및

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

and

etc. can be However, the present invention is not limited thereto.

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

In the present specification, the description of the monocyclic aryl group may be cited except that the monocyclic arylene group is a divalent group.

In the present specification, the bicyclic arylene group may be a naphthylene group.

In the present specification, the heterocyclic group includes one or more atoms other than carbon and heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, S and P, and the like. The number of carbon atoms is not particularly limited, but preferably has 1 to 50 carbon atoms, further 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 ring condensed therewith. 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, Triazolyl group, acridyl group, pyridazinyl group, pyrazinyl group, quinolyl group, quinazolyl group, quinoxalyl group, phthalazinyl group, pyridopyrimidyl group, pyridopyrazinyl group, pyrazinopyrazinyl group group, isoquinolyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, A phenanthroline group, an isoxazolyl group, a thiadiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, the description of the above-mentioned heterocyclic group may be cited except that the divalent heterocyclic group is divalent.

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, and 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, etc., but are limited thereto it is not

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

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C30. 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 and the like may be used, but is not limited thereto.

In the present specification, the amine group is -NH ₂ ; an alkylamine group; N-alkylarylamine group; arylamine group; N-aryl heteroarylamine 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, and the like, but is not limited thereto.

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

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

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

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

In one embodiment of the present specification, Z is O or S.

In one embodiment of the present specification, Z is O.

In one embodiment of the present specification, Z is S.

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

In an exemplary embodiment of the present specification, a is 2.

In an exemplary embodiment of the present specification, a is 3.

In one embodiment of the present specification, L is a direct bond; monocyclic arylene group; or a bicyclic arylene group.

In one embodiment of the present specification, L is a direct bond; monocyclic arylene group having 6 to 30 carbon atoms; or an arylene group having 2 rings.

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

In an exemplary embodiment of the present specification, X1 to X3 are the same as or different from each other, and each independently represent CR3 or N, provided that at least two of X1 to X3 are N.

In the exemplary embodiment of the present specification, each of X1 to X3 is N.

In an exemplary embodiment of the present specification, X1 and X2 are N, and X3 is CR3.

In an exemplary embodiment of the present specification, X1 and X3 are N, and X2 is CR3.

In an exemplary embodiment of the present specification, X2 and X3 are N, and X1 is CR3.

In an exemplary embodiment of the present specification, R3 is hydrogen; a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group.

In an exemplary embodiment of the present specification, R3 is hydrogen; an alkyl group; or an aryl group.

In an exemplary embodiment of the present specification, R3 is hydrogen; an alkyl group having 1 to 30 carbon atoms; or an aryl group having 6 to 30 carbon atoms.

In an exemplary embodiment of the present specification, R3 is hydrogen; methyl group; ethyl group; or a phenyl 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 alkyl group, or combine with each other to form an aliphatic ring.

In an exemplary 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 C1-C30 alkyl group.

In an exemplary 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 C1-C20 alkyl group.

In an exemplary 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 C 1 to C 10 alkyl group.

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

In an exemplary embodiment of the present specification, R1 and R2 are bonded to each other to form an aliphatic ring.

In an exemplary embodiment of the present specification, R1 and R2 are combined with each other to form a 3- to 10-membered aliphatic ring.

In an exemplary embodiment of the present specification, R1 and R2 are combined with each other to form a 3- to 6-membered aliphatic ring.

In an exemplary embodiment of the present specification, R1 and R2 are bonded to each other to form a 6-membered ring.

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

In an exemplary embodiment of the present specification, G1 and G2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In an exemplary embodiment of the present specification, G1 and G2 are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 30 alkyl group; a substituted or unsubstituted C6-C30 aryl group; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms.

In an exemplary embodiment of the present specification, G1 and G2 are the same as or different from each other, and each independently a substituted or unsubstituted C 1 to C 30 alkyl group; a substituted or unsubstituted C6-C30 aryl group; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms including at least one of N, O and S.

In an exemplary embodiment of the present specification, G1 and G2 are the same as or different from each other, and each independently an alkyl group unsubstituted or substituted with one or more selected from the group consisting of deuterium, a cyano group, an alkyl group, an aryl group, and a heterocyclic group. ; an aryl group unsubstituted or substituted with one or more selected from the group consisting of deuterium, a cyano group, an alkyl group, an aryl group, and a heterocyclic group; or a heterocyclic group unsubstituted or substituted with one or more selected from the group consisting of deuterium, a cyano group, an alkyl group, an aryl group, and a heterocyclic group.

In an exemplary embodiment of the present specification, G1 and G2 are the same as or different from each other, and each independently substituted or unsubstituted aryl with one or more selected from the group consisting of deuterium, a cyano group, an alkyl group, an aryl group, and a heterocyclic group. energy; or a heterocyclic group unsubstituted or substituted with one or more selected from the group consisting of deuterium, a cyano group, an alkyl group, an aryl group, and a heterocyclic group.

In an exemplary embodiment of the present specification, G1 and G2 are the same as or different from each other, and each independently a phenyl group; biphenyl group; naphthyl group; phenalene group; phenanthrene group; fluoranthene group; triphenylene group; terphenyl group; pyridine group; pyrimidine group; triazine group; quinoline group; fluorenyl group; dibenzofuran group; dibenzothiophene group; a carbazole group; benzocarbazole group; phenoxazine; phenothiazine group; quinoline group; and any one or two or more selected from the group consisting of a phenazine group, wherein G1 and G2 are deuterium; cyano group; It is unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group and an aryl group.

In an exemplary embodiment of the present specification, G1 and G2 are the same as or different from each other, and each independently any one or two or more of the following structures are linked.

In the above structure, X10 is NR10; CR10R11; S; or O;

R10 and R11 are the same as or different from each other, and each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group,

The structure is deuterium; cyano group; It is unsubstituted or substituted with one or more substituents selected from the group consisting of an alkyl group and an aryl group.

In one embodiment of the present specification, the structure is deuterium; cyano group; an alkyl group having 1 to 10 carbon atoms; It is unsubstituted or substituted with one or more substituents selected from the group consisting of an aryl group having 6 to 30 carbon atoms.

In one embodiment of the present specification, the structure is deuterium; methyl group; phenyl group; Or substituted or unsubstituted with a cyano 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 the exemplary embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-3.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3,

Z, R1, R2, L, a, X1 to X3, G1 and G2 are the same as defined in Formula 1.

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

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

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

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 exemplary embodiment of the present specification may be prepared as shown in the following reaction scheme, the substituents may be combined by methods known in the art, and the type, position or number of the substituents may be determined in the art. It can be changed according to the known technique.

<reaction formula>

In the above reaction formula,

Z, L, a, R1, R2, G1, G2 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 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 organic material layer of the organic material layer provides an organic light-emitting device including the above-described heterocyclic compound.

The organic light emitting device of the present specification is prepared by 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 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 metal oxide having conductivity or an alloy thereof is deposited on the substrate. It may 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 may be manufactured 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 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 application method refers to spin coating, dip coating, doctor blading, inkjet printing, screen printing, spray method, roll coating, and the like, but is not limited thereto.

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 multilayer structure including a hole injection layer, a hole transport layer, a layer that injects and transports holes at the same time, an electron suppression layer, a light emitting layer and an electron transport layer, an electron injection layer, a layer that simultaneously injects and transports electrons, etc. However, the present invention is not limited thereto and may have a single-layer structure. In addition, the organic layer is formed using a variety of polymer materials in a smaller number by a solvent process rather than a vapor deposition method, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer method. It can be made 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 injects and transports electrons, and the electron injection layer, the electron transport layer, or a layer that simultaneously injects and transports electrons and the heterocyclic compound.

In an exemplary 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 the exemplary 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 diode of the present specification may have the structure shown in FIGS. 1 to 4 , but is not limited thereto.

1 illustrates a structure of an organic light emitting diode 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 the organic light emitting device stacked in this order is exemplified. 2 is an exemplary structure according to an embodiment of the present specification, and may further include another organic material layer.

3 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, an electron injection and The structure of the 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 the organic light emitting device in which the electron injection and 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.

Specifically, the organic light emitting device may have, for example, the following stacked structure 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 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 blocking layer / light emitting layer / hole blocking layer / electron transport layer / electron injection layer / cathode

In an exemplary 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 comprising different materials.

The anode is an electrode for injecting holes, and as the anode material, a material having a large 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, 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 the cathode material is preferably a material having a small work function 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; and a multi-layered material such as LiF/Al or LiO ₂ /Al, but is not limited thereto.

The hole injection layer is a layer that facilitates injection of holes from the anode to the light emitting layer. As the hole injection material, holes can be well injected from the anode at a low voltage, and the highest occupied (HOMO) of the hole injection material is The molecular orbital) is preferably between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Examples of the hole injection material include metal porphyrine, oligothiophene, arylamine-based organic material, hexanitrile hexaazatriphenylene-based organic material, quinacridone-based organic material, and perylene-based organic material. Organic materials, carbazole-based organic materials, fluorene-based organic materials, anthraquinone, polyaniline and polythiophene-based conductive polymers, etc., but are not limited thereto. Specifically, as the hole injection material, a compound including a substituted or unsubstituted carbazole and a 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. When the thickness of the hole injection layer is 1 nm or more, there is an advantage in that the hole injection characteristics can be prevented from being deteriorated, and when it is 150 nm or less, the thickness of the hole injection layer is too thick, so that the driving voltage is increased to improve hole movement There are advantages to avoiding this.

The hole transport layer may serve to facilitate hole transport. As the hole transport material, a material capable of transporting holes from the anode or the hole injection layer to the light emitting layer is suitable, and a material having high hole mobility is suitable. Examples of the hole transport material include an arylamine-based organic material, a carbazole-based organic material, a quinoxaline-based organic material, a fluorene-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together. is not limited to Specifically, the hole transport material includes, but is not limited to, a quinoxazoline-based compound and an arylamine-based compound.

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

An electron blocking layer may be provided between the hole transport layer and the light emitting layer. For the electron-blocking layer, the above-described compound or a material 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 compound, dimerized styryl compound, BAlq, 10-hydroxybenzoquinoline-metal compound, benzoxazole-based compound, benz There are thiazole-based compounds, benzimidazole-based compounds, poly(p-phenylenevinylene) (PPV)-based polymers, spiro compounds, polyfluorene and rubrene, etc., but are limited to these no.

In an exemplary 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, heterocyclic-containing compounds, and the like. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., 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, PIQIr(acac)(bis(1-phenylisoquinoline)acetylacetonateiridium), PQIr(acac)(bis(1-phenylquinoline)acetylacetonate iridium), PQIr(tris(1-phenylquinoline)iridium), PtOEP(octaethylporphyrin platinum) and The same phosphorescent material or a _{fluorescent material such as Alq 3} (tris(8-hydroxyquinolino)aluminum) may be used, but is not limited thereto. When the emission layer emits green light, a _{phosphor 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 emission dopant. However, the present invention is not limited thereto. When the light emitting layer emits blue light, as a light emitting dopant, (4,6-F ₂ ppy) ₂ Irpic, spiro-DPVBi, spiro-6P, distylbenzene (DSB), distrylarylene (DSA), PFO-based polymer , PPV-based, pyrene-based, arylamine-based compounds, etc. may be used, but is 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 the transport of electrons. As the electron transport material, a material capable of receiving electrons from the cathode and transferring them to the light emitting layer is suitable, and a material having high electron mobility is suitable. Specific examples include, but are not limited to, an Al complex of 8-hydroxyquinoline _{, a complex including Alq 3} , an organic radical compound, an anthracene-based compound, an imidazole-based compound, and a hydroxyflavone-metal complex. 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 that the electron transport properties can be prevented from being deteriorated, and if it is 50 nm or less, the thickness of the electron transport layer is too thick to prevent the driving voltage from being raised to improve the movement of electrons. There are advantages that can be

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

In an exemplary embodiment of the present specification, the organic material layer including 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 electron injection and The layer that simultaneously transports electrons further includes a metal complex.

In the exemplary embodiment of the present specification, examples of the metal complex include _{, but are not limited to, Al complex of 8-hydroxyquinoline (Alq 3} ), LiQ, and a metal complex compound.

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-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, and bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, However, the present invention 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 layer that simultaneously injects and transports electrons 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 the 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 is not limited thereto.

An exemplary embodiment of the present specification is a compound represented by Formula 1; And it provides a composition comprising a metal complex.

Description of the metal complex included in the composition is the same as described above in the electron injection layer, the electron transport layer, or the layer that simultaneously injects and transports electrons.

In an exemplary 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 back emission type, or a double side emission type depending on the material used.

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

production example 1-1: Preparation of compound E1

In a nitrogen atmosphere, E1-A (20 g, 78.7 mmol) and E1-B (27.1 g, 78.7 mmol) were placed in 400 ml of tetrahydrofuran, stirred and refluxed. After that, potassium carbonate (32.6 g, 236.1 mmol) was dissolved in 33 ml of water, stirred sufficiently, and then tetrakistriphenyl-phosphinopalladium (2.7 g, 2.4 mmol) was added. After reaction for 1 hour, after cooling to room temperature, the organic layer and the water layer were separated, and the organic layer was distilled. This was again put in 815 mL of chloroform 20 times to dissolve, 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 from chloroform and ethyl acetate to prepare a white solid compound E1 (24.4 g, 60%, MS: [M+H] + = 518).

production 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 prepared as in the above reaction scheme.

MS: [M+H] ⁺ = 518

production 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 as in the above reaction scheme.

MS: [M+H] ⁺ = 594

production 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 as in the above reaction scheme.

MS: [M+H] ⁺ = 594

production 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 prepared as in the above reaction scheme.

MS: [M+H] ⁺ = 608

production 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 prepared as in the above reaction scheme.

MS: [M+H] ⁺ = 518

production 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 as in the above reaction scheme.

MS: [M+H] ⁺ = 568

production 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 as in the above reaction scheme.

MS: [M+H] ⁺ = 683

production 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 as in the above reaction scheme.

MS: [M+H] ⁺ = 568

production 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 prepared as in the above reaction scheme.

MS: [M+H] ⁺ = 619

production 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 prepared as in the above reaction scheme.

MS: [M+H] ⁺ = 517

production 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 prepared as in the above reaction scheme.

MS: [M+H] ⁺ = 556

production 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 as in the above reaction scheme.

MS: [M+H] ⁺ = 596

production 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 prepared as in the above reaction scheme.

MS: [M+H] ⁺ = 634

production 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 as in the above reaction scheme.

MS: [M+H] ⁺ = 608

production example 1-16: Preparation of compound E16

Compound E16 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.

MS: [M+H] ⁺ = 535

production example 1-17: Preparation of compound E17

Compound E17 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.

MS: [M+H] ⁺ = 640

production example 1-18: Preparation of compound E18

Compound E18 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.

MS: [M+H] ⁺ = 609

production example 1-19: Preparation of compound E19

Compound E19 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.

MS: [M+H] ⁺ = 659

production example 1-20: Preparation of compound E20

Compound E20 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.

MS: [M+H] ⁺ = 684

production example 1-21: Preparation of compound E21

Compound E21 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.

MS: [M+H] ⁺ = 660

production example 1-22: Preparation of compound E22

Compound E22 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.

MS: [M+H] ⁺ = 526

production example 1-23: Preparation of compound E23

Compound E23 was prepared in the same manner as in Preparation Example 1-1, except that each starting material was prepared as in the above reaction scheme.

MS: [M+H] ⁺ = 660

[ Example 1-1]

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, it was transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

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

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

On the light emitting layer, the compound E1 prepared in Preparation Example 1-1 and the following LiQ compound were vacuum deposited in a weight ratio of 1:1 to form an electron injection and transport layer to 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 the organic material was maintained at 0.4 Å/sec to 0.9 Å/sec, the deposition rate of lithium fluoride of the negative electrode was 0.3 Å/sec, and the deposition rate of aluminum was 2 Å/sec, and the vacuum degree during deposition was By maintaining 1×10 ^-7 torr to 5×10 ^-5 torr, an organic light emitting diode was manufactured.

Example 1-2 to 1-23

An organic light emitting diode was manufactured in the same manner as in Example 1-1, except that compounds E2 to E23 of Table 1 were used instead of compound E1 of Example 1-1, respectively.

comparative example 1-1 to 1-10

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

For the organic light emitting diodes prepared in Examples 1-1 to 1-23 and Comparative Examples 1-1 to 1-10, the driving voltage and luminous efficiency were measured at a current density of ^{10 mA/cm 2 , and 20 mA/cm 2} The time (T90) at which the current density becomes 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) Life (h)
T90 at 20 mA/cm ² ) Example 1-1 E1 4.36 5.01 (0.140, 0.092) 122 Example 1-2 E2 4.58 5.31 (0.140, 0.093) 105 Examples 1-3 E3 4.80 5.61 (0.140, 0.093) 83 Examples 1-4 E4 4.23 5.26 (0.141, 0.092) 112 Examples 1-5 E5 4.41 4.86 (0.140, 0.092) 151 Examples 1-6 E6 4.19 5.21 (0.140, 0.093) 119 Examples 1-7 E7 4.19 5.26 (0.140, 0.093) 99 Examples 1-8 E8 4.32 4.91 (0.141, 0.092) 126 Examples 1-9 E9 4.27 5.11 (0.140, 0.092) 93 Examples 1-10 E10 4.40 4.91 (0.140, 0.093) 172 Examples 1-11 E11 4.67 5.20 (0.140, 0.093) 95 Examples 1-12 E12 4.49 4.71 (0.140, 0.092) 157 Examples 1-13 E13 4.45 4.96 (0.140, 0.093) 129 Examples 1-14 E14 4.40 4.94 (0.140, 0.093) 137 Examples 1-15 E15 4.41 4.98 (0.140, 0.092) 131 Examples 1-16 E16 4.31 5.13 (0.140, 0.093) 102 Examples 1-17 E17 4.53 5.24 (0.140, 0.093) 107 Examples 1-18 E18 4.58 5.34 (0.141, 0.092) 90 Examples 1-19 E19 4.62 5.41 (0.140, 0.092) 88 Examples 1-20 E20 4.42 4.93 (0.140, 0.093) 139 Example 1-21 E21 4.65 4.64 (0.140, 0.093) 190 Example 1-22 E22 4.32 4.91 (0.140, 0.092) 125 Example 1-23 E23 4.62 5.43 (0.140, 0.093) 109 Comparative Example 1-1 ET-A 4.42 4.36 (0.140, 0.093) 19 Comparative Example 1-2 ET-B 4.51 4.27 (0.141, 0.092) 28 Comparative Example 1-3 ET-C 4.36 4.31 (0.140, 0.092) 23 Comparative Example 1-4 ET-D 4.98 4.32 (0.140, 0.093) 52 Comparative Example 1-5 ET-E 4.72 4.24 (0.140, 0.093) 14 Comparative Example 1-6 ET-F 4.74 3.56 (0.141, 0.092) 74 Comparative Example 1-7 ET-G 5.08 3.50 (0.140, 0.092) 78 Comparative Examples 1-8 ET-H 4.84 3.28 (0.140, 0.093) 95 Comparative Example 1-9 ET-I 5.24 2.56 (0.140, 0.093) 75 Comparative Example 1-10 ET-J 5.34 2.24 (0.141, 0.092) 18

As shown in Table 1, the compound represented by Formula 1 according to the present specification may be used in an organic material layer capable of simultaneously injecting and transporting electrons of the organic light emitting device.

Comparing Examples 1-1 to 1-23 of Table 1 and Comparative Examples 1-1, 1-2 and 1-5, the organic light emitting device including the heterocyclic compound of Formula 1 according to the present specification is fluorene It was confirmed that the organic light emitting device including the group-substituted compound showed significantly superior characteristics in terms of lifespan.

Comparing Examples 1-1 to 1-23 of Table 1 and Comparative Examples 1-3 and 1-4, in the organic light emitting device including the heterocyclic compound of Formula 1 according to the present specification, R1 and R2 are aryl groups Or, it was confirmed that the organic light emitting device including a compound having an aromatic ring bonded to each other showed significantly superior characteristics in terms of lifespan.

Comparing Examples 1-1 to 1-23 of Table 1 and Comparative Examples 1-6, the organic light emitting device including the heterocyclic compound of Formula 1 according to the present specification is a heterocyclic compound at the 4th position of xanthene or thioxanthene. It was confirmed that the organic light-emitting device including the compound substituted with a ring group showed significantly superior characteristics in terms of efficiency.

Comparing Examples 1-1 to 1-23 of Table 1 and Comparative Examples 1-7 to 1-10, in the organic light emitting device including the heterocyclic compound of Formula 1 according to the present specification, L is a heterocyclic group It was confirmed that the organic light emitting device including a compound having an aryl group, a three-ring or more aryl group, or a heterocyclic group showed significantly superior properties in terms of efficiency.

[ Example 2-1]

A glass substrate coated with indium tin oxide (ITO) to a thickness of 1000 Å was placed in distilled water in which detergent was dissolved and washed with ultrasonic waves. At this time, a product manufactured by Fischer Co. was used as the detergent, and distilled water that was secondarily filtered with a filter manufactured by Millipore Co. was used as the distilled water. After washing ITO for 30 minutes, ultrasonic cleaning was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed with a solvent of isopropyl alcohol, acetone, and methanol, and after drying, it was transported to a plasma cleaner. In addition, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

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

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

The compound E1 prepared in Preparation Example 1-1 was vacuum deposited on the light emitting layer to a thickness of 50 Å to form a hole blocking layer, and ET-K and the following LiQ compound were vacuum deposited in a weight ratio of 1:1 to a thickness of 300 Å. An 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 the organic material was maintained at 0.4 to 0.9 Å/sec, the deposition rate of lithium fluoride of the negative electrode was maintained at 0.3 Å/sec, and the deposition rate of aluminum was maintained at 2 Å/sec, and the vacuum degree during deposition was 1×10 ^{By maintaining -7} torr to 5×10 ^-5 torr, an organic light emitting diode was manufactured.

Example 2-2 to 2-23

An organic light emitting diode was manufactured in the same manner as in Example 2-1, except that compounds E2 to E23 of Table 2 were used instead of compound E1 of Example 2-1.

comparative example 2-1 to 2-10

An organic light emitting diode was manufactured in the same manner as in Example 2-1, except that compounds ET-A to ET-J in Table 2 below were used instead of compound E1 of Example 2-1.

For the organic light emitting diodes prepared in Examples 2-1 to 2-23 and Comparative Examples 2-1 to 2-10, the driving voltage and luminous efficiency were measured at a current density of ^{10 mA/cm 2 , and 20 mA/cm 2} The time (T90) at which the current density becomes 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) Life (h)
T90 at 20 mA/cm ² ) Example 2-1 E1 4.22 5.18 (0.140, 0.092) 112 Example 2-2 E2 4.13 5.49 (0.140, 0.093) 96 Example 2-3 E3 4.06 5.80 (0.140, 0.093) 76 Example 2-4 E4 4.15 5.29 (0.141, 0.092) 107 Example 2-5 E5 4.27 5.08 (0.140, 0.092) 135 Example 2-6 E6 4.11 5.24 (0.140, 0.093) 113 Example 2-7 E7 4.13 5.44 (0.140, 0.093) 91 Examples 2-8 E8 4.17 5.28 (0.141, 0.092) 107 Examples 2-9 E9 4.13 5.28 (0.140, 0.092) 86 Example 2-10 E10 4.47 4.87 (0.140, 0.093) 173 Example 2-11 E11 4.21 5.38 (0.140, 0.093) 87 Example 2-12 E12 4.47 4.87 (0.140, 0.092) 144 Examples 2-13 E13 4.30 5.13 (0.140, 0.093) 118 Examples 2-14 E14 4.26 5.11 (0.140, 0.093) 125 Examples 2-15 E15 4.26 5.15 (0.140, 0.092) 120 Examples 2-16 E16 4.23 5.16 (0.140, 0.093) 98 Example 2-17 E17 4.09 5.41 (0.140, 0.093) 98 Example 2-18 E18 4.13 5.52 (0.141, 0.092) 82 Examples 2-19 E19 4.04 5.71 (0.140, 0.092) 80 Examples 2-20 E20 4.17 5.24 (0.140, 0.093) 106 Example 2-21 E21 4.86 4.69 (0.140, 0.093) 226 Example 2-22 E22 4.17 5.08 (0.140, 0.092) 114 Example 2-23 E23 4.09 5.62 (0.140, 0.093) 102 Comparative Example 2-1 ET-A 4.27 4.51 (0.140, 0.093) 18 Comparative Example 2-2 ET-B 4.36 4.41 (0.141, 0.092) 25 Comparative Example 2-3 ET-C 4.27 4.34 (0.140, 0.092) 22 Comparative Example 2-4 ET-D 5.29 4.60 (0.140, 0.093) 39 Comparative Example 2-5 ET-E 4.26 4.38 (0.140, 0.093) 13 Comparative Example 2-6 ET-F 4.65 3.58 (0.141, 0.092) 70 Comparative Example 2-7 ET-G 4.59 3.62 (0.140, 0.092) 71 Comparative Example 2-8 ET-H 4.68 3.39 (0.140, 0.093) 87 Comparative Example 2-9 ET-I 5.06 2.64 (0.140, 0.093) 68 Comparative Example 2-10 ET-J 5.16 2.32 (0.141, 0.092) 16

As shown in Table 2, the compound represented by Chemical Formula 1 according to the present specification may be used in an organic material layer capable of simultaneously injecting and transporting electrons of the organic light emitting device.

Comparing Examples 2-1 to 2-2 of Table 2 and Comparative Examples 2-1, 2-2 and 2-5, the organic light-emitting device including the heterocyclic compound of Formula 1 according to the present specification is fluorene It was confirmed that the organic light emitting device including the group-substituted compound showed significantly superior characteristics in terms of lifespan.

Comparing Examples 2-1 to 2-23 of Table 2 and Comparative Examples 2-3 and 2-4, in the organic light emitting device including the heterocyclic compound of Formula 1 according to the present specification, R1 and R2 are aryl groups Or, it was confirmed that the organic light emitting device including a compound having an aromatic ring bonded to each other showed significantly superior characteristics in terms of lifespan.

Comparing Examples 2-1 to 2-23 of Table 2 and Comparative Examples 2-6, the organic light emitting device including the heterocyclic compound of Formula 1 according to the present specification is a xanthene or thioxanthene 4-position heterocyclic compound. It was confirmed that the organic light-emitting device including the compound substituted with a ring group showed significantly superior characteristics in terms of efficiency.

Comparing Examples 2-1 to 2-23 and Comparative Examples 2-7 to 2-10 of Table 2, in the organic light emitting device including the heterocyclic compound of Formula 1 according to the present specification, L is a heterocyclic group It was confirmed that the organic light emitting device including a compound having an aryl group, a three-ring or more aryl group, or a heterocyclic group showed significantly superior properties in terms of efficiency.

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
10: hole blocking layer

Claims (9)

Heterocyclic compound of formula (1):
[Formula 1]

In Formula 1,
b is an integer of 1 to 3, and when b is 2 or more, the structures in parentheses are the same as or different from each other,
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 alkyl group, or combine with each other to form an aliphatic ring;
L is a direct bond; monocyclic arylene group; or a bicyclic arylene group;
a is an integer of 1 to 3, and when a is 2 or more, L of 2 or more are the same as or different from each other,
X1 to X3 are the same as or different from each other, and each independently represent CR3 or N, provided that at least two of X1 to X3 are N;
R3 is hydrogen; a substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group,
G1 and G2 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group. The method according to claim 1, wherein L is a direct bond; phenylene group; Or a naphthylene group, the heterocyclic compound. The heterocyclic compound according to claim 1, wherein Chemical Formula 1 is represented by any one of Chemical Formulas 1-1 to 1-3:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

In Formulas 1-1 to 1-3,
Z, R1, R2, L, a, X1 to X3, G1 and G2 are the same as defined in formula (1). The method according to claim 1, wherein G1 and G2 are the same as or different from each other, and each independently an alkyl group unsubstituted or substituted with one or more selected from the group consisting of deuterium, a cyano group, an alkyl group, an aryl group and a heterocyclic group; an aryl group unsubstituted or substituted with one or more selected from the group consisting of deuterium, a cyano group, an alkyl group, an aryl group, and a heterocyclic group; Or a heterocyclic compound that is a heterocyclic group unsubstituted or substituted with one or more selected from the group consisting of deuterium, a cyano group, an alkyl group, an aryl group, and a heterocyclic group. The heterocyclic compound according to claim 1, wherein 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 at least one organic material layer provided between the first electrode and the second electrode, wherein at least one layer of the organic material layer comprises the heterocyclic compound of any one of claims 1 to 5. device. The method according to claim 6, wherein the organic layer comprises 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 is the heterocyclic compound An organic light emitting device comprising a. The organic light-emitting device according to claim 7, wherein the electron injection layer, the electron transport layer, or the layer for simultaneously injecting and transporting electrons further comprises a metal complex. 7. The method of claim 6,
The organic material layer includes a hole blocking layer, the hole blocking layer is an organic light emitting device that includes the heterocyclic compound.

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