KR20200021428A - Organic light emitting device - Google Patents

Abstract

The present specification provides an organic light emitting device comprising: a first electrode; a second electrode provided to face the first electrode; a light emitting layer provided between the first electrode and the second electrode; and an organic layer including a hole blocking layer. The light emitting layer contains a compound represented by chemical formula 1, and the hole blocking layer contains a compound represented by chemical formula 2.

Description

Organic light emitting device {ORGANIC LIGHT EMITTING DEVICE}

This application claims the benefit of the filing date of Korean Patent Application No. 10-2018-0096922 filed with the Korea Intellectual Property Office on August 20, 2018, the entire contents of which are incorporated herein.

The present specification relates to an organic light emitting device.

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 two electrodes are combined in the organic thin film to form a pair, then disappear and emit light. The organic thin film may be composed of a single layer or multiple layers as necessary.

Most of the materials used in the organic light emitting device are pure organic materials or complex compounds in which organic materials and metals are complexed, and depending on the purpose, hole injection materials, hole transport materials, light emitting materials, electron transport materials, electron injection materials, etc. It 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 which 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, organic materials having n-type properties, that is, organic materials that are easily reduced and have an electrochemically stable state at the time of reduction are mainly used. As the light emitting layer material, a material having a p-type property and an n-type property at the same time, that is, a material having a stable form in both oxidation and reduction states, and excitons formed by recombination of holes and electrons in the light emitting layer are formed. It is preferable that the material having a high luminous efficiency to convert it into light when it is used.

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

Korean Patent Publication No. 10-2017-113808

Herein, an organic light emitting device having low driving voltage, high efficiency and long life characteristics is described.

Herein is a first electrode; A second electrode provided to face the first electrode; And an organic material layer including a light emitting layer and a hole blocking layer provided between the first electrode and the second electrode, wherein the light emitting layer comprises a compound represented by the following Chemical Formula 1, and the hole blocking layer includes: It provides an organic light emitting device comprising a compound represented by the formula (2).

[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,

X is O or S,

Ar is a substituted or unsubstituted aryl group,

Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or combine with an adjacent group to form a substituted or unsubstituted ring,

L1 to L3 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group,

Ar3 and Ar4 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

A is a substituted or unsubstituted tricyclic or higher condensed ring,

k1 to k3 are each an integer of 0 to 2, and when k1 to k3 are 2, the substituents in the two parentheses are the same as or different from each other,

n1 is an integer of 0 to 4, when n1 is 2 or more, two or more Ar1 are the same as or different from each other,

n2 is an integer of 0 to 8, and when n2 is 2 or more, two or more Ar2 are the same as or different from each other.

The organic light emitting device of the present invention includes the compound represented by the formula (1) in the light emitting layer, and by including the compound represented by the formula (2) in the hole blocking layer, it is possible to obtain an organic light emitting device having a low driving voltage, high efficiency and long life. Specifically, by including a compound represented by the formula (1) including a heterocyclic ring in the light emitting layer, it has a characteristic that facilitates the flow of holes in the device. In addition, since the compound represented by Formula 2 has a deep HOMO energy level, when included in the hole blocking layer, the difference between the compound represented by Formula 1 included in the emission layer and the HOMO energy level is large. As a result, it is possible to prevent holes from moving from the light emitting layer to the surrounding layer to form more excitons, and to obtain a high efficiency and long life device.

FIG. 1 shows an example of an organic light emitting device composed of a substrate 1, an anode 2, a light emitting layer 5, a hole blocking layer 6 and a cathode 8. As shown in FIG.
2 shows a substrate 1, an anode 2, a hole injection layer 3, a hole transport layer 4, a light emitting layer 5, a hole blocking layer 6, an electron injection and transport layer 7 and a cathode 8. An example of an organic light emitting device is shown.

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

The organic light emitting device of the present invention comprises a first electrode; A second electrode provided to face the first electrode; And an organic material layer including a light emitting layer and a hole blocking layer provided between the first electrode and the second electrode, wherein the light emitting layer includes a compound represented by Formula 1 below, and the hole blocking layer is represented by Formula 2 below. It includes the compound represented.

By including a compound represented by the following formula (1) in the light emitting layer of the organic light emitting device, and by including a compound represented by the following formula (2) in the hole blocking layer, the organic light emitting device has a low driving voltage, the effect of improving the life of the device Has

[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,

X is O or S,

Ar is a substituted or unsubstituted aryl group,

Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or combine with an adjacent group to form a substituted or unsubstituted ring,

L1 to L3 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group,

Ar3 and Ar4 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

A is a substituted or unsubstituted tricyclic or higher condensed ring,

k1 to k3 are each an integer of 0 to 2, and when k1 to k3 are 2, the substituents in the two parentheses are the same as or different from each other,

n1 is an integer of 0 to 4, when n1 is 2 or more, two or more Ar1 are the same as or different from each other,

n2 is an integer of 0 to 8, and when n2 is 2 or more, two or more Ar2 are the same as or different from each other.

In the present specification, when a part "includes" a certain component, this means that it may further include other components, without excluding other components, unless specifically stated otherwise.

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

Examples of substituents herein are described below, but are not limited thereto.

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

As used herein, the term "substituted or unsubstituted" is deuterium; Halogen group; Cyano group (-CN); Nitro group; Hydroxyl group; Silyl groups; Boron group; Alkyl groups; Amine groups; Cycloalkyl group; Phosphine oxide groups; Aryl group; And it is substituted with one or two or more substituents selected from the group consisting of a heterocyclic group or two or more of the substituents exemplified above are substituted with a substituent, or means that do not have any substituents. For example, "a substituent to which two or more substituents are linked" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are linked.

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

In the present specification, examples of the halogen group include fluorine (-F), chlorine (-Cl), bromine (-Br) or iodine (-I).

In the present specification, the silyl group may be represented by a chemical formula of -SiY _a Y _b Y _c , wherein Y _a , Y _b and Y _c are each hydrogen; Substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group. Specifically, the silyl group includes, but is not limited to, trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, and phenylsilyl group.

In the present specification, the boron group may be represented by a chemical formula of -BY _d Y _e , wherein Y _d and Y _e are each hydrogen; Substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group. The boron group may include, but is not limited to, trimethylboron, triethylboron, tert-butyldimethylboron, triphenylboron, and phenylboron.

In the present specification, the alkyl group may be linear or branched chain, carbon number is not particularly limited, but is preferably 1 to 60. According to an exemplary embodiment, the alkyl group has 1 to 30 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 20 carbon atoms. According to another exemplary embodiment, the alkyl group has 1 to 10 carbon atoms. Specific examples of the alkyl group include methyl group, ethyl group, propyl group, n-propyl group, isopropyl group, butyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, n-pentyl group, hexyl group, n -Hexyl group, heptyl group, n-heptyl group, octyl group, n-octyl group and the like, but are not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, and according to one embodiment, the cycloalkyl group has 3 to 30 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 20 carbon atoms. According to another exemplary embodiment, the cycloalkyl group has 3 to 6 carbon atoms. Specifically, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group and the like, but is not limited thereto.

In the present specification, the aryl group is not particularly limited, but preferably has 6 to 60 carbon atoms, and may be a monocyclic aryl group or a polycyclic aryl group. According to an exemplary embodiment, the aryl group has 6 to 30 carbon atoms. According to an exemplary embodiment, the aryl group has 6 to 20 carbon atoms. The aryl group may be a monocyclic aryl group, but may be a phenyl group, a biphenyl group, a terphenyl group, a quarterphenyl group, or the like, but is not limited thereto. The polycyclic aryl group may be naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, peryllenyl group, triphenyl group, chrysenyl group, fluorenyl group, triphenylenyl group, etc., but is not limited thereto. no.

In the present specification, a fluorenyl group may be substituted, and two substituents may be bonded to each other to form a spiro structure.

,

등의 스피로플루오레닐기,

(9,9-디메틸플루오레닐기), 및

(9,9-디페닐플루오레닐기) 등의 치환된 플루오레닐기가 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

Spirofluorenyl groups, such as these,

(9,9-dimethylfluorenyl group), and

It may be a substituted fluorenyl group such as (9,9-diphenyl fluorenyl group). However, the present invention is not limited thereto.

In the present specification, the heterocyclic group is a ring group containing one or more of N, O, S and Si as heteroatoms, and the carbon number is not particularly limited, but is preferably 2 to 60 carbon atoms. According to an exemplary embodiment, the heterocyclic group has 2 to 30 carbon atoms. Examples of the heterocyclic group include, for example, pyridine group, pyrrole group, pyrimidine group, quinoline group, pyridazinyl group, furan group, thiophene group, imidazole group, pyrazole group, dibenzofuran group, dibenzothiophene group , Carbazole groups, benzocarbazole groups, naphthobenzofuran groups, benzonaphthothiophene groups, indenocarbazole groups and the like, but are not limited thereto.

In the present specification, the amine group may be represented by the formula of -NY _f Y _g , wherein Y _f and Y _g are each hydrogen; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group. The amine group is an alkylamine group; Arylalkylamine group; Arylamine group; Aryl heteroaryl amine group; Alkyl heteroaryl amine group; And it may be selected from the group consisting of a heteroarylamine group, more specifically dimethylamine group; Diphenylamine group; It may be a dicyclohexylamine group and the like, but is not limited thereto.

In the present specification, the phosphine oxide group specifically includes a diphenylphosphine oxide group, dinaphthylphosphine oxide, and the like, but is not limited thereto.

In the present specification, the description of the aforementioned heterocyclic group may be applied except that the heteroaryl group is aromatic.

In the present specification, in a substituted or unsubstituted ring formed by bonding to each other, a “ring” means a hydrocarbon ring; Or hetero ring.

The hydrocarbon ring may be an aromatic, aliphatic or a condensed ring of aromatic and aliphatic, and may be selected from examples of the cycloalkyl group or aryl group except for the divalent group.

In the present specification, the description of the aryl group may be applied except that the aromatic hydrocarbon ring is divalent.

In the present specification, the description of the heterocyclic group may be applied except that the hetero ring is divalent.

In the present specification, the description regarding the heteroaryl group may be applied except that the aromatic hetero ring is divalent.

In the present specification, the description regarding the aryl group may be applied except that the arylene group is divalent.

In the present specification, the description regarding the heteroaryl group may be applied except that the heteroarylene group is divalent.

Hereinafter, Formula 1 will be described in detail.

According to an exemplary embodiment of the present specification, Ar is a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

According to another exemplary embodiment, Ar is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

In another exemplary embodiment, Ar is a substituted or unsubstituted phenyl group; Substituted or unsubstituted naphthyl group; Substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted phenanthrenyl group.

According to another exemplary embodiment, Ar is a phenyl group unsubstituted or substituted with a phenyl group, a naphthyl group or a phenanthrenyl group; A naphthyl group unsubstituted or substituted with a phenyl group, a naphthyl group or a phenanthrenyl group; A biphenyl group unsubstituted or substituted with a phenyl group, a naphthyl group or a phenanthrenyl group; Or a phenanthrenyl group unsubstituted or substituted with a phenyl group, a naphthyl group or a phenanthrenyl group.

In another exemplary embodiment, Ar is a phenyl group unsubstituted or substituted with a naphthyl group or a phenanthrenyl group; A naphthyl group unsubstituted or substituted with a phenyl group; Biphenyl group; Or a phenanthrenyl group.

In another exemplary embodiment, Ar is represented by any one of the following structural formulas.

In the above structural formula, a dotted line means a bonding position.

According to an exemplary embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms; Substituted or unsubstituted silyl group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 60 carbon atoms, or combine with an adjacent group to form a substituted or unsubstituted ring having 2 to 60 carbon atoms.

In one embodiment of the present specification, Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms; Substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or combine with an adjacent group to form a substituted or unsubstituted ring having 2 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, Ar1 is hydrogen; heavy hydrogen; Halogen group; Cyano group; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms; Substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or when n1 is 2 or more, two or more Ar1 combine with each other to form a substituted or unsubstituted heterocyclic ring having 2 to 30 carbon atoms.

In another exemplary embodiment, Ar1 is hydrogen; heavy hydrogen; Halogen group; Cyano group; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms; Substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heterocyclic group having 2 to 30 carbon atoms, or when n1 is 2 or more, two or more Ar1 are bonded to each other to form benzofuran; Benzothiophene; Dihydrobenzofuran; Or dihydrobenzothiophene.

In another exemplary embodiment, Ar1 is hydrogen or deuterium, or when n1 is 2 or more, two or more Ar1 are bonded to each other to form benzofuran; Benzothiophene; Dihydrobenzofuran; Or dihydrobenzothiophene.

In one embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Chemical Formulas 1-1 to 1-4.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In Chemical Formulas 1-1 to 1-4,

X, Ar, Ar2 and n2 are the same as defined in the formula (1),

X 'is O; Or S.

In one embodiment of the present specification, n1 is an integer of 0 to 3, and when n1 is 2 or more, two or more Ar1 are the same as or different from each other.

In one embodiment of the present specification, n1 is an integer of 0 to 2.

In one embodiment of the present specification, n1 is 1 or 2.

According to an exemplary embodiment of the present specification, Ar2 is hydrogen.

In one embodiment of the present specification, n2 is an integer of 0 to 2, and when n2 is 2, two Ar2 are the same as or different from each other.

In another exemplary embodiment, n2 is 0 or 1.

Hereinafter, Formula 2 will be described in detail.

According to an exemplary embodiment of the present specification, the L1 to L3 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group having 6 to 60 carbon atoms.

According to another exemplary embodiment, the L1 to L3 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group having 6 to 30 carbon atoms.

In another exemplary embodiment, L1 to L3 are the same as or different from each other, and each independently a direct bond; Substituted or unsubstituted phenylene group; Substituted or unsubstituted biphenylene group; Substituted or unsubstituted terphenylene group; Or a substituted or unsubstituted naphthylene group.

According to another exemplary embodiment, the L1 to L3 are the same as or different from each other, and each independently a direct bond; Phenylene group; Biphenylene group; Terphenylene group; Or a naphthylene group.

According to another exemplary embodiment, L1 to L3 are the same as or different from each other, and each independently a direct bond or any one of the following structural formulas.

In the above structural formula, a dotted line means a bonding position.

According to the exemplary embodiment of the present specification, k1 is an integer of 0 to 2, and when k1 is 2, two L1 are the same as or different from each other.

According to an exemplary embodiment of the present specification, k1 is 1 or 2.

According to an exemplary embodiment of the present disclosure, wherein k2 is an integer of 0 to 2, when k2 is 2 two L2 are the same as or different from each other.

According to an exemplary embodiment of the present specification, k2 is 1 or 2.

According to an exemplary embodiment of the present disclosure, wherein k3 is an integer of 0 to 2, when k3 is 2 two L3 are the same as or different from each other.

According to an exemplary embodiment of the present specification, k3 is 1 or 2.

According to an exemplary embodiment of the present specification, Ar3 and Ar4 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In one embodiment of the present specification, Ar3 and Ar4 are the same as or different from each other, and are each independently a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

In another exemplary embodiment, Ar3 and Ar4 are the same as or different from each other, and are each independently a substituted or unsubstituted phenyl group; Substituted or unsubstituted biphenyl group; Or a substituted or unsubstituted terphenyl group.

According to another exemplary embodiment, Ar3 and Ar4 are the same as or different from each other, and each independently a phenyl group; Biphenyl group; Or a terphenyl group.

In another exemplary embodiment, at least one of Ar3 and Ar4 is any one of the following structural formulas.

In the above structural formula, a dotted line means a bonding position.

According to an exemplary embodiment of the present specification, A is a substituted or unsubstituted tricyclic or more condensed hydrocarbon ring; Or a substituted or unsubstituted tricyclic or higher condensed hetero ring. As A includes three or more condensed rings, the compound has thermochemical and electrochemical stability, which has advantages in the manufacturing process and life of the organic light emitting device.

In another exemplary embodiment, A is represented by the following Formula A-1.

[Formula A-1]

In Chemical Formula A-1,

또는

이고,X1 is

or

ego,

Y and Z are the same as or different from each other, and each independently hydrogen or deuterium, or combine with each other to form a direct bond or -W- connected ring,

W is C (Ra) (Rb), Si (Rc) (Rd), N (Re), O or S,

Ra, Rb, Rc, Rd, Re and R1 to R18 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or combine with an adjacent group to form a substituted or unsubstituted ring,

인 경우, R1 내지 R10 중 하나와 L3가 연결되고,X1

When, one of R1 to R10 and L3 is connected,

인 경우, R1 내지 R8 및 R11 내지 R18 중 하나와 L3가 연결되며,X1

When is one of R1 to R8 and R11 to R18 and L3 is connected,

* Means the position to be combined.

'인 경우, 상기 화학식 A-1은 하기 화학식 A-1-1과 같은 구조를 이루며, 상기 X1이 '

'인 경우, 상기 화학식 A-1은 하기 화학식 A-1-2와 같은 구조를 이룬다.According to an exemplary embodiment of the present specification, X1 is'

', Formula A-1 has the same structure as in Formula A-1-1, wherein X1 is'

', Formula A-1 has the same structure as in Formula A-1-2.

 [Formula A-1-1]

[Formula A-1-2]

In Chemical Formulas A-1-1 and A-1-2-,

Definitions of R1 to R18, Y and Z are the same as in the general formula (A-1).

According to an exemplary embodiment of the present disclosure, the Y and Z are the same as or different from each other, and each independently hydrogen or deuterium, or directly bonded to each other to form a five-membered ring or bonded to each other to form a hexagonal ring connected by -W- .

In another exemplary embodiment, W is C (Ra) (Rb), Si (Rc) (Rd), N (Re), O, or S.

According to another exemplary embodiment, Ra, Rb, Rc, Rd, and Re are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or combine with adjacent groups to form a substituted or unsubstituted ring.

In another exemplary embodiment, Ra, Rb, Rc, Rd, and Re are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, or Ra, Rb, and Re combine with adjacent groups to form a substituted or unsubstituted hydrocarbon ring.

According to another exemplary embodiment, Ra, Rb, Rc, Rd, and Re are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted phenyl group, Ra and Rb combine with each other to form a substituted or unsubstituted hydrocarbon ring having 12 to 30 carbon atoms, and Re combines with R18 adjacent to each other to form a hetero ring having 6 to 30 heterocyclic rings; .

According to an exemplary embodiment of the present specification, the R1 to R18 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms, or combine with an adjacent group to form a substituted or unsubstituted ring.

According to another exemplary embodiment, R1 to R18 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, or combine with adjacent groups to form a substituted or unsubstituted ring.

According to another exemplary embodiment, R1 to R18 are the same as or different from each other, and each independently hydrogen; Or deuterium or combine with adjacent groups to form a substituted or unsubstituted hydrocarbon ring having 6 to 60 carbon atoms.

In another exemplary embodiment, R1 to R18 are the same as or different from each other, and each independently hydrogen; Or deuterium, or combine with adjacent groups to form a substituted or unsubstituted hydrocarbon ring of 6 to 30 carbon atoms.

R1 to R18 are the same as or different from each other, and each independently hydrogen; Or deuterium, or combine with adjacent groups to form a substituted or unsubstituted benzene ring.

According to an exemplary embodiment of the present specification, A is one of the following structures.

In the above structures,

는 L3와 연결되는 위치를 의미하며, 상기 구조들은 수소; 중수소; 시아노기; 치환 또는 비치환된 알킬기; 치환 또는 비치환된 아릴기; 또는 치환 또는 비치환된 헤테로아릴기로 치환될 수 있다.

Means a position connected to L3, the structures are hydrogen; heavy hydrogen; Cyano group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

The structures are hydrogen; heavy hydrogen; Cyano group; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; Substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, A is one of the following structures.

In the above structures,

The dotted line means a position connected to L3, wherein the structures are hydrogen; heavy hydrogen; Cyano group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

The structures are hydrogen; heavy hydrogen; Cyano group; A substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; Substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

According to an exemplary embodiment of the present specification, Formula 1 is represented by any one of the following compounds.

In one embodiment of the present specification, Chemical Formula 2 is represented by any one of the following compounds.

According to an exemplary embodiment of the present specification, the light emitting layer includes a compound represented by Chemical Formula 1, and further includes a compound represented by Chemical Formula 3 or 4.

[Formula 3]

In Chemical Formula 3,

Cy1 and Cy2 are the same as or different from each other, and each independently a substituted or unsubstituted aromatic hydrocarbon ring; Or a substituted or unsubstituted heterocycle,

L101, L102 and L11 to L14 are the same as or different from each other, and each independently a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,

R101 to R104 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or may be combined with an adjacent group to form a substituted or unsubstituted ring,

Y1 to Y13 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Y4 and Y5 can combine to form a five-membered ring,

m and n are integers of 0 or 1,

at least one of m and n is an integer of 1,

[Formula 4]

In Chemical Formula 4,

Q1 and Q2 are the same as or different from each other, and each independently O, S or C (Rf) (Rg),

R201 to R206, Rf and Rg are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted amine group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,

Cy3 and Cy4 are the same as or different from each other, and each independently a monocyclic or polycyclic substituted or unsubstituted ring,

m1 and m2 are each an integer of 0 to 2, and when m1 and m2 are each 2, the substituents in brackets are the same or different from each other.

According to an exemplary embodiment of the present specification, m and n is 1.

According to an exemplary embodiment of the present specification, the triplet energy value of the compound represented by Formula 1 is less than or equal to the triplet energy value of the compound represented by Formula 2.

According to one embodiment of the present specification, when the compound represented by Chemical Formula 1 is used as a host material of the emission layer, excitons are generated by the combination of holes and electrons injected from the holes and the electron injection layer. In this case, singlet excitons and triplet excitons are formed in a ratio of 1: 3. After energy is transferred from the excitons formed in the host to the dopant material through an energy transfer process, the excited dopant material is returned to the ground state and releases energy. In general, in the case of organic compounds, the transition from the triplet excited state to the singlet ground state is limited because the direction of the spin orbital must be reversed. However, triplet-triplet annihilation of the host material can produce another singlet excitons, which can help improve device efficiency.

Therefore, if the triplet excitons of the host material can be trapped in the light emitting layer to increase the possibility of collision between the triplet and triplet, it can play a big role in increasing the device efficiency. When the triplet energy of the compound represented by Formula 2 is equal to or higher than the triplet energy of the host material represented by Formula 1, triplet energy is discharged to the electron blocking layer including the compound represented by Formula 2 Since it reduces, the efficiency of an element can be raised.

In one embodiment of the present specification, the light emitting layer includes a compound represented by Chemical Formula 1, further includes a compound represented by Chemical Formula 3 or 4, and an LUMO energy level of the compound represented by Chemical Formulas 3 and 4 The absolute value is less than or equal to the absolute value of the LUMO energy level of the compound represented by Formula 1.

In this specification, "energy level" means the magnitude of energy. Therefore, even when the energy level is displayed in the negative (-) direction from the vacuum level, the energy level is interpreted to mean the absolute value of the corresponding energy value. For example, the highest occupied molecular orbital (HOMO) energy level means the distance from the vacuum level to the highest occupied molecular orbital. In addition, the LUMO (lowest unoccupied molecular orbital) energy level means the distance from the vacuum level to the lowest unoccupied molecular orbital.

In the present specification, HOMO (Highest Occupied Molecular Orbital) energy level and LUMO (Lowest Unoccupied Molecular Orbital) energy level were measured as follows.

In order to determine the molecular structure of a chemical, the inputted structure is optimized using density functional theory (DFT). The BPW91 calculation (Becke exchange and Perdew correlation-correlation functional) and the DNP (double numerical basis set including polarization functional) basis set are used for the DFT calculation. BPW91 calculations are described in the papers A. D. Becke, Phys. Rev. A, 38, 3098 (1988) and 'J. P. Perdew and Y. Wang, Phys. Rev. B, 45, 13244 (1992), and the DNP base set is the paper 'B. Delley, J. Chem. Phys., 92, 508 (1990).

Biovia's “DMol3” package can be used to perform calculations using the density function method. Determining the optimal molecular structure using the method given above results in the energy levels that the electrons can occupy. HOMO energy refers to the orbital energy of the highest energy level among the electron-filled molecular orbitals when the neutral state energy is obtained, and LUMO energy corresponds to the lowest energy orbital energy among the molecular orbitals without electrons.

* HOMO / LUMO calculation

Experimentally, the HOMO energy level uses IP (Ionization Potential) value (Equation-1) measured using UPS (ultraviolet photoemission spectroscopy), and the LUMO energy level is generally an optical gap in the HOMO energy level. Use the value minus (Equation-2 below).

[Equation-1]

HOMO = IP (Ionization Potential)

[Equation-2]

LUMO = IP-Optical Gap

Computationally, we provide HOMO and LUMO in theoretical neutral state and the values calculated in the following two methods according to actual measured values in the experiment.

Method 1) Using IP and Optical Gap

According to the method obtained in the experiment, the IP and the optical gap of the X molecule are obtained using the following equations-3 and-4.

Equation-3

IP (Ionization potential) = E ^{X +} _cation -E ^x _neutral

[Equation-4]

Optical Gap = E ^S1 _S0 -E ^S0 _S0

'는 기하학(geometry)이 양이온(cation), 음이온(anion) 또는 중성(neutral)으로 최적화된 구조에서 전하(charge)가 0, X⁺, 또는 X^-인 에너지를 의미한다. 즉, 전자친화도는 중성 구조의 가장 안전한 구조의 에너지에서 음이온의 가장 안전한 에너지의 차이를 의미하며, 중성 상태에서 전자 한 개를 추가할 때 방출한 에너지를 의미할 수 있다.In the above formula-3

'Means energy with charge of 0, X ⁺ , or X ⁻ in a structure whose geometry is optimized to cation, anion or neutral. That is, electron affinity means the difference between the safest energy of the anion and the safest energy of the neutral structure, and may mean the energy released when one electron is added in the neutral state.

In Equation 4, S0 denotes a single term of the ground state, S1 denotes a single term of the first excited state, and E ^S1 _S0 denotes a single term energy of the ground state and the 1st excited state. Mean single energy difference, E ^S0 _S0 means energy difference inside the singlet of the ground state. In this case, E ^S0 _S0 means an energy difference due to a change in the geometry of the single term in the ground state. Also, under the assumption that the structural change of S0 and S1 is not large, the energy of absorption and the fluorescence value are similar. Accordingly, the opctical gap corresponds to the S0-S1 gap. The energy of the ground and excited states is based on values calculated using a density function.

Method 2) Using Solid State IP and Optical Gap

When the layer is implemented, since it becomes a solid state rather than a single molecule, the effect at that time is corrected as shown in Equation-5 below in consideration of molecular shape and the like. A value can be obtained, and the LUMO energy level is obtained by substituting this value as the IP value of Equation-2. However, transition metal cannot be calculated.

Equation-5

HOMO calc. = IP + △ (solid / molecule)

△ (solid / molecule) in the equation-5 means the energy difference between the molecular state (solid state) and the solid state (solid state), aspheric (Asphericity), Radius of gyration, molecular weight (Molecular weight) may affect this.

In the present specification, triplet energy can also be calculated using a pan density function. The triplet energy can be obtained through the energy difference of SO-T1, where T1 means the triplet in the first excited state.

The organic light emitting diode of the present specification includes the compound represented by Chemical Formula 1 as a host of the light emitting layer, and the compound represented by Chemical Formula 3 or 4 as a dopant of the light emitting layer. In this case, the content of the dopant is included in 0.5 parts by weight to 10 parts by weight, preferably 1 to 5 parts by weight based on 100 parts by weight of the host. When the dopant is included in the content range in the light emitting layer of the organic light emitting device, the driving voltage of the manufactured organic light emitting device is low, has a long life, and has an excellent luminous efficiency.

According to an exemplary embodiment of the present specification, Cy1 and Cy2 are the same as or different from each other, and each independently a substituted or unsubstituted aromatic hydrocarbon ring; Or a substituted or unsubstituted heterocycle.

According to another exemplary embodiment, the Cy1 and Cy2 are the same as or different from each other, and each independently substituted or unsubstituted aromatic hydrocarbon ring having 6 to 60 carbon atoms; Or a substituted or unsubstituted hetero ring having 2 to 60 carbon atoms.

In another exemplary embodiment, Cy1 and Cy2 are the same as or different from each other, and each independently substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms; Or a substituted or unsubstituted hetero ring having 2 to 30 carbon atoms.

In one embodiment of the present specification, Cy1 and Cy2 may be the same as or different from each other, and each independently may be any one selected from the following structural formulas, and the following structures are alkyl groups having 1 to 20 carbon atoms and aryl having 6 to 60 carbon atoms It may be substituted with one or more substituents selected from the group consisting of groups.

In one embodiment of the present specification, Cy1 and Cy2 are the same as or different from each other, and each independently a dibenzofuran ring; Dibenzothiophene ring; Naphthobenzofuran ring; Naphthobenzothiophene ring; Dimethylfluorene ring; Or a dimethylbenzofluorene ring.

According to an exemplary embodiment of the present specification, the L101, L102 and L11 to L14 are the same as or different from each other, and each independently a direct bond; A substituted or unsubstituted arylene group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroarylene group having 2 to 30 carbon atoms.

In another exemplary embodiment, L101, L102, and L11 to L14 are direct bonds.

According to an exemplary embodiment of the present specification, R101 to R104 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; Substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, or combine with an adjacent group to form a substituted or unsubstituted hetero ring.

According to another exemplary embodiment, R101 to R104 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms; Substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms, or combine with an adjacent group to form a substituted or unsubstituted hetero ring.

In another exemplary embodiment, R101 to R104 are the same as or different from each other, and are each independently substituted with deuterium, fluorine, cyano, trimethylsilyl, an alkyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 30 carbon atoms, or Unsubstituted phenyl group; A biphenyl group unsubstituted or substituted with deuterium, fluorine, cyano group, trimethylsilyl group, alkyl group having 1 to 10 carbon atoms or aryl group having 6 to 30 carbon atoms; Deuterium, fluorine, cyano group, trimethylsilyl group, terphenyl group unsubstituted or substituted with an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms; Naphthyl group which is unsubstituted or substituted with deuterium, fluorine, cyano group, trimethylsilyl group, alkyl group having 1 to 10 carbon atoms or aryl group having 6 to 30 carbon atoms; Fluorenyl groups unsubstituted or substituted with deuterium, fluorine, cyano groups, trimethylsilyl groups, alkyl groups having 1 to 10 carbon atoms or aryl groups having 6 to 30 carbon atoms; Dibenzofuran group unsubstituted or substituted with deuterium, fluorine, cyano group, trimethylsilyl group, alkyl group having 1 to 10 carbon atoms or aryl group having 6 to 30 carbon atoms; Dibenzothiophene group unsubstituted or substituted with deuterium, fluorine, cyano group, trimethylsilyl group, alkyl group having 1 to 10 carbon atoms or aryl group having 6 to 30 carbon atoms; Pyridyl groups unsubstituted or substituted with deuterium, fluorine, cyano groups, trimethylsilyl groups, alkyl groups having 1 to 10 carbon atoms or aryl groups having 6 to 30 carbon atoms; Or a naphthobenzofuran group unsubstituted or substituted with a deuterium, fluorine, cyano group, trimethylsilyl group, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 30 carbon atoms, or a group having 1 to 20 carbon atoms bonded together with an adjacent group. To form a substituted or unsubstituted carbazole group.

In another exemplary embodiment, R101 to R104 are the same as or different from each other, and each independently deuterium, fluorine, cyano group, trimethylsilyl group, methyl group, propyl group or butyl group, phenyl group, naphthyl group or biphenyl group Substituted or unsubstituted phenyl group; Biphenyl groups unsubstituted or substituted with deuterium, fluorine, cyano, trimethylsilyl, methyl, propyl or butyl, phenyl, naphthyl or biphenyl groups; Terphenyl groups unsubstituted or substituted with deuterium, fluorine, cyano, trimethylsilyl, methyl, propyl or butyl, phenyl, naphthyl or biphenyl groups; Naphthyl groups unsubstituted or substituted with deuterium, fluorine, cyano, trimethylsilyl, methyl, propyl or butyl, phenyl, naphthyl or biphenyl groups; Fluorenyl groups unsubstituted or substituted with deuterium, fluorine, cyano, trimethylsilyl, methyl, propyl or butyl, phenyl, naphthyl or biphenyl groups; Dibenzofuran groups unsubstituted or substituted with deuterium, fluorine, cyano, trimethylsilyl, methyl, propyl or butyl, phenyl, naphthyl or biphenyl groups; Dibenzothiophene group unsubstituted or substituted with deuterium, fluorine, cyano group, trimethylsilyl group, methyl group, propyl group or butyl group, phenyl group, naphthyl group or biphenyl group; Pyridyl groups unsubstituted or substituted with deuterium, fluorine, cyano, trimethylsilyl, methyl, propyl or butyl, phenyl, naphthyl or biphenyl groups; Or a naphthobenzofuran group unsubstituted or substituted with deuterium, fluorine, cyano group, trimethylsilyl group, methyl group, propyl group or butyl group, phenyl group, naphthyl group or biphenyl group, or combine with an adjacent group to form a propyl group or a butyl group To form a substituted or unsubstituted carbazole group.

According to an exemplary embodiment of the present specification, Y1 to Y13 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, Y4 and Y5 may be bonded to form a five-membered ring.

According to an exemplary embodiment of the present specification, Y1 to Y13 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted alkyl group.

According to another exemplary embodiment, the Y1 to Y13 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

According to another exemplary embodiment, the Y1 to Y13 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Substituted or unsubstituted methyl group; A substituted or unsubstituted ethyl group; Or a substituted or unsubstituted tert-butyl group.

In one embodiment of the present specification, Y1 to Y13 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Or tert-butyl group.

In one embodiment of the present specification, Y4 and Y5 may be combined to form a pentagonal ring.

According to an exemplary embodiment of the present specification, Formula 3 is represented by the following formula 3-1 or 3-2.

[Formula 3-1]

[Formula 3-2]

In Chemical Formulas 3-1 and 3-2,

L101, L102, L11 to L14, R101 to R104, Y1 to Y13, m and n are the same as defined in Chemical Formula 3,

One of X11 and X12 is a direct bond, the other is O, S, C (R31) (R32) or Si (R33) (R34),

One of X13 and X14 is a direct bond, the other is O, S, C (R35) (R36) or Si (R37) (R38),

W1 to W4 are the same as or different from each other, each independently N or C (R39), at least one of W1 to W4 is N,

R21 to R39 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or combine with adjacent groups to form a substituted or unsubstituted ring.

According to an exemplary embodiment of the present disclosure, any one of the X11 and X12 is a direct bond, the other is O, S, C (R31) (R32) or Si (R33) (R34).

In one embodiment of the present specification, X11 is O and X12 is a direct bond.

In one embodiment of the present specification, X11 is S and X12 is a direct bond.

In one embodiment of the present specification, X11 is C (R31) (R32), and X12 is a direct bond.

In one embodiment of the present specification, X11 is Si (R33) (R34), and X12 is a direct bond.

In one embodiment of the present specification, X11 is a direct bond, X12 is O.

In one embodiment of the present specification, X11 is a direct bond, X12 is S.

In one embodiment of the present specification, X11 is a direct bond, X12 is C (R31) (R32).

In one embodiment of the present specification, X11 is a direct bond, X12 is Si (R33) (R34).

In one embodiment of the present specification, any one of X13 and X14 is a direct bond, and the others are O, S, C (R35) (R36) or Si (R37) (R38).

In one embodiment of the present specification, X13 is O and X14 is a direct bond.

In one embodiment of the present specification, X13 is S and X14 is a direct bond.

In one embodiment of the present specification, X13 is C (R35) (R36), and X14 is a direct bond.

In one embodiment of the present specification, X13 is Si (R37) (R38), and X14 is a direct bond.

In one embodiment of the present specification, X13 is a direct bond, X14 is O.

In one embodiment of the present specification, X13 is a direct bond, X14 is S.

In one embodiment of the present specification, X13 is a direct bond, and X14 is C (R35) (R36).

In one embodiment of the present specification, X13 is a direct bond, and X14 is Si (R37) (R38).

In one embodiment of the present specification, R39 is hydrogen.

In one embodiment of the present specification, R31 and R32 are the same as or different from each other, and are each independently a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R31 and R32 are the same as or different from each other, and are each independently a methyl group.

In one embodiment of the present specification, R35 and R36 are the same as or different from each other, and are each independently a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R35 and R36 are the same as or different from each other, and are each independently a methyl group.

In one embodiment of the present specification, R33 and R34 are the same as or different from each other, and are each independently a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R33 and R34 are the same as or different from each other, and are each independently a methyl group.

In one embodiment of the present specification, R37 and R38 are the same as or different from each other, and are each independently a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R37 and R38 are the same as or different from each other, and are each independently a methyl group.

In one embodiment of the present specification, R21 to R30 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group, or combine with adjacent groups to form a substituted or unsubstituted aromatic hydrocarbon ring.

In another exemplary embodiment, R21 to R30 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group having 1 to 40 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 40 carbon atoms, or combine with an adjacent group to form a substituted or unsubstituted aromatic hydrocarbon ring having 6 to 30 carbon atoms.

In one embodiment of the present specification, R21 to R30 are hydrogen, or combine with adjacent groups to form a benzene ring.

According to an exemplary embodiment of the present specification, Formula 3 is represented by any one of the following compounds.

According to an exemplary embodiment of the present specification, Q1 and Q2 are the same as or different from each other, and are each independently O, S, or C (Rf) (Rg).

According to an exemplary embodiment of the present specification, the Q1 and Q2 are the same as or different from each other, and each independently O; Or S.

According to an exemplary embodiment of the present specification, Rf and Rg are the same as or different from each other, and each independently represent a substituted or unsubstituted alkyl group having 1 to 20 carbon atoms.

In another exemplary embodiment, Rf and Rg are the same as or different from each other, and are each independently a substituted or unsubstituted methyl group.

In one embodiment of the present specification, R201 to R204 are the same as or different from each other, and each independently hydrogen; Halogen group; Cyano group (-CN); Substituted or unsubstituted alkyl group; Or a substituted or unsubstituted aryl group.

According to another exemplary embodiment, the R201 to R204 are the same as or different from each other, and each independently hydrogen; Halogen group; Cyano group (-CN); A substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 60 carbon atoms.

In another exemplary embodiment, R201 to R204 are the same as or different from each other, and each independently hydrogen; Halogen group; Cyano group (-CN); A substituted or unsubstituted alkyl group having 1 to 30 carbon atoms; Or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms.

According to another exemplary embodiment, the R201 to R204 are the same as or different from each other, and each independently hydrogen; Halogen group; Cyano group (-CN); An alkyl group having 1 to 30 carbon atoms; Or an aryl group having 6 to 30 carbon atoms.

In another exemplary embodiment, R201 to R204 are the same as or different from each other, and each independently hydrogen; Halogen group; Cyano group (-CN); Methyl group; Ethyl group; Profile group; Isopropyl group; Butyl group; tert-butyl group; Pentyl group; Hexyl group; Phenyl group; Biphenyl group; Terphenyl group; Or a naphthyl group.

According to an exemplary embodiment of the present specification, the R201 to R204 is hydrogen or cyano group.

According to an exemplary embodiment of the present specification, the R201 to R204 is hydrogen.

In one embodiment of the present specification, R205 and R206 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group (-CN); Substituted or unsubstituted alkyl group having 1 to 60 carbon atoms; A substituted or unsubstituted cycloalkyl group having 2 to 60 carbon atoms; Substituted or unsubstituted amine group; Substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In another exemplary embodiment, R205 and R206 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted amine group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

According to another exemplary embodiment, R205 and R206 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted amine group; Substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In another exemplary embodiment, R205 and R206 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted amine group; Substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

According to another exemplary embodiment, R205 and R206 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted arylamine group; A substituted or unsubstituted arylheteroarylamine group; Substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

In another exemplary embodiment, R205 and R206 are the same as or different from each other, and each independently hydrogen; An arylamine group unsubstituted or substituted with an alkyl group; An arylheteroarylamine group unsubstituted or substituted with an alkyl group; An aryl group having 6 to 30 carbon atoms unsubstituted or substituted with an aryl group; Or a heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with an alkyl group.

In another exemplary embodiment, R205 and R206 are the same as or different from each other, and each independently hydrogen; An arylamine group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms; An arylheteroarylamine group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms; An aryl group having 6 to 30 carbon atoms substituted or unsubstituted with an aryl group having 6 to 30 carbon atoms; Or a heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms.

According to another exemplary embodiment, R205 and R206 are the same as or different from each other, and each independently hydrogen; A diphenylamine group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms; A phenylnaphthylamine group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms; A biphenylphenylamine group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms; A fluorenylphenylamine group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms; Dibenzofuranphenylamine group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms; A phenyl group unsubstituted or substituted with an aryl group having 6 to 30 carbon atoms; A naphthyl group unsubstituted or substituted with an aryl group having 6 to 30 carbon atoms; Anthracenyl group unsubstituted or substituted with an aryl group having 6 to 30 carbon atoms; Phenanthrenyl group unsubstituted or substituted with an aryl group having 6 to 30 carbon atoms; Or a carbazole group unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms.

In another exemplary embodiment, R205 and R206 are the same as or different from each other, and each independently hydrogen; A diphenylamine group unsubstituted or substituted with one or more from the group consisting of a methyl group and a tert-butyl group; A phenylnaphthylamine group unsubstituted or substituted with one or more from the group consisting of a methyl group and a tert-butyl group; A biphenylphenylamine group unsubstituted or substituted with one or more from the group consisting of a methyl group and a tert-butyl group; A fluorenylphenylamine group unsubstituted or substituted with one or more from the group consisting of a methyl group and a tert-butyl group; A dibenzofuranphenylamine group unsubstituted or substituted with one or more from the group consisting of a methyl group and a tert-butyl group; Phenyl group; Naphthyl group; Anthracenyl group unsubstituted or substituted with a phenyl group; Phenanthrenyl group unsubstituted or substituted with a phenyl group; Or a carbazole group unsubstituted or substituted with a phenyl group.

According to an exemplary embodiment of the present specification, m1 and m2 are each 1 or 2, when m1 is 2, R205 is the same as or different from each other, and when m2 is 2, R206 is the same as or different from each other.

According to an exemplary embodiment of the present specification, Cy3 and Cy4 are the same as or different from each other, and each independently a monocyclic or polycyclic substituted or hydrocarbon ring; Or a monocyclic or polycyclic substituted or unsubstituted hetero ring.

According to another exemplary embodiment, the Cy3 and Cy4 are the same as or different from each other, and each independently a monocyclic or polycyclic substituted or unsubstituted hydrocarbon ring having 6 to 60 carbon atoms; Or a monocyclic or polycyclic substituted or unsubstituted hetero ring having 2 to 60 carbon atoms.

In another exemplary embodiment, Cy3 and Cy4 are the same as or different from each other, and each independently a monocyclic or polycyclic substituted or unsubstituted hydrocarbon ring having 6 to 30 carbon atoms; Or a monocyclic or polycyclic substituted or unsubstituted hetero ring having 2 to 30 carbon atoms.

According to one embodiment, the Cy3 and Cy4 are substituted or unsubstituted benzene ring; Substituted or unsubstituted naphthalene ring; Substituted or unsubstituted benzofuran ring; Substituted or unsubstituted benzothiophene ring; Or a substituted or unsubstituted indene ring.

In yet one embodiment, the Cy3 and Cy4 is a benzene ring; Naphthalene ring; Benzofuran ring; Benzothiophene ring; Or an indene ring substituted with an alkyl group.

According to one embodiment, the Cy3 and Cy4 is a benzene ring; Naphthalene ring; Benzofuran ring; Benzothiophene ring; Or an indene ring substituted with a methyl group.

According to an exemplary embodiment of the present specification, Formula 4 is represented by the following formula 4-1 or 4-2.

[Formula 4-1]

[Formula 4-2]

In Chemical Formulas 4-1 and 4-2,

Q1, Q2, R201 to R204, Cy1 and Cy2 are as defined in Formula 4,

R301, R302 and Ar11 to Ar14 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group.

According to an exemplary embodiment of the present specification, the R301 and R302 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In another exemplary embodiment, R301 and R302 are the same as or different from each other, and are each independently hydrogen; Substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

According to another exemplary embodiment, the R301 and the R302 are the same as or different from each other, and each independently hydrogen; An aryl group having 6 to 30 carbon atoms unsubstituted or substituted with an alkyl group; Or a heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with an alkyl group.

In another exemplary embodiment, R301 and R302 are the same as or different from each other, and are each independently hydrogen; Aryl groups having 6 to 30 carbon atoms; Or a heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms.

According to another exemplary embodiment, the R301 and the R302 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted phenyl group; A substituted or unsubstituted biphenyl group; Substituted or unsubstituted naphthyl group; Substituted or unsubstituted anthracenyl group; Substituted or unsubstituted phenanthrenyl group; It is a carbazole group unsubstituted or substituted by a C1-C20 alkyl group.

In another exemplary embodiment, R301 and R302 are the same as or different from each other, and are each independently hydrogen; Phenyl group; Biphenyl group; Naphthyl group; Anthracenyl group substituted with a phenyl group; Phenanthrenyl group; Carbazole groups; Or a ditert-butylcarbazole group.

According to an exemplary embodiment of the present specification, Ar11 to Ar14 are the same as or different from each other, and each independently hydrogen; Substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

According to another exemplary embodiment, Ar11 to Ar14 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 60 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 60 carbon atoms.

In another exemplary embodiment, Ar11 to Ar14 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 6 to 30 carbon atoms; Or a substituted or unsubstituted heteroaryl group having 2 to 30 carbon atoms.

According to another exemplary embodiment, Ar11 to Ar14 are the same as or different from each other, and each independently an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with an alkyl group; Or a heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with an alkyl group.

In another exemplary embodiment, Ar11 to Ar14 are the same as or different from each other, and each independently an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms; Or a heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with an alkyl group having 1 to 20 carbon atoms.

According to another exemplary embodiment, Ar11 to Ar14 are the same as or different from each other, and each independently an aryl group having 6 to 30 carbon atoms unsubstituted or substituted with one or more from the group consisting of a methyl group and a tert-butyl group; Or a heteroaryl group having 2 to 30 carbon atoms unsubstituted or substituted with one or more from the group consisting of a methyl group and a tert-butyl group.

According to another exemplary embodiment, Ar11 to Ar14 are the same as or different from each other, and each independently a phenyl group unsubstituted or substituted with one or more from the group consisting of a methyl group and a tert-butyl group; A biphenyl group unsubstituted or substituted with one or more from the group consisting of a methyl group and a tert-butyl group; A naphthyl group unsubstituted or substituted with one or more from the group consisting of a methyl group and a tert-butyl group; A fluorenyl group unsubstituted or substituted with one or more from the group consisting of a methyl group and a tert-butyl group; Or a dibenzofuran group unsubstituted or substituted with one or more from the group consisting of a methyl group and a tert-butyl group.

In one embodiment of the present specification, Chemical Formula 4 may be represented by any one of the following structures.

In the present specification, compounds having various energy band gaps may be synthesized by introducing various substituents into the core structures of Chemical Formulas 1 and 2. In addition, in the present invention, the HOMO and LUMO energy levels of the compound may be adjusted by introducing various substituents into the core structure of the above structure.

Compounds of Chemical Formulas 1 and 2 of the present invention may be prepared in the core structure as shown in Schemes 1 and 2, respectively. Substituents may be combined by methods known in the art, and the type, position, and number of substituents may be changed according to techniques known in the art.

Scheme 1

In Scheme 1, X, Ar1, Ar2 and Ar are the same as defined in Formula 1 and Y is halogen, preferably bromo or chloro. The reaction is a Suzuki coupling reaction, preferably performed in the presence of a palladium catalyst, and the reactor for the Suzuki coupling reaction can be modified as known in the art. The manufacturing method may be more specific in the production examples to be described later.

Scheme 2

In Scheme 2, the definitions for L1 to L3, k1 to k3, Ar3, Ar4 and A are as defined in Chemical Formula 3, Y is halogen, preferably bromo or chloro. The reaction is a Suzuki coupling reaction, preferably performed in the presence of a palladium catalyst, and the reactor for the Suzuki coupling reaction can be modified as known in the art. The manufacturing method may be more specific in the production examples to be described later.

The organic light emitting device of the present specification is a conventional organic light emitting device except that the light emitting layer is formed using the compound represented by Chemical Formula 1, and the hole blocking layer is formed using the compound represented by Chemical Formula 2 described above. It can be prepared by the method and material of the preparation.

When the organic light emitting device including the light emitting layer including the compound represented by Chemical Formula 1 and the hole blocking layer including the compound represented by Chemical Formula 2 is formed, the organic material layer may be formed by a solution coating method as well as a vacuum deposition method. Here, the solution coating method means spin coating, dip coating, inkjet printing, screen printing, spraying method, roll coating and the like, but is not limited thereto.

The organic material layer of the organic light emitting device of the present invention may be formed of a single layer structure, but may be formed of a multilayer structure in which two or more organic material layers are stacked. For example, the organic light emitting device of the present invention includes at least one of a hole transport layer, a hole injection layer, an electron blocking layer electron transport and injection layer, an electron transport layer, an electron injection layer, a hole blocking layer, and an electron transport and injection layer as an organic material layer. It may have a structure to. However, the structure of the organic light emitting device is not limited thereto, and may include fewer or more organic layers.

The organic light emitting device of the present invention includes a light emitting layer and a hole blocking layer, the light emitting layer comprises a compound represented by the formula (1), the hole blocking layer comprises a compound represented by the formula (2).

According to one embodiment, the thickness of the light emitting layer including the compound represented by Formula 1 is 50 kPa to 500 kPa, preferably 100 kPa to 400 kPa.

According to one example, the thickness of the hole blocking layer including the compound represented by Formula 2 is 10 kPa to 500 kPa, preferably 20 kPa to 200 kPa.

According to an exemplary embodiment of the present invention, the maximum emission peak of the emission layer is 400 nm to 500 nm.

According to an exemplary embodiment of the present invention, the organic light emitting device further includes one or more light emitting layers. The at least one light emitting layer may further include a compound represented by Formula 3 or 4 as a dopant, respectively.

According to an exemplary embodiment of the present invention, the light emitting layer and the hole blocking layer may be provided in contact with each other. In this case, the contact means that there is no other organic material layer between the light emitting layer and the hole blocking layer.

The organic light emitting device of the present specification includes a hole transporting layer, a hole injection layer, an electron blocking layer, a hole transporting layer and a hole transporting and hole injection simultaneously, an electron injection layer, an electron transporting layer, and an electron transporting and electron injection at the same time in addition to the light emitting layer and the hole blocking layer. It may further comprise one or more of the layers. However, the structure of the organic light emitting device of the present disclosure is not limited thereto and may include a greater number of organic material layers.

In the organic light emitting device of the present invention, the organic material layer may include an electron blocking layer, and the electron blocking layer may be a material known in the art.

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 organic light emitting diode may have a laminate structure as described below, 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 transport layer / light emitting layer / electron transport layer / cathode

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

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

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

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

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

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

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

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

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

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

(14) Anode / hole injection layer / hole transport layer / light emitting layer / hole blocking layer / electron transport layer / electron injection 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

The structure of the organic light emitting device of the present invention may have a structure as shown in FIG. 1 or 2, but is not limited thereto.

1 illustrates a structure of an organic light emitting device in which an anode 2, a light emitting layer 5, a hole blocking layer 6, and a cathode 8 are sequentially stacked on a substrate 1. The emission layer 5 includes the compound represented by Chemical Formula 1, and the hole blocking layer 6 includes the compound represented by Chemical Formula 2 described above.

2 shows the anode 2, the hole injection layer 3, the hole transport layer 4, the light emitting layer 5, the hole blocking layer 6, the electron injection and transport layer 7 and the cathode 8 on the substrate 1. The structure of this sequentially stacked organic light emitting element is illustrated. The emission layer 5 includes the compound represented by Chemical Formula 1, and the hole blocking layer 6 includes the compound represented by Chemical Formula 2 described above.

The organic light emitting device according to the present specification deposits a metal or conductive metal oxide or an alloy thereof on a substrate by using a physical vapor deposition (PVD) method such as sputtering or e-beam evaporation. To form an anode, including one or more layers of a hole injection layer, a hole transport layer, a light emitting layer, an electron blocking layer, an electron transport layer, a hole transport and injection layer, an electron transport layer, an electron transport and injection layer, and an electron injection layer thereon. After forming the organic material layer can be prepared by depositing a material that can be used as a cathode thereon. In addition to the above method, an organic light emitting device may be manufactured by sequentially depositing a cathode material, an organic material layer, and an anode material on a substrate.

The organic material layer includes a hole injection layer, a hole transport layer, a layer for simultaneously injecting holes and transporting holes, an electron blocking layer, a hole blocking layer, a light emitting layer, an electron transporting layer, an electron injection layer, a layer for simultaneously injecting and transporting electrons, and the like. It may have a multilayer structure, but is not limited thereto and may have a single layer structure.

The anode is an electrode for injecting holes, and a material having a large work function is preferable as the anode material so that hole injection can be smoothly performed into an organic material layer. Specific examples of the positive electrode 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); A combination of a metal and an oxide such as ZnO: Al or SnO ₂ : Sb; Conductive polymers such as poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (PEDOT), polypyrrole and polyaniline, and the like, 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 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; Multilayer structure materials such as LiF / Al or LiO ₂ / Al, and the like, but are not limited thereto. In addition, the cathode may be formed of one layer or two layers.

The hole injection layer is a layer that facilitates the injection of holes from the anode to the light emitting layer, and the hole injection material is a material capable of well injecting holes from the anode at a low voltage, HOMO (highest occupied) of the hole injection material The molecular orbital) is preferably between the work function of the positive electrode material and the HOMO of the surrounding organic material layer. Specific 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 materials, anthraquinone and polyaniline and polythiophene-based conductive polymers, but are not limited thereto. The hole injection layer may have a thickness of 1 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 characteristic is prevented from being lowered. When the thickness of the hole injection layer is 150 nm or less, the thickness of the hole injection layer is too thick, so that the driving voltage is increased to improve the movement of holes. There is an advantage that can be prevented.

The hole transport layer may serve to facilitate the transport of holes. As a hole transport material, a material capable of receiving holes from an anode or a hole injection layer and transferring the holes to a light emitting layer is suitable. Specific examples thereof include an arylamine-based organic material, a conductive polymer, and a block copolymer having a conjugated portion and a non-conjugated portion together, 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 material known in the art.

An electron blocking layer may be provided between the hole transport layer and the light emitting layer. The electron blocking layer may be a material known in the art.

The emission layer may emit blue, and may be formed of the compound represented by Chemical Formula 1, and may further include the compound represented by Chemical Formula 3 or 4. The material of the light emitting layer is a material capable of emitting light in the visible light region by transporting and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and corresponds to a material having good quantum efficiency with respect to fluorescence or phosphorescence.

The electron transport layer may serve to facilitate the transport of electrons. As the electron transporting material, a material capable of injecting electrons well from the cathode and transferring the electrons to the light emitting layer is suitable. Specific examples include Al complexes of 8-hydroxyquinoline; Complexes including Alq ₃ ; Organic radical compounds; Hydroxyflavone-metal complexes and the like, but are not limited thereto. The thickness of the electron transport layer may be 1 to 50 nm. If the thickness of the electron transporting layer is 1 nm or more, there is an advantage that the electron transporting property can be prevented from being lowered. If the thickness of the electron transporting layer is 50 nm or less, the thickness of the electron transporting layer is too thick to prevent the driving voltage from increasing to improve the movement of electrons. There is an advantage to this.

The electron injection layer may play a role of smoothly injecting electrons. As the electron injection material, it has the ability of transporting 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 movement of excitons generated in the light emitting layer to the hole injection layer, and The compound which is excellent in thin film formation ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone and the derivatives thereof, metal Complex compounds, nitrogen-containing five-membered ring derivatives, and the like, 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-hydroxybenzo [h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-cresolato) gallium, bis (2-methyl-8-quinolinato) (1-naphtholato) aluminum, bis (2-methyl-8-quinolinato) (2-naphtolato) gallium, etc. It is not limited to this.

The hole blocking layer is a layer that blocks the reaching of the cathode of the hole, and may be provided between the electron transport layer and the light emitting layer, and may be generally formed under the same conditions as the hole injection layer. Specifically, although there may be an oxadiazole derivative, a triazole derivative, a phenanthroline derivative, a BCP, an aluminum complex, and the like, the compound represented by Formula 2 may be included.

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

Hereinafter, the present invention will be described in detail with reference to Examples and Comparative Examples. However, the examples and comparative examples according to the present disclosure may be modified in many different forms, and the scope of the present specification is not interpreted to be limited to the examples and comparative examples described below. The examples and comparative examples herein are provided to more fully describe the present specification to those skilled in the art.

Preparation Example 1 Preparation of Compound 1-1

10 g (1 equivalent) of Compound A1-1 and 5.53 g (1 equivalent) of Compound B1-1 were added to tetrahydrofuran (150 mL). 2M K ₂ CO ₃ (100 mL), tris (dibenzylideneacetone) dipalladium (0) (Pd (dba) ₂ , 0.6 g), and tetracyclohexylphosphine (PCy _3, 0.6 g) were added thereto. It was stirred and refluxed for 5 hours. After cooling to room temperature, the solid produced by filtration was recrystallized with chloroform and ethanol to prepare 9.8 g (yield 80%) of the compound 1-1.

MS: [M + H] ⁺ = 471

Preparation Example 2 Preparation of Compound 1-2

10 g (1 equivalent) of Compound A1-2 and 4.62 g (1 equivalent) of Compound B1-2 were added to tetrahydrofuran (150 mL). 2M K ₂ CO ₃ (100 mL), tris (dibenzylideneacetone) dipalladium (0) (Pd (dba) ₂ , 0.6 g), and tetracyclohexylphosphine (PCy _3, 0.6 g) were added thereto. It was stirred and refluxed for 5 hours. After cooling to room temperature, the solid produced by filtration was recrystallized with chloroform and ethanol to prepare 9.3 g (yield 78%) of the above compound 1-2.

MS: [M + H] ⁺ = 547

Preparation Example 3 Preparation of Compound 1-3

10 g (1 equivalent) of Compound A1-3 and 4.15 g (1 equivalent) of Compound B1-3 were added to tetrahydrofuran (150 mL). 2M K ₂ CO ₃ (100 mL), tris (dibenzylideneacetone) dipalladium (0) (Pd (dba) ₂ , 0.6 g), and tetracyclohexylphosphine (PCy _3, 0.6 g) were added thereto. It was stirred and refluxed for 5 hours. After cooling to room temperature, the solid produced by filtration was recrystallized with chloroform and ethanol to prepare 7.37 g (yield 72%) of the compound 1-3.

MS: [M + H] ⁺ = 563

Preparation Example 4 Preparation of Compound 1-4

10 g (1 equivalent) of Compound A1-4 and 9.07 g (1 equivalent) of Compound B1-4 were added to tetrahydrofuran (150 mL). 2M K ₂ CO ₃ (100 mL), tris (dibenzylideneacetone) dipalladium (0) (Pd (dba) ₂ , 0.6 g), and tetracyclohexylphosphine (PCy _3, 0.6 g) were added thereto. It was stirred and refluxed for 5 hours. After cooling to room temperature, the solid produced by filtration was recrystallized with chloroform and ethanol to prepare 13.18 g (yield 86%) of the compound 1-4.

MS: [M + H] ⁺ = 511

Preparation Example 5 Preparation of Compound 1-5

10 g (1 equivalent) of Compound A1-5 and 7.28 g (1 equivalent) of Compound B1-5 were added to tetrahydrofuran (150 mL). 2M K ₂ CO ₃ (100 mL), tris (dibenzylideneacetone) dipalladium (0) (Pd (dba) ₂ , 0.6 g), and tetracyclohexylphosphine (PCy _3, 0.6 g) were added thereto. It was stirred and refluxed for 5 hours. After cooling to room temperature, the solid produced by filtration was recrystallized with chloroform and ethanol to prepare 11.21 g (yield 77%) of the compound 1-5.

MS: [M + H] ⁺ = 669

Preparation Example 6 Preparation of Compound 1-6

10 g (1 equivalent) of Compound A1-6 and 7.77 g (1 equivalent) of Compound B1-6 were added to tetrahydrofuran (150 mL). 2M K ₂ CO ₃ (100 mL), tris (dibenzylideneacetone) dipalladium (0) (Pd (dba) ₂ , 0.6 g), and tetracyclohexylphosphine (PCy _3, 0.6 g) were added thereto. It was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was filtered and recrystallized with chloroform and ethanol to prepare 10.16 g (yield 69%) of the compound 1-6.

MS: [M + H] ⁺ = 603

Preparation Example 7 Preparation of Compound 1-7

10 g (1 equivalent) of Compound A1-7 and 8.3 g (1 equivalent) of Compound B1-7 were added to tetrahydrofuran (150 mL). 2M K ₂ CO ₃ (100 mL), tris (dibenzylideneacetone) dipalladium (0) (Pd (dba) ₂ , 0.6 g), and tetracyclohexylphosphine (PCy _3, 0.6 g) were added thereto. It was stirred and refluxed for 5 hours. After cooling to room temperature, the solid produced by filtration was recrystallized with chloroform and ethanol to prepare 12.63 g (yield 84%) of the compound 1-7.

MS: [M + H] ⁺ = 577

Preparation Example 8 Preparation of Compound 2-1

10 g (1 equivalent) of Compound A2-1 and 11 g (1 equivalent) of Compound B2-1 were added to tetrahydrofuran (150 mL). 2M K ₂ CO ₃ (100 mL), tris (dibenzylideneacetone) dipalladium (0) (Pd (dba) ₂ , 0.6 g), and tetracyclohexylphosphine (PCy _3, 0.6 g) were added thereto. It was stirred and refluxed for 5 hours. After cooling to room temperature, the resulting solid was filtered and recrystallized with chloroform and ethanol to prepare 12.9 g (yield 82%) of the compound 2-1.

MS: [M + H] ⁺ = 626

Preparation Example 9 Preparation of Compound 2-2

10 g (1 equivalent) of Compound A2-2 and 11.43 g (1 equivalent) of Compound B2-2 were added to tetrahydrofuran (150 mL). 2M K ₂ CO ₃ (100 mL), Pd (dba) ₂ (0.5 g), and PCy ₃ (0.5 g) were added, followed by stirring and reflux for 5 hours. After cooling to room temperature, the solid produced by filtration was recrystallized with chloroform and ethanol to prepare 12.59 g (yield 75%) of the compound 2-2.

MS: [M + H] ⁺ = 752

Preparation Example 10 Preparation of Compound 2-3

10 g (1 equivalent) of Compound A2-3 and 14.3 g (1 equivalent) of Compound B2-3 were added to tetrahydrofuran (150 mL). 2M K ₂ CO ₃ (100 mL), Pd (dba) ₂ (0.6 g), and PCy ₃ (0.6 g) were added, followed by stirring and reflux for 5 hours. After cooling to room temperature, the solid produced by filtration was recrystallized with chloroform and ethanol to prepare 13.1 g (yield 68%) of the above compound 2-3.

MS: [M + H] ⁺ = 792

Preparation Example 11 Preparation of Compound 2-4

10 g (1 equivalent) of Compound A2-4 and 10.56 g (1 equivalent) of Compound B2-4 were added to tetrahydrofuran (150 mL). 2M K ₂ CO ₃ (100 mL), Pd (dba) ₂ (0.6 g), and PCy ₃ (0.6 g) were added, followed by stirring and reflux for 5 hours. After cooling to room temperature, the solid produced by filtration was recrystallized with chloroform and ethanol to prepare 12.7 g (yield 78%) of the compound 2-4.

MS: [M + H] ⁺ = 789

Preparation Example 12 Preparation of Compound 2-5

10 g (1 equivalent) of Compound A2-5 and 10.6 g (1 equivalent) of Compound B2-5 were added to tetrahydrofuran (150 mL). 2M K ₂ CO ₃ (100 mL), Pd (dba) ₂ (0.5 g), and PCy ₃ (0.5 g) were added, followed by stirring and reflux for 5 hours. After cooling to room temperature, the solid produced by filtration was recrystallized with chloroform and ethanol to prepare Compound 2-5 (12.8 g, yield 82%).

MS: [M + H] ⁺ = 640

Preparation Example 13 Preparation of Compound 2-6

10 g (1 equivalent) of the compound A2-3 and 12.4 g (1 equivalent) of the compound B2-6 were added to tetrahydrofuran (150 mL). 2M K ₂ CO ₃ (100 mL), Pd (dba) ₂ (0.6 g), and PCy ₃ (0.6 g) were added, followed by stirring and reflux for 5 hours. After cooling to room temperature, the solid produced by filtration was recrystallized with chloroform and ethanol to prepare 15.0 g (yield 86%) of the compound 2-6.

MS: [M + H] ⁺ = 716

Preparation Example 14 Preparation of Compound 3-1

2.9 g (1 equiv. 3.90 mmol), B3-1 2.23 g, (2.2 equiv.) Sodium tert-butoxide 1.87 g (5 equiv.), Bis (tri-tert-butylphosphine) in a 0.1 L flask in a nitrogen atmosphere 0.20 g (0.1 equiv) of palladium (0) was added to 50 mL of toluene and refluxed and stirred. After the reaction was completed, the mixture was cooled to room temperature, extracted with toluene and water, and the water layer was removed. After treatment with anhydrous magnesium sulfate, the residue was filtered and concentrated under reduced pressure. The product was separated and purified by column chromatography, and recrystallized with toluene and normal hexane to obtain 2.1 g of Compound 3-1, (yield 49%).

Mass [M + 1] = 1100

Preparation Example 15 Preparation of Compound 3-2

Compound 3-2 was synthesized in the same manner as in Preparation Example 14 using A3-1 and B3-2.

Mass [M + 1] = 1032

Preparation Example 16 Preparation of Compound 3-3

Sodium tert-butoxide 7.2g, 75.3mmol was put into 80 mL of toluene, B3-3 16.2g, (2.2 equiv.) Was thrown in, and it stirred, A3-2 12.0g, (1 equiv.), Bis (tri-tert- butylforce) Pin) palladium (0) 0.22 g (0.02 equiv) was added and stirred under reflux. After cooling to room temperature, the mixture was extracted with ethyl acetate [EtOAc] and water, and the obtained organic layer was dried over anhydrous magnesium sulfate, concentrated under reduced pressure, and purified by column chromatography (n-Hexane: EtOAc). Compound 3-3 12.5 g (yield 50%) was obtained.

MS: [M + H] < + > = 1169

Experimental Example 1

A glass substrate (corning 7059 glass) coated with ITO (Indium Tin Oxide) at a thickness of 1000 Å was placed in distilled water in which a dispersant was dissolved, and washed with ultrasonic waves. Fischer Co. was used for the detergent, and Millipore Co. Secondary filtered distilled water was used as a filter of the product. After ITO was washed for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After the distilled water was washed, the ultrasonic washing in the order of isopropyl alcohol, acetone, methanol solvent and dried.

Hexanitrile hexaazatriphenylene (HATCN) was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer. After evaporating HT1 (400 kPa), a material for transporting holes thereon, the host compound 1-1 and the dopant compound 3-2 prepared in Preparation Example 1 were vacuumed at a weight ratio of 25: 1 and 300 kPa as the host of the light emitting layer. Deposited. The hole blocking layer was formed by depositing the compound 2-6 prepared on the light emitting layer to a thickness of 50 Å, and vacuum injection of Alq ₃ and LiQ (Lithium Quinolate) at a weight ratio of 1: 1 to form an electron injection and transport layer having a thickness of 310 Å. It was. An organic light emitting device was manufactured by sequentially depositing lithium fluoride (LiF) and aluminum at a thickness of 2,000 Å on the electron injection and transport layer sequentially to form a cathode.

Was maintained at the deposition rate was 0.4 ~ 0.7Å / sec for organic material in the above process, the lithium fluoride of the cathode was 0.3Å / sec, aluminum is deposited at a rate of 2Å / sec, the degree of vacuum upon deposition ⅹ10 2 ^-7 An organic light emitting device was manufactured by maintaining ˜5 × 10 ⁻⁶ torr.

Experimental Examples 1 to 20

The organic light emitting device was manufactured by the same method as Experimental Example 1, except that the compound shown in Table 1 was used as the host, the dopant, and the hole blocking layer in Experimental Example 1, respectively.

Experimental Example Host Dopant Hole blocking layer One Compound 1-1 Compound 3-2 Compound 2-6 2 Compound 1-2 Compound 3-3 Compound 2-5 3 Compound 1-3 Compound 3-1 Compound 2-4 4 Compound 1-4 Compound 3-2 Compound 2-3 5 Compound 1-5 Compound 3-1 Compound 2-2 6 Compound 1-6 Compound 3-3 Compound 2-1 7 Compound 1-7 Compound 3-3 Compound 2-1 8 Compound 1-1 Compound 3-1 Compound 2-5 9 Compound 1-2 Compound 3-3 Compound 2-6 10 Compound 1-3 Compound 3-2 Compound 2-3 11 Compound 1-4 Compound 3-3 Compound 2-4 12 Compound 1-5 Compound 3-1 Compound 2-1 13 Compound 1-6 Compound 3-2 Compound 2-2 14 Compound 1-2 Compound 3-1 Compound 2-5 15 Compound 1-1 Compound 3-3 Compound 2-6 16 Compound 1-1 Compound 3-2 Compound 2-5 17 Compound 1-4 Compound 3-3 Compound 2-2 18 Compound 1-3 Compound 3-3 Compound 2-6 19 Compound 1-6 Compound 3-1 Compound 2-1 20 Compound 1-5 Compound 3-1 Compound 2-4

Comparative Examples 1 to 19

The organic light emitting device was manufactured by the same method as Experimental Example 1, except that the compound shown in Table 2 was used as the host, the dopant, and the hole blocking layer in Experimental Example 1, respectively.

Comparative example Host Dopant Hole blocking layer One Compound 1-1 Compound 3-2 HB-01 2 Compound 1-2 Compound 3-3 HB-01 3 Compound 1-3 Compound 3-1 HB-01 4 Compound 1-4 Compound 3-2 HB-01 5 Compound 1-5 Compound 3-3 HB-01 6 Compound 1-6 Compound 3-1 HB-01 7 Compound 1-7 Compound 3-3 HB-01 8 BH-01 Compound 3-1 Compound 2-4 9 BH-01 Compound 3-2 Compound 2-1 10 BH-01 Compound 3-1 Compound 2-2 11 BH-01 Compound 3-2 Compound 2-5 12 BH-01 Compound 3-1 Compound 2-3 13 BH-01 Compound 3-3 Compound 2-6 14 BH-01 Compound 3-1 Compound 2-5 15 BH-01 Compound 3-3 Compound 2-2 16 BH-01 Compound 3-2 Compound 2-6 17 BH-01 Compound 3-1 Compound 2-1 18 BH-01 Compound 3-2 Compound 2-4 19 BH-01 Compound 3-3 Compound 2-3

As in Experimental Examples 1 to 20 and Comparative Examples 1 to 19, the driving voltage and the luminous efficiency of the organic light emitting diodes manufactured using the respective compounds were measured at a current density of 10 mA / cm ² , and a current of 20 mA / cm ² . The time (LT98) which becomes 98% of initial luminance in density was measured.

The results are shown in Table 3 below.

division Voltage (V)
at 10 mA / cm ² Luminous Efficiency (cd / A)
at 10 mA / cm ² Life Time 98
at 20mA / cm ² Experimental Example 1 3.83 5.30 60 Experimental Example 2 3.85 5.32 62 Experimental Example 3 3.71 5.48 63 Experimental Example 4 3.89 5.26 56 Experimental Example 5 3.88 5.55 59 Experimental Example 6 3.78 5.32 63 Experimental Example 7 3.81 5.39 58 Experimental Example 8 3.86 5.43 56 Experimental Example 9 3.75 5.40 63 Experimental Example 10 3.83 5.54 67 Experimental Example 11 3.86 5.50 62 Experimental Example 12 3.76 5.61 70 Experimental Example 13 3.80 5.38 68 Experimental Example 14 3.74 5.42 65 Experimental Example 15 3.69 5.46 69 Experimental Example 16 3.84 5.39 72 Experimental Example 17 3.68 5.48 68 Experimental Example 18 3.70 5.51 59 Experimental Example 19 3.72 5.49 62 Experimental Example 20 3.67 5.65 61 Comparative Example 1 4.91 4.53 35 Comparative Example 2 4.88 4.63 36 Comparative Example 3 4.78 4.61 34 Comparative Example 4 4.76 4.59 39 Comparative Example 5 4.68 4.62 32 Comparative Example 6 4.70 4.57 40 Comparative Example 7 4.90 4.68 38 Comparative Example 8 4.86 4.70 41 Comparative Example 9 4.69 4.61 43 Comparative Example 10 4.72 4.55 37 Comparative Example 11 4.77 4.70 36 Comparative Example 12 4.79 4.62 42 Comparative Example 13 4.80 4.50 32 Comparative Example 14 4.88 4.62 30 Comparative Example 15 4.82 4.60 36 Comparative Example 16 4.85 4.58 37 Comparative Example 17 4.75 4.50 34 Comparative Example 18 4.76 4.47 40 Comparative Example 19 4.69 4.44 31

As shown in Table 1, Experimental Examples 1 to 20 show the characteristics of the device using the compound of Formula 1 as a host of the light emitting layer, the compound of Formula 2 in the electron transport layer. Comparative Examples 1 to 7 show the properties of the device using only the compound of the formula (1) of the present invention, Comparative Examples 8 to 19 show the properties of the device using only the compound of the formula (2) of the present invention.

In comparison with Comparative Examples 1 to 19, the organic light emitting diodes of Experimental Examples 1 to 20 basically exhibit low voltage, high efficiency, and long life. Specifically, the organic light emitting device of Experimental Examples 1 to 20 compared to Comparative Examples 1 to 19, the voltage is reduced by up to about 25%, the luminous efficiency is increased by up to about 30%, the lifetime is up to about 140% Indicated.

1: substrate
2: anode
3: hole injection layer
4: hole transport layer
5: light emitting layer
6: hole blocking layer
7: electron injection and transport layer
8: cathode

Claims (10)

A first electrode; A second electrode provided to face the first electrode; And an organic material layer including a light emitting layer and a hole blocking layer provided between the first electrode and the second electrode.
The emission layer includes a compound represented by the following formula (1),
The hole blocking layer is an organic light emitting device comprising a compound represented by the following formula (2):
[Formula 1]

[Formula 2]

In Chemical Formulas 1 and 2,
X is O or S,
Ar is a substituted or unsubstituted aryl group,
Ar1 and Ar2 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group, or combine with an adjacent group to form a substituted or unsubstituted ring,
L1 to L3 are the same as or different from each other, and each independently a direct bond; Or a substituted or unsubstituted arylene group,
Ar3 and Ar4 are the same as or different from each other, and each independently a substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
A is a substituted or unsubstituted tricyclic or higher condensed ring,
k1 to k3 are each an integer of 0 to 2, and when k1 to k3 are 2, the substituents in the two parentheses are the same as or different from each other,
n1 is an integer of 0 to 4, when n1 is 2 or more, two or more Ar1 are the same as or different from each other,
n2 is an integer of 0 to 8, and when n2 is 2 or more, two or more Ar2 are the same as or different from each other. The method according to claim 1,
The A is an organic light emitting device represented by the formula A-1:
[Formula A-1]

In Chemical Formula A-1,
X1 is

or

ego,
Y and Z are the same as or different from each other, and each independently hydrogen or deuterium, or combine with each other to form a direct bond or -W- connected ring,
W is C (Ra) (Rb), Si (Rc) (Rd), N (Re), O or S,
Ra, Rb, Rc, Rd, Re and R1 to R18 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or combine with an adjacent group to form a substituted or unsubstituted ring,
X1

When, one of R1 to R10 and L3 is connected,
X1

When is one of R1 to R8 and R11 to R18 and L3 is connected,
* Means the position to be combined. The method according to claim 1,
Wherein A is represented by any one of the following structures:

In the above structures,

Means a position connected to L3, the structures are hydrogen; heavy hydrogen; Cyano group; Substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group. The method according to claim 1,
Ar3 and Ar4 are the same as or different from each other, and each independently an substituted or unsubstituted aryl group having 6 to 60 carbon atoms. The method according to claim 1,
Formula 1 is an organic light emitting device represented by any one of the following compounds:

. The method according to claim 1,
Formula 2 is an organic light emitting device represented by any one of the following compounds:

. The method according to claim 1,
The light emitting layer is an organic light emitting device further comprising a compound represented by the following formula (3) or:
[Formula 3]

In Chemical Formula 3,
Cy1 and Cy2 are the same as or different from each other, and each independently a substituted or unsubstituted aromatic hydrocarbon ring; Or a substituted or unsubstituted heterocycle,
L101, L102 and L11 to L14 are the same as or different from each other, and each independently a direct bond; Substituted or unsubstituted arylene group; Or a substituted or unsubstituted heteroarylene group,
R101 to R104 are the same as or different from each other, and each independently a substituted or unsubstituted alkyl group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group, or may be combined with adjacent groups to form a substituted or unsubstituted ring,
Y1 to Y13 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Nitro group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted silyl group; Substituted or unsubstituted phosphine oxide group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
Y4 and Y5 can combine to form a five-membered ring,
m and n are integers of 0 or 1,
at least one of m and n is an integer of 1,
[Formula 4]

In Chemical Formula 4,
Q1 and Q2 are the same as or different from each other, and each independently O, S or C (Rf) (Rg),
R201 to R206, Rf and Rg are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Cyano group; Substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; Substituted or unsubstituted amine group; Substituted or unsubstituted aryl group; Or a substituted or unsubstituted heteroaryl group,
Cy3 and Cy4 are the same as or different from each other, and each independently a monocyclic or polycyclic substituted or unsubstituted ring,
m1 and m2 are each an integer of 0 to 2, and when m1 and m2 are each 2, the substituents in parentheses are the same or different from each other. The method according to claim 7,
The absolute value of the LUMO energy level of the compound represented by the formula (3) and 4 is less than or equal to the absolute value of the LUMO energy level of the compound represented by the formula (1). The method according to claim 1,
The triplet energy value of the compound represented by Formula 1 is less than or equal to the triplet energy value of the compound represented by Formula 2. The method according to claim 1,
The organic material layer further includes at least one of a hole transport layer, a hole injection layer, an electron blocking layer, a layer for simultaneously transporting holes and holes, an electron injection layer, an electron transport layer, and a layer for simultaneously transporting and transporting electrons. Phosphorescent organic light-emitting device.

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