KR20210093625A - Organic electroluminescent device - Google Patents

Abstract

The present specification relates to an organic electroluminescent element. The organic electroluminescent element comprises a cathode, an anode and a light emitting layer between the cathode and the anode. Therefore, the organic electroluminescent element can increase element efficiency and improve driving voltage features or lifespan features.

Description

Organic electroluminescent device {ORGANIC ELECTROLUMINESCENT DEVICE}

The present specification relates to an organic electroluminescent device.

The organic electroluminescent device has a structure in which an organic thin film is disposed between two electrodes. When a voltage is applied to the organic electroluminescent device having such a structure, electrons and holes injected from the two electrodes combine in the organic thin film to form a pair, and then disappear and emit light. The organic thin film may be composed of a single layer or multiple layers, if necessary.

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

In order to improve the performance, lifespan or efficiency of an organic electroluminescent device, the development of a material for an organic thin film is continuously required.

Korean Publication No. 10-2013-117449

The present specification provides an organic electroluminescent device.

One embodiment of the present specification is a cathode; anode; And an organic electroluminescent device comprising a light emitting layer provided between the cathode and the anode, further comprising an organic material layer provided between the anode and the light emitting layer and comprising a compound of Formula 1, wherein the light emitting layer is of Formula 2 It provides an organic electroluminescent device comprising a compound.

[Formula 1]

In Formula 1,

Ar1 is a substituted or unsubstituted aryl group having 5 to 50 carbon atoms; a substituted or unsubstituted heteroaryl group having 1 to 50 carbon atoms; Or a substituted or unsubstituted amine group,

Ar2 and Ar3 are the same as or different from each other and each independently a substituted or unsubstituted C5 to C50 aryl group; or a substituted or unsubstituted heteroaryl group having 1 to 50 carbon atoms, which are bonded to each other directly or through CRR', O, S or NR, or one of Ar2 and Ar3 is directly or CRR', O, S or CRR', O, S or may be bound through NR;

Ar4 and Ar5 are the same as or different from each other and each independently a substituted or unsubstituted C5 to C50 aryl group; or a substituted or unsubstituted C1 to C50 heteroaryl group, which is bonded to each other directly or through CRR', O, S or NR, or one of Ar4 and Ar5 is directly or CRR', O, S or CRR', O, S or may be bound through NR;

L1 to L3 are the same as or different from each other and each independently a substituted or unsubstituted C5 to C50 arylene group; Or a substituted or unsubstituted C 1 to C 50 heteroarylene group,

a to e are each an integer of 0 to 3,

X is CR11R12, O, S or NR13, p is 0 or 1, and when p is 0, two benzenes bonded to X are directly bonded;

R, R', R11 to R13, R1 and R2 are the same as or different from each other and each independently represent hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 5 to C 50 aryl group, A substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 1 to C 50 heteroaryl group, a substituted or unsubstituted amine group, a substituted or unsubstituted C 1 to C 30 alkylsilyl group, substituted or an unsubstituted C5 to C30 arylsilyl group, a cyano group, a nitro group, a hydroxyl group and a halogen group,

[Formula 2]

In Formula 2,

At least one of A and B is a substituted or unsubstituted two or more aromatic hydrocarbon ring or a substituted or unsubstituted two or more heterocyclic ring, and the rest is a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heterocycle; ,

Ra is hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 5 to C 50 aryl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C A heteroaryl group of 1 to 50, a substituted or unsubstituted amine group, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms, a cyano group, a nitro group, selected from the group consisting of a hydroxyl group and a halogen group,

La is a substituted or unsubstituted arylene group having 5 to 50 carbon atoms; Or a substituted or unsubstituted C 1 to C 50 heteroarylene group,

r and u are each an integer from 1 to 9, q is an integer from 0 to 5,

However, the compound of Formula 2 includes at least one deuterium.

The organic electroluminescent device according to the embodiments described herein can improve device efficiency, driving voltage characteristics, or lifespan characteristics by using the compound of Formula 1 and the compound of Formula 2 in the hole transport region and the light emitting layer, respectively. .

1 and 3 show an organic electroluminescent device according to an embodiment of the present specification.
2 is a TLC-MS graph for calculating the deuterium substitution rate.

Hereinafter, the present specification will be described in detail.

An organic electroluminescent device according to an exemplary embodiment of the present specification includes a cathode; anode; And an organic electroluminescent device comprising a light emitting layer provided between the cathode and the anode, further comprising an organic material layer provided between the anode and the light emitting layer and comprising the compound of Formula 1, wherein the light emitting layer is of Formula 2 compounds.

The organic electroluminescent device according to the embodiment includes the compound of Formula 1 between the anode and the light emitting layer, that is, in the hole transport region, and the compound of Formula 2 is included in the light emitting layer. By including the compound of Formula 1 in the hole transport region of the organic electroluminescent device, it is possible to increase the efficiency of the light emitting layer by speeding injection and transport of holes and maximizing carrier transport into the light emitting layer, and including the compound of Formula 2 in the light emitting layer By doing so, an element having an excellent lifetime can be obtained.

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

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

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

As used herein, the term "substituted or unsubstituted" refers to deuterium; halogen group; cyano group; nitro group; imid; amide group; carbonyl group; ester group; hydroxyl group; a substituted or unsubstituted alkyl group; a substituted or unsubstituted cycloalkyl group; a substituted or unsubstituted alkoxy group; a substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthio group; a substituted or unsubstituted arylthioxy group; A substituted or unsubstituted alkylsulfoxy group; a substituted or unsubstituted arylsulfoxy group; a substituted or unsubstituted alkenyl group; a substituted or unsubstituted silyl group; a substituted or unsubstituted boron group; a substituted or unsubstituted amine group; a substituted or unsubstituted arylphosphine group; a substituted or unsubstituted phosphine oxide group; a substituted or unsubstituted aryl group; And it means that it is substituted with one or two or more substituents selected from the group consisting of a substituted or unsubstituted heterocyclic group, is substituted with a substituent to which two or more of the above-exemplified substituents are connected, or does not have any substituents. For example, "a substituent to which two or more substituents are connected" includes a heteroaryl group substituted with an aryl group; Or it may be an aryl group substituted with a heteroaryl group. In addition, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

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

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

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

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. Although carbon number of an alkoxy group is not specifically limited, It is preferable that it is C1-C30. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, isopentyloxy, n -hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy and the like may be used, but is not limited thereto.

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

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

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

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

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

The number of carbon atoms of the acyl thiooxy group is not particularly limited, but is preferably 1 to 30. Specific examples include methyl thiooxy group, ethyl thiooxy group, tert-butyl thioxy group, hexyl thioxy group, octyl thiooxy group, etc., and the alkyl sulfoxy group includes mesyl, ethyl sulfoxy group, propyl sulfoxy group, butyl sulfoxy group, etc., The present invention is not limited thereto.

In the present specification, the alkenyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2-( naphthyl-1-yl)vinyl-1-yl, 2,2-bis(diphenyl-1-yl)vinyl-1-yl, and the like, but is not limited thereto.

In the present specification, the alkynyl group may be linear or branched, and the number of carbon atoms is not particularly limited, but is preferably 2 to 20. Specific examples include ethynyl, propynyl, butynyl, pentynyl, hexynyl, heptynyl, octynyl, nonynyl and the like, but is not limited thereto.

In the present specification, the silyl group may be an alkylsilyl group or an arylsilyl group, and further may be a trialkylsilyl group or a triarylsilyl group. The number of carbon atoms of the silyl group is not particularly limited, but preferably 1 to 30, the alkylsilyl group may have 1 to 30 carbon atoms, and the arylsilyl group may have 5 to 30 carbon atoms. Specifically, there are trimethylsilyl group, triethylsilyl group, tert-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc., but is not limited thereto. .

In the present specification, the boron group _{may be -BR 100} R ₁₀₁ , wherein R ₁₀₀ and R ₁₀₁ are the same or different, and each independently hydrogen; heavy hydrogen; halogen; nitrile group; a substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; a substituted or unsubstituted C1-C30 linear or branched alkyl group; a substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; And it may be selected from the group consisting of a substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms.

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

In the present specification, the aryl group is not particularly limited, but preferably has 5 to 50 carbon atoms, such as 6 to 30 carbon atoms, and the aryl group may be monocyclic or polycyclic.

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

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it is C10-30. Specifically, the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, triphenyl group, pyrenyl group, phenalenyl group, perylenyl group, chrysenyl group, fluorenyl group, fluoranthenyl group, etc. , but is not limited thereto.

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

,

,

,

,

및

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

,

,

,

,

and

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

The description of the above-described aryl group may be cited except that the arylene group is divalent.

In the present specification, the aryl group in the aryloxy group, the arylthioxy group, the arylsulfoxy group, the N-arylalkylamine group, the N-arylheteroarylamine group, and the arylphosphine group is the same as the above-described aryl group.

The number of carbon atoms of the aryloxy group is not particularly limited, but is preferably 6 to 30. Specific examples include a phenoxy group, p-tolyloxy group, m-tolyloxy group, 3,5-dimethyl-phenoxy group, 2,4,6-trimethylphenoxy group, p-tert-butylphenoxy group, 3-biphenylox Group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryloxy group, 2- anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group, 9-phenanthryloxy group, and the like.

The number of carbon atoms of the arylthioxy group is not particularly limited, but is preferably 5 to 30, more preferably 6 to 30. Specific examples of the arylthioxy group include a phenylthioxy group, a 2-methylphenylthioxy group, a 4-tert-butylphenylthioxy group, and the like, and the arylsulfoxy group includes a benzenesulfoxy group and a p-toluenesulfoxy group, but are limited thereto. it's not going to be

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, or a substituted or unsubstituted diarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group including two or more aryl groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time. For example, the aryl group in the arylamine group may be selected from the examples of the aryl group described above.

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

The heteroaryl group refers to a monovalent aromatic heterocyclic group, and the heteroarylene group refers to a divalent aromatic heterocyclic group. The description of the above-mentioned heterocyclic group may be cited, except that the heteroaryl group and the heteroarylene group are aromatic heterocyclic groups.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, or a substituted or unsubstituted diheteroarylamine group. The heteroarylamine group including two or more heteroaryl groups may include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group at the same time. For example, the heteroaryl group in the heteroarylamine group may be selected from the examples of the heteroaryl group described above.

In the present specification, examples of the heteroaryl group in the N-arylheteroarylamine group and the N-alkylheteroarylamine group are the same as the examples of the heteroaryl group described above.

According to an exemplary embodiment of the present specification, Formula 1 is represented by Formula 11 below:

[Formula 11]

Definitions of the substituents of Chemical Formula 11 are the same as in Chemical Formula 1.

According to an exemplary embodiment of the present specification, Ar1 in Formula 1 is a substituted or unsubstituted aryl group having 5 to 50 carbon atoms; Or a substituted or unsubstituted C 1 to C 50 heteroaryl group.

According to an exemplary embodiment of the present specification, Ar1 in Formula 1 is a substituted or unsubstituted aryl group having 5 to 50 carbon atoms.

According to an exemplary embodiment of the present specification, Ar1 in Formula 1 is an aryl group having 5 to 50 carbon atoms which is unsubstituted or substituted with an alkyl group.

According to an exemplary embodiment of the present specification, Ar1 in Formula 1 is phenyl, biphenyl, terphenyl, naphthyl, fluorenyl unsubstituted or substituted with an alkyl group, or phenanthryl.

According to an exemplary embodiment of the present specification, L3 is an arylene group having 5 to 50 carbon atoms; or a heteroarylene group having 1 to 50 carbon atoms.

According to an exemplary embodiment of the present specification, L3 is a phenylene group, a naphthylene group, or a biphenylrylene group.

According to an exemplary embodiment of the present specification, e is 0 or 1.

According to an exemplary embodiment of the present specification, e is 0.

According to an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently an arylene group having 5 to 50 carbon atoms; or a heteroarylene group having 1 to 50 carbon atoms.

According to an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and are each independently an arylene group having 5 to 50 carbon atoms.

According to an exemplary embodiment of the present specification, L1 and L2 are the same as or different from each other, and each independently represents a phenylene group, a naphthylene group, or a biphenylrylene group.

According to an exemplary embodiment of the present specification, a and b are 0 or 1, respectively.

According to an exemplary embodiment of the present specification, a and b are 1.

According to an exemplary embodiment of the present specification, Ar2 to Ar5 in Formula 1 are the same as or different from each other, and each independently a substituted or unsubstituted C5 to C50 aryl group; Or a substituted or unsubstituted C 1 to C 50 heteroaryl group.

According to an exemplary embodiment of the present specification, Ar2 to Ar5 of Formula 1 are the same as or different from each other, and each independently represent a substituted or unsubstituted C5 to C50 aryl group.

According to an exemplary embodiment of the present specification, Ar2 to Ar5 in Formula 1 are the same as or different from each other, and each independently represents an aryl group having 5 to 50 carbon atoms that is unsubstituted or substituted with an alkyl group.

According to an exemplary embodiment of the present specification, Ar2 to Ar5 of Formula 1 are the same as or different from each other, and each independently phenyl, biphenyl, terphenyl, naphthyl, fluorenyl unsubstituted or substituted with an alkyl group, or phenane It's thrilling.

According to an exemplary embodiment of the present specification, at least one of *-NAr2Ar3 and *-NAr4Ar5 in Formula 1 may be represented by Formula 12 below.

[Formula 12]

In the formula (12),

Z is CR14R15, O, S or NR16, w is 0 or 1, and when w is 0, two benzenes bonded to Z are directly bonded;

R14 to R16, R3 and R4 are the same as or different from each other and each independently represent hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 5 to C 50 aryl group, a substituted or unsubstituted A cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 50 carbon atoms, a substituted or unsubstituted amine group, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted carbon number 5 to 30 are selected from the group consisting of an arylsilyl group, a cyano group, a nitro group, a hydroxyl group and a halogen group, and f and g are each an integer of 0 to 4.

According to an exemplary embodiment of the present specification, Chemical Formula 12 may be represented by the following Chemical Formula 13 or Chemical Formula 14.

[Formula 13]

[Formula 14]

In Formulas 13 and 14, the definition of a substituent is the same as in Formula 12.

According to an exemplary embodiment of the present specification, at least one of *-(L2)bNAr2Ar3 and *-(L1)aNAr4Ar5 of Formula 1 may be represented by Formula 15 below.

[Formula 15]

In the formula (15),

Z is CR14R15, O, S or NR16, w is 0 or 1, and when w is 0, two benzenes bonded to Z are directly bonded;

R14 to R16, R3, R4 and Ar6 are the same as or different from each other and each independently represent hydrogen, deuterium, a substituted or unsubstituted C1-C30 alkyl group, a substituted or unsubstituted C5-C50 aryl group, substituted or unsubstituted A substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 1 to C 50 heteroaryl group, a substituted or unsubstituted amine group, a substituted or unsubstituted C 1 to C 30 alkylsilyl group, a substituted or unsubstituted selected from the group consisting of an arylsilyl group having 5 to 30 carbon atoms, a cyano group, a nitro group, a hydroxyl group and a halogen group, g is an integer from 0 to 4, and h is an integer from 0 to 3.

According to an exemplary embodiment of the present specification, R1 to R4 are hydrogen.

According to an exemplary embodiment of the present specification, Ar6 is an aryl group having 5 to 50 carbon atoms.

According to another exemplary embodiment, Ar6 is a phenyl group.

According to an exemplary embodiment of the present specification, R14 to R16 are the same as or different from each other, and each independently represents an alkyl group having 1 to 30 carbon atoms, or an aryl group having 5 to 60 carbon atoms.

In one embodiment of the present specification, c, d, f, g and h are each 0 or 1.

According to an exemplary embodiment, the compound of Formula 1 may be selected from the following compounds.

According to an exemplary embodiment of the present specification, the organic material layer including the compound of Formula 1 is a hole transport layer.

According to an exemplary embodiment of the present specification, a hole control layer provided between the light emitting layer and the organic material layer including the compound of Formula 1 is further included.

As a material of the hole control layer, a material known in the art may be used. For example, it may be a carbazole derivative, a fluorene derivative, an aryl derivative, a heteroaryl derivative, and the like, but is not limited thereto.

According to an exemplary embodiment of the present specification, the organic material layer including the compound of Formula 1 is provided in contact with the anode.

According to another exemplary embodiment, an additional organic layer is included between the organic layer including the compound of Formula 1 and the anode.

In the embodiment, the hole transport layer preferably has a thickness of 50 nm to 200 nm. In addition, it is preferable that the hole control layer has a thickness of 10 nm to 150 nm.

According to an exemplary embodiment of the present specification, at least one deuterium directly bonded to anthracene of Formula 2 is included.

에 각각 중수소가 1개 이상씩 결합되어 있다.According to an exemplary embodiment of the present specification, the anthracene of Formula 2 and

At least one deuterium is bonded to each.

According to an exemplary embodiment of the present specification, the deuterium substitution rate of Formula 2 is 10% to 100%. More preferably, the deuterium substitution rate of Formula 2 is 30% to 99%, and more preferably 41% to 100%. The light emitting layer of the organic electroluminescent device is a region that emits light and has a large loss of molecules due to energy. Since the carbon-deuterium bond is stronger than the carbon-hydrogen bond, and deuterium has a higher mass value than hydrogen, the zero point energy with carbon is lowered and the energy of the bond is high, so the molecule of the compound of Formula 2 By replacing the carbon-hydrogen bond contained in the carbon-deuterium bond with the carbon-deuterium bond, it is possible to obtain a device having an excellent lifespan by increasing the molecular binding energy.

In the present specification, the deuterium substitution ratio refers to a substitution ratio of deuterium in a molecule, and the following two methods are followed to determine the substitution distribution of deuterium in a molecule. Among the following two methods, TLC-MS is a method for controlling the substitution ratio of deuterium in the process of synthesizing a compound.

1. TLC-MS (Thin-Layer Chromatography/Mass Spectrometry) is used (synthesis process confirmation method)

The substitution rate can be calculated based on the maximum value (max. value) of the distribution of molecular weights at the end of the reaction.

For example, in the case of the compound shown in FIG. 2, 527 is viewed as the median value in the MS graph, and since a total of 21 Hs are substituted with D, it can be calculated as 21/26 * 100 = 81%.

2. Quantitative analysis using NMR

DMF (dimethylformamide) is added as an internal standard, and the D substitution rate can be calculated from the integral amount of 　 total 　 peak using the integration ratio on 1H　NMR.

According to an exemplary embodiment of the present specification, the compound of Formula 2 may be represented by one of Formulas 21 to 23 below.

[Formula 21]

[Formula 22]

[Formula 23]

In Formulas 21 to 23, the definitions of A, B, Ra, La and q are the same as in Formula 2, r' and r" are each an integer of 1 to 8, r"' is an integer of 1 to 7, , q' is an integer from 0 to 5,

At least one of A' and B' is a substituted or unsubstituted two or more aromatic hydrocarbon ring or a substituted or unsubstituted two or more heterocyclic ring, and the remainder is a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heterocyclic ring. is a ring,

Rf and Rg are the same as or different from each other and each independently represent a substituted or unsubstituted C5 to C50 aryl group, or a substituted or unsubstituted C1 to C50 heteroaryl group,

Lb is a substituted or unsubstituted arylene group having 5 to 50 carbon atoms; Or a substituted or unsubstituted C 1 to C 50 heteroarylene group,

However, the compounds of Chemical Formulas 21, 22 and 23 each contain at least one deuterium.

According to an exemplary embodiment of the present specification, Rf and Rg are the same as or different from each other, and each independently a substituted or unsubstituted aryl group having 5 to 50 carbon atoms; It is a substituted or unsubstituted heteroaryl group having 1 to 50 carbon atoms.

According to an exemplary embodiment of the present specification, Rf and Rg are the same as or different from each other, and each independently represents a substituted or unsubstituted C5 to C50 aryl group.

According to an exemplary embodiment of the present specification, Rf and Rg are the same as or different from each other, and each independently represents an aryl group having 5 to 50 carbon atoms that is unsubstituted or substituted with deuterium or an alkyl group.

According to an exemplary embodiment of the present specification, Rf and Rg are the same as or different from each other, and each independently phenyl, biphenyl, terphenyl, naphthyl, fluorenyl unsubstituted or substituted with an alkyl group, phenanthryl, triphenylenyl , or dibenzofuranyl, which may be substituted with deuterium.

According to an exemplary embodiment of the present specification, La and Lb are the same as or different from each other, and each independently an arylene group having 5 to 50 carbon atoms; Or a heteroarylene group having 1 to 50 carbon atoms, which may be substituted with deuterium.

According to an exemplary embodiment of the present specification, La and Lb are the same as or different from each other, and are each independently a phenylene group, a naphthylene group, or a biphenylrylene group, which may be substituted with deuterium.

According to an exemplary embodiment of the present specification, q and q' are 0 or 1, respectively.

According to an exemplary embodiment of the present specification, at least one of A and B is substituted or unsubstituted naphthalene, substituted or unsubstituted benzofuran, substituted or unsubstituted benzothiophene, substituted or unsubstituted indene, substituted or unsubstituted substituted indole, substituted or unsubstituted phenanthrene, or substituted or unsubstituted triphenylene, the remainder being substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted benzofuran, substituted or unsubstituted substituted or unsubstituted indene, substituted or unsubstituted indole, substituted or unsubstituted phenanthrene, or substituted or unsubstituted triphenylene. A and B may be unsubstituted or substituted with a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 5 to C 50 aryl group, or a substituted or unsubstituted C 1 to C 50 heteroaryl group there is.

According to an exemplary embodiment of the present specification, at least one of A' and B' is substituted or unsubstituted naphthalene, substituted or unsubstituted benzofuran, substituted or unsubstituted benzothiophene, substituted or unsubstituted indene, substituted or unsubstituted indole, substituted or unsubstituted phenanthrene, or substituted or unsubstituted triphenylene, the remainder being substituted or unsubstituted benzene, substituted or unsubstituted naphthalene, substituted or unsubstituted benzofuran, substituted or unsubstituted benzothiophene, substituted or unsubstituted indene, substituted or unsubstituted indole, substituted or unsubstituted phenanthrene, or substituted or unsubstituted triphenylene. Wherein A' and B' are substituted or unsubstituted with a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 5 to C 50 aryl group, or a substituted or unsubstituted C 1 to C 50 heteroaryl group can be

는 하기 구조 A 중에서 선택될 수 있다. According to an exemplary embodiment of the present specification,

may be selected from the following structure A.

[Structure A]

Wherein Y and Y' are O, S, NR, CRR',

R and R' are each independently a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 5 to C 50 aryl group, or a substituted or unsubstituted C 1 to C 50 heteroaryl group,

The structure A may be unsubstituted or substituted with deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 5 to C 50 aryl group, or a substituted or unsubstituted C 1 to C 50 heteroaryl group can

는 하기 구조 B 중에서 선택될 수 있다. According to an exemplary embodiment of the present specification,

may be selected from the following structure B.

[Structure B]

The structure B is deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 5 to C 50 aryl group, or a substituted or unsubstituted C 1 to C 50 heteroaryl group substituted or unsubstituted can

According to an exemplary embodiment of the present specification, the compound of Formula 2 may be represented by the following structural formulas.

According to an exemplary embodiment of the present specification, the light emitting layer further includes one or more dopants.

According to an exemplary embodiment of the present specification, the light emitting layer includes two or more types of hosts, and at least one of the hosts is a compound represented by Formula 2 above.

One of the two or more types of hosts may be a compound of Formula 2, and two of them may be a compound of Formula 2. In the case of including a host other than the compound of Formula 2, a host material known in the art may be used. For example, it may be an anthracene derivative, an aryl derivative, etc., but is not limited thereto.

When the light emitting layer includes two types of hosts, the mass ratio of the two types of hosts may be 1:3 to 3:1, preferably 1:2 to 2:1, or 1:1.

According to an exemplary embodiment of the present specification, the emission spectrum of the emission layer including the compound of Formula 2 has λmax within 400 nm to 470 nm.

According to an exemplary embodiment of the present specification, the dopant is a fluorescent dopant.

According to an exemplary embodiment of the present specification, the dopant includes a pyrene-based compound.

According to an exemplary embodiment of the present specification, the dopant includes a non-pyrene-based compound.

According to an exemplary embodiment of the present specification, the non-pyrene-based compound includes a boron-based compound.

According to an exemplary embodiment of the present specification, the dopant may be a compound substituted with deuterium.

According to an exemplary embodiment of the present specification, the dopant is a pyrene-based compound substituted with deuterium, or a non-pyrene-based compound substituted with deuterium.

The organic electroluminescent device according to an exemplary embodiment of the present specification may further include an organic material layer disposed between the light emitting layer and the cathode and including a compound of Formula 3 below.

[Formula 3]

In Formula 3,

X1 to X3 are CR21R22 or N, and at least one of X1 to X3 is N,

Ara to Arc, R21 and R22 are the same or different from each other, and each independently represents hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 5 to C 50 aryl group, substituted or unsubstituted an alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 50 carbon atoms, substituted or an unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C5 to C30 aryloxy group, a substituted or unsubstituted C1 to C30 alkylthioxy group, a substituted or unsubstituted C5 to C30 It is selected from an arylthioxy group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C5-C30 arylsilyl group, a cyano group, a nitro group, a hydroxyl group, and a halogen group.

According to a further exemplary embodiment, the organic material layer including the compound of Formula 3 may further include an organic alkali metal complex. At this time, the organic alkali metal complex may be lithium quinolate or aluminum quinolate, but is not limited thereto, and the content of the organic alkali metal complex is 10 to 90 wt%, preferably 30 to 70 wt%, based on the material of the organic layer. included in %.

The organic material layer of the organic electroluminescent device of the present specification may have a structure further comprising a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an electron control layer, a hole control layer, and the like, in addition to the above-described organic material layer.

In an exemplary embodiment of the present specification, the organic electroluminescent device may be an organic electroluminescent device of a structure (normal type) in which an anode, one or more organic material layers, and a cathode are sequentially stacked on a substrate.

In one embodiment of the present specification, the organic electroluminescent device may be an organic electroluminescent device of an inverted type in which a cathode, one or more organic material layers, and an anode are sequentially stacked on a substrate.

For example, the structure of the organic electroluminescent device according to an exemplary embodiment of the present specification is illustrated in FIGS. 1 and 3 . 1 and 3 illustrate an organic electroluminescent device, but is not limited thereto.

1 illustrates a structure of an organic electroluminescent device 10 in which a substrate 20, an anode 30, a hole transport layer 70, a light emitting layer 40, and a cathode 50 are sequentially stacked.

3 shows a substrate 20, an anode 30, a hole injection layer 60, a hole transport layer 70, a hole control layer 80, a light emitting layer 40, an electron control layer 90, an electron transport layer 100. , the electron injection layer 110 , the cathode 50 and the capping layer 120 are sequentially stacked and the structure of the organic electroluminescent device is exemplified.

The organic electroluminescent device of the present specification may be manufactured using materials and methods known in the art, except for including an organic material layer containing the compound of Formula 1 and a light emitting layer containing the compound of Formula 2.

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

For example, the organic electroluminescent device according to the present specification uses a PVD (physical vapor deposition) method such as sputtering or e-beam evaporation, to form a metal or a metal oxide having conductivity on a substrate or a metal oxide or these An anode is formed by depositing an alloy, and an organic material layer including a hole injection layer, a hole transport layer, a light emitting layer, an electron control layer, a hole control layer, an electron transport layer, an electron injection layer, etc. is formed thereon, and then it can be used as a cathode It can be prepared by depositing a material with In addition to this method, an organic electroluminescent 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 that simultaneously injects and transports electrons, an electron control layer, a hole control layer, a light emitting layer, an electron transport layer, an electron injection layer, and a layer that simultaneously injects and transports electrons. It may have a multi-layer structure, but is not limited thereto and may have a single-layer structure. In addition, the organic layer is formed using a variety of polymer materials in a smaller number by a solvent process rather than a deposition method, such as spin coating, dip coating, doctor blading, screen printing, inkjet printing, or thermal transfer method. It can be made in layers.

The anode is an electrode for injecting holes, and as the anode material, a material having a large work function is preferable so that holes can be smoothly injected into the organic layer. Specific examples of the anode material that can be used in the present invention include metals such as vanadium, chromium, copper, zinc, gold, or alloys thereof; metal oxides such as zinc oxide, indium oxide, indium tin oxide (ITO, Indium Tin Oxide), and indium zinc oxide (IZO, Indium Zinc Oxide); ZnO: Al or SnO ₂ : Combination of metals and oxides such as Sb; conductive polymers such as poly(3-methylthiophene), poly[3,4-(ethylene-1,2-dioxy)thiophene](PEDOT), polypyrrole, and polyaniline, but are not limited thereto.

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

The hole injection layer is a layer that facilitates the injection of holes from the anode to the light emitting layer. As the hole injection material, holes can be well injected from the anode at a low voltage, and the highest occupied (HOMO) of the hole injection material is The molecular orbital) is preferably between the work function of the anode material and the HOMO of the surrounding organic 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 material. of organic substances, anthraquinones, and conductive polymers of polyaniline and polythiophene series, but are not limited thereto. The thickness of the hole injection layer may be 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 characteristics can be prevented from being deteriorated, and when it is 150 nm or less, the thickness of the hole injection layer is too thick, so that the driving voltage is increased to improve hole movement There are advantages to avoiding this.

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

A hole control layer may be provided between the hole transport layer and the light emitting layer. For the hole control layer, a material known in the art may be used.

The light emitting layer may emit red, green, or blue light, and may be made of a phosphorescent material or a fluorescent material. The light emitting material is a material capable of emitting light in the visible ray region by receiving and combining holes and electrons from the hole transport layer and the electron transport layer, respectively, and a material having good quantum efficiency for fluorescence or phosphorescence is preferable.

Examples of the host material for the light emitting layer other than the compound represented by the above formula (2) include a condensed aromatic ring derivative or a heterocyclic compound containing compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, and the like, and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder-type compounds. Furan compounds, pyrimidine derivatives, and the like, but are not limited thereto.

When the emission layer emits red light, the emission dopant is PIQIr(acac)(bis(1-phenylisoquinoline)acetylacetonateiridium), PQIr(acac)(bis(1-phenylquinoline)acetylacetonate iridium), PQIr(tris(1-phenylquinoline)iridium) ), a phosphorescent material such as octaethylporphyrin platinum (PtOEP), or a _{fluorescent material such as Alq 3} (tris(8-hydroxyquinolino)aluminum) may be used, but is not limited thereto. When the light-emitting layer emits green light, the light-emitting dopant is a _{phosphor such as Ir(ppy) 3} (fac tris(2-phenylpyridine)iridium), Alq3(tris(8-hydroxyquinolino)aluminum), anthracene-based compound, or pyrene-based compound. A fluorescent material such as a compound or a boron-based compound may be used, but is not limited thereto. When the light emitting layer emits blue light, the light emitting dopant includes a _{phosphorescent material such as (4,6-F2ppy) 2} Irpic, spiro-DPVBi, spiro-6P, distylbenzene (DSB), distrylarylene (DSA), A fluorescent material such as a PFO-based polymer, a PPV-based polymer, an anthracene-based compound, a pyrene-based compound, or a boron-based compound may be used, but is not limited thereto.

The electron transport layer may serve to facilitate the transport of electrons. As the electron transport material, a material capable of well injecting electrons from the cathode and transferring them to the light emitting layer, and a material having high electron mobility is suitable. Specific examples include Al complex of 8-hydroxyquinoline; complexes containing 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 transport layer is 1 nm or more, there is an advantage that the electron transport characteristics can be prevented from being lowered, and if it is 50 nm or less, the thickness of the electron transport layer is too thick to prevent the driving voltage from being increased to improve the movement of electrons. There are advantages that can be In addition, the compound of Formula 1 described above may be used.

The electron injection layer may serve to facilitate injection of electrons. The electron injection material has the ability to transport electrons, has an electron injection effect from the cathode, an excellent electron injection effect on the light emitting layer or the light emitting material, prevents the movement of excitons generated in the light emitting layer to the hole injection layer, and , a compound having excellent thin film forming ability is preferable. Specifically, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, preorenylidene methane, anthrone, etc., derivatives thereof, metals complex compounds and nitrogen-containing 5-membered ring derivatives, but are not limited thereto. In addition, the above-mentioned compound of Formula 1 may be used.

Examples of the metal complex compound include 8-hydroxyquinolinato lithium, bis(8-hydroxyquinolinato)zinc, bis(8-hydroxyquinolinato)copper, bis(8-hydroxyquinolinato)manganese, Tris(8-hydroxyquinolinato)aluminum, tris(2-methyl-8-hydroxyquinolinato)aluminum, tris(8-hydroxyquinolinato)gallium, bis(10-hydroxybenzo[h] Quinolinato) beryllium, bis (10-hydroxybenzo [h] quinolinato) zinc, bis (2-methyl-8-quinolinato) chlorogallium, bis (2-methyl-8-quinolinato) ( o-crezolato)gallium, bis(2-methyl-8-quinolinato)(1-naphtolato)aluminum, bis(2-methyl-8-quinolinato)(2-naphtolato)gallium, etc. However, the present invention is not limited thereto.

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

For the capping layer, a material known in the art may be used.

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

Hereinafter, the present specification will be described in more detail through examples. However, the following examples are only for illustrating the present specification, and not for limiting the present specification.

[Production Example]

The reactant (leq), Trifluoromethanesulfonic acid (cat.) was put in C ₆ D ₆ (10-50 times the mass ratio of the reactant) and stirred at 70° C. for 1 to 100 minutes. After completion of the reaction, D ₂ O (excess) was added and stirred for 30 minutes, followed by dropwise addition of trimethylamine (excess). The reaction solution was transferred to a separatory funnel, and extracted with water and chloroform. The extract _{was dried over MgSO 4} , and recrystallized by heating with toluene to obtain the products shown in Table 1 below.

compare
heavy hydrogen
compound reactant product reactant
m/z product
theory
max m/z reaction
time
(min) product
real
max m/z entire
number of hydrogens D
substitution
Count D substitution
ratio
(%) synthesis
yield
(%) compound
1-1

470 492 50 490 22 20 91% 65% compound
1-2

470 492 30 486 22 16 73% 70% compound
1-3

546 572 50 569 26 23 88% 71% compound
1-4

570 596 30 590 26 20 77% 65% compound
1-5

470 492 40 489 22 19 86% 66% compound
1-6

622 652 50 649 30 27 90% 71% compound
1-7

546 572 35 567 26 21 81% 70% compound
1-8

596 624 40 619 28 23 82% 75% compound
1-9

520 544 60 543 24 23 96% 69% compound
1-10

570 596 60 594 26 24 92% 68% compound
1-11

520 544 35 538 24 18 75% 63% compound
1-12

510 532 60 531 22 21 95% 66% compound
1-13

560 584 15 572 24 12 50% 65% compound
1-14

586 612 40 607 26 21 81% 67% compound
1-15

560 584 75 584 24 24 100% 70% compound
1-16

586 612 60 610 26 24 92% 70% compound
1-17

596 624 15 609 28 13 46% 65% compound
1-18

560 584 60 580 24 20 83% 69% compound
1-19

470 492 5 478 22 8 36% 65% compound
1-20

520 544 3 527 24 7 29% 69% compound
1-21

560 584 One 563 24 3 13% 65% compound
1-22

622 652 3 628 30 6 20% 71%

Each product had a different degree of deuterium substitution depending on the reaction time, and the substitution rate was determined according to the maximum m/z (M+) value.

Deuterium (-D) bound to the product synthesized in Table 1 means that it can be bound to the indicated position, and does not necessarily mean that it must be bound to the indicated position.

The reactants were synthesized with reference to their prior literatures such as KR 1994238 B1, KR 1670193 B1, KR1754445 B1, and KR 1368164 B1. In addition, for the substitution of deuterium for the above product, the prior literature of KR 1538534 B1 was referred.

The compound of Formula 2 included in the following hole transport region was synthesized with reference to the prior document KR 2019-0070064 A.

[ Example One] OLED manufacture of

As an anode, a substrate on which ITO/Ag/ITO was deposited to a thickness of 70/1000/70Å was cut into a size of 50 mm x 50 mm x 0.5 mm, placed in distilled water in which a dispersant was dissolved, and washed with ultrasonic waves. The detergent used was a product of Fischer Co., and the distilled water was manufactured by Millipore Co. Secondary filtered distilled water was used as a filter of the product. After washing ITO for 30 minutes, ultrasonic washing was performed for 10 minutes by repeating twice with distilled water. After washing with distilled water, ultrasonic washing was performed in the order of isopropyl alcohol, acetone, and methanol, followed by drying.

A hole injection layer was formed by thermal vacuum deposition of HI-1 to a thickness of 50 Å on the prepared anode, and compound 2-1, which is a material for transporting holes synthesized in Preparation Example, was vacuum-deposited to a thickness of 1150 Å to form a hole transport layer. formed. Then, a hole control layer was formed using EB1 (150 Å), and then the host compound 1-1 and dopant BD1 (2 wt %) synthesized in Preparation Example were vacuum deposited to a thickness of 360 Å to form a light emitting layer. . Thereafter, HB1 was deposited by 50 Å to form an electron control layer, and the compound ET1 and Liq were mixed in a ratio of 5:5 (mass ratio) to form an electron transport layer having a thickness of 250 Å. After sequentially forming a film of 50 Å thick magnesium and lithium fluoride (LiF) as an electron injection layer, 200 Å of magnesium and silver (1:4) were formed as an anode, and then CP1 was deposited (capping layer) of 600 Å to complete the device. . In the above process, the deposition rate of the organic material was maintained at 1 Å/sec.

[ Example 2 to 51 and comparative example 1 to 11]

Prepared in the same manner as in Example 1, but compounds 2-1 to 2-9 synthesized in Preparation Example as a hole transport layer material, Compounds 1-1 to 1-22 synthesized in Preparation Example as a host of the emission layer, dopant of the emission layer The experimental device structures of organic electroluminescent devices prepared using BD1 and BD2 as materials are shown in Table 2 below. Specifically, in Examples 2 to 51 and Comparative Examples 1 to 11, the material shown in Table 2 was used instead of the material of Example 1 described in Table 2 below.

Experimental example hole transport area light emitting layer electron transport area hole transport layer hole control layer host dopant electronic control layer electron transport layer Comparative Example 1 HT1 EB1 BH1 BD1 HB1 ET1 Comparative Example 2 HT1 EB1 BH2 BD1 HB1 ET1 Comparative Example 3 HT1 EB1 BH1 BD1 HB1 ET2 Comparative Example 4 HT2 EB1 BH1 BD1 HB1 ET2 Comparative Example 5 HT1 EB2 BH2 BD1 HB1 ET1 Comparative Example 6 HT2 EB3 BH1 BD1 HB1 ET2 Comparative Example 7 HT1 EB1 BH1 BD2 HB1 ET1 Comparative Example 8 compound 2-1 EB1 BH2 BD2 HB1 ET1 Comparative Example 9 HT1 EB1 compound 1-1 BD2 HB1 ET1 Comparative Example 10 HT1 EB1 BH1:BH2
(1:1) BD1 HB1 ET1 Comparative Example 11 HT1 EB1 BH1:BH2
(1:1) BD2 HB1 ET1 Example 1 compound 2-1 EB1 compound 1-1 BD1 HB1 ET1 Example 2 compound 2-1 EB1 compound 1-19 BD1 HB1 ET1 Example 3 compound 2-1 EB1 compound 1-13 BD1 HB1 ET1 Example 4 compound 2-1 EB2 compound 1-14 BD2 HB1 ET1 Example 5 compound 2-1 EB1 compound 1-3 BD2 HB1 ET2 Example 6 compound 2-2 EB3 compound 1-2 BD1 HB1 ET1 Example 7 compound 2-2 EB1 compound 1-9 BD1 HB1 ET1 Example 8 compound 2-2 EB1 compound 1-20 BD1 HB1 ET1 Example 9 compound 2-2 EB2 compound 1-2 BD2 HB1 ET1 Example 10 compound 2-2 EB1 compound 1-10 BD2 HB1 ET1 Example 11 compound 2-3 EB1 compound 1-7 BD1 HB1 ET1 Example 12 compound 2-3 EB3 compound 1-12 BD1 HB1 ET1 Example 13 compound 2-3 EB1 compound 1-16 BD1 HB1 ET1 Example 14 compound 2-3 EB1 compound 1-13 BD2 HB1 ET1 Example 15 compound 2-3 EB2 compound 1-21 BD2 HB1 ET1 Example 16 compound 2-4 EB1 compound 1-15 BD1 HB1 ET1 Example 17 compound 2-4 EB1 compound 1-4 BD1 HB1 ET2 Example 18 compound 2-4 EB1 compound 1-5 BD1 HB1 ET1 Example 19 compound 2-4 EB1 compound 1-6 BD2 HB1 ET1 Example 20 compound 2-4 EB3 compound 1-22 BD2 HB1 ET1 Example 21 compound 2-5 EB1 compound 1-8 BD1 HB1 ET1 Example 22 compound 2-5 EB1 compound 1-11 BD1 HB1 ET1 Example 23 compound 2-5 EB1 compound 1-17 BD1 HB1 ET1 Example 24 compound 2-5 EB2 compound 1-18 BD2 HB1 ET1 Example 25 compound 2-5 EB1 compound 1-1 BD2 HB1 ET1 Example 26 compound 2-6 EB3 compound 1-3 BD1 HB1 ET2 Example 27 compound 2-6 EB1 compound 1-12 BD1 HB1 ET1 Example 28 compound 2-6 EB1 compound 1-14 BD1 HB1 ET1 Example 29 compound 2-6 EB1 compound 1-15 BD2 HB1 ET1 Example 30 compound 2-6 EB1 compound 1-7 BD2 HB1 ET1 Example 31 compound 2-7 EB1 compound 1-1 BD1 HB1 ET1 Example 32 compound 2-7 EB1 compound 1-19 BD1 HB1 ET1 Example 33 compound 2-7 EB1 compound 1-10 BD1 HB1 ET1 Example 34 compound 2-7 EB2 compound 1-3 BD2 HB1 ET2 Example 35 compound 2-7 EB1 compound 1-16 BD2 HB1 ET1 Example 36 compound 2-8 EB1 compound 1-3 BD1 HB1 ET1 Example 37 compound 2-8 EB1 compound 1-9 BD1 HB1 ET1 Example 38 compound 2-8 EB2 compound 1-20 BD1 HB1 ET1 Example 39 compound 2-8 EB1 compound 1-4 BD2 HB1 ET1 Example 40 compound 2-8 EB3 compound 1-9 BD2 HB1 ET1 Example 41 compound 2-9 EB1 compound 1-2 BD1 HB1 ET1 Example 42 compound 2-9 EB2 compound 1-7 BD1 HB1 ET1 Example 43 compound 2-9 EB1 compound 1-3 BD1 HB1 ET1 Example 44 compound 2-9 EB1 compound 1-13 BD2 HB1 ET1 Example 45 compound 2-9 EB3 compound 1-21 BD2 HB1 ET2 Example 46 compound 2-3 EB1 Compound 1-1: BH1
(1:1) BD1 HB1 ET1 Example 47 compound 2-7 EB1 Compound 1-17: BH1
(1:1) BD2 HB1 ET1 Example 48 compound 2-9 EB1 Compound 1-17: BH1
(2:1) BD2 HB1 ET1 Example 49 compound 2-1 EB1 Compound 1-17: BH1
(1:2) BD2 HB1 ET1 Example 50 compound 2-3 EB1 Compound 1-11: BH2
(1:1) BD2 HB1 ET1 Example 51 compound 2-7 EB1 Compound 1-13: Formula 1-15
(1:1) BD2 HB1 ET1

For the devices manufactured in Examples 1 to 51 and Comparative Examples 1 to 11 at ^{a current density of 20 mA/cm 2} , the driving voltage, luminous efficiency, color coordinates, and the time (LT95) to become 95% compared to the initial luminance were measured. The results are shown in Table 3 below.

Experimental example
20 mA/cm2 device result Voltage (V)
(@20mA/cm ² ) Cd/A
(@20mA/cm ² ) color coordinates
(x,y) life span
(T95, h)
(@20mA/cm ² ) Comparative Example 1 4.52 4.80 (0.135, 0.138) 40.1 Comparative Example 2 4.12 4.70 (0.135, 0.138) 45.2 Comparative Example 3 4.78 4.81 (0.135, 0.138) 42.2 Comparative Example 4 4.44 4.90 (0.135, 0.138) 40.2 Comparative Example 5 4.10 4.77 (0.135, 0.138) 44.8 Comparative Example 6 4.38 4.81 (0.135, 0.138) 48.0 Comparative Example 7 4.50 5.23 (0.136, 0.120) 32.0 Comparative Example 8 4.32 5.12 (0.136, 0.120) 38.0 Comparative Example 9 4.29 5.08 (0.136, 0.120) 34.9 Comparative Example 10 3.86 5.23 (0.135, 0.138) 48.4 Comparative Example 11 3.74 5.48 (0.136, 0.120) 35.8 Example 1 3.72 5.65 (0.135, 0.138) 73.1 Example 2 3.72 5.65 (0.135, 0.138) 60.3 Example 3 3.65 5.71 (0.135, 0.138) 75.3 Example 4 3.73 6.23 (0.136, 0.120) 64.2 Example 5 3.91 6.30 (0.136, 0.120) 63.1 Example 6 3.70 5.75 (0.135, 0.138) 78.2 Example 7 3.61 5.61 (0.135, 0.138) 80.2 Example 8 3.61 5.61 (0.135, 0.138) 69.1 Example 9 3.70 6.28 (0.136, 0.120) 65.4 Example 10 3.66 6.32 (0.136, 0.120) 67.2 Example 11 3.59 5.61 (0.135, 0.138) 83.1 Example 12 3.68 5.79 (0.135, 0.138) 75.3 Example 13 3.53 5.80 (0.135, 0.138) 79.2 Example 14 3.64 6.24 (0.136, 0.120) 65.8 Example 15 3.64 6.24 (0.136, 0.120) 51.3 Example 16 3.68 5.52 (0.135, 0.138) 79.1 Example 17 3.51 5.89 (0.135, 0.138) 73.9 Example 18 3.62 5.66 (0.135, 0.138) 80.1 Example 19 3.78 6.38 (0.136, 0.120) 63.9 Example 20 3.78 6.38 (0.136, 0.120) 52.8 Example 21 3.72 5.80 (0.135, 0.138) 78.1 Example 22 3.80 5.81 (0.135, 0.138) 74.5 Example 23 3.61 5.74 (0.135, 0.138) 80.5 Example 24 3.70 6.22 (0.136, 0.120) 70.1 Example 25 3.68 6.11 (0.136, 0.120) 72.3 Example 26 3.91 5.90 (0.135, 0.138) 70.2 Example 27 3.73 5.81 (0.135, 0.138) 71.5 Example 28 3.68 5.71 (0.135, 0.138) 75.8 Example 29 3.58 6.32 (0.136, 0.120) 67.4 Example 30 3.71 6.23 (0.136, 0.120) 68.9 Example 31 3.65 5.66 (0.135, 0.138) 79.1 Example 32 3.65 5.66 (0.135, 0.138) 68.1 Example 33 3.51 5.81 (0.135, 0.138) 80.2 Example 34 3.80 6.41 (0.136, 0.120) 63.8 Example 35 3.84 6.34 (0.136, 0.120) 67.5 Example 36 3.70 5.90 (0.135, 0.138) 73.1 Example 37 3.68 5.77 (0.135, 0.138) 77.4 Example 38 3.68 5.77 (0.135, 0.138) 65.1 Example 39 3.71 6.28 (0.136, 0.120) 63.1 Example 40 3.62 6.30 (0.136, 0.120) 65.1 Example 41 3.66 5.98 (0.135, 0.138) 71.0 Example 42 3.71 5.84 (0.135, 0.138) 78.9 Example 43 3.75 5.77 (0.135, 0.138) 80.1 Example 44 3.55 6.35 (0.136, 0.120) 67.1 Example 45 3.80 6.35 (0.136, 0.120) 60.0 Example 46 3.57 6.00 (0.135, 0.138) 88.1 Example 47 3.64 6.38 (0.136, 0.120) 75.1 Example 48 3.80 6.50 (0.136, 0.120) 78.3 Example 49 3.71 6.24 (0.136, 0.120) 71.5 Example 50 3.51 6.33 (0.136, 0.120) 75.8 Example 51 3.50 6.41 (0.136, 0.120) 80.5

The organic electroluminescent device according to the present invention induces excellent hole injection and transport into the light emitting layer by using the compound of Formula 1 applied to the hole control region of the blue organic light emitting device and Formula 2 applied as a host of the light emitting layer. Through the balance of holes and electrons of the organic electroluminescent device according to the chemical structure, the device according to the present invention exhibits excellent characteristics in terms of efficiency, driving voltage, and stability.

In Examples 1 to 45, devices were fabricated by using the compound of Formula 1 as the hole transport layer and the compound of Formula 2 as the host of the emission layer. The device configuration shows that various hole control layers EB1 to EB3 and blue fluorescent dopants BD1 to BD2 can be applied.

Comparative Example 1 is a result of a device made of a compound, not a combination of the present invention, and an aryl-based anthracene was used as the host of the light emitting layer, and in Comparative Example 2, a heteroaryl-based anthracene was used. In both cases, high voltage, low efficiency, and low lifetime indicate poor performance of the device.

Comparative Example 3 exhibits a relatively high voltage due to the low electron transport ability because the electron transport layer is not an azine-based compound in the configuration of Comparative Example 1.

Comparative Examples 5 to 6 show the result that various hole control layers may be used in addition to the hole transport layer of Chemical Formula 1, and the performance of the device is more affected by the change of Chemical Formula 1.

Comparative Examples 7 to 9 may be applied with a non-pyrene-based blue dopant, and among them, Comparative Examples 8 to 9 show insufficient improvement in performance of the manufactured device when only one of the combinations of the present application is applied.

Comparative Examples 10 to 11 are comparative examples of mixed hosts.

Examples 1 to 45 are combinations of compounds of the present invention and results of application of a single host. Compared to Comparative Examples 1 to 9, it shows an improvement in the performance of the fabricated device, and in particular, a distinct difference in lifespan. It was observed that the substitution of deuterium in the host of the light emitting layer has a significant effect on the lifetime increase of the manufactured organic electroluminescent device.

Examples 2, 8, 15, 20, 32, 38, and 45 are cases in which the substitution rate of deuterium in the compound of Formula 2 is less than 40%, which shows lower voltage and higher efficiency compared to Comparative Examples, and shows improvement in lifespan. 7, 14, 19, 31, 37, 44 shows a lower increase in lifespan. It seems that the substitution rate of deuterium in the host of the light emitting layer also affects the lifetime increase of the manufactured organic electroluminescent device.

In Examples 46 to 51, it was observed that the compound of Formula 2 was used in combination with another host, and it was observed that the performance of the device could be improved by mixing the two hosts. In addition, as in Example 51, it can be seen that the mixture of the two hosts of Chemical Formula 2 (the mixture of two deuterium-substituted hosts) greatly improves the device lifespan.

10: organic electroluminescent device
20: substrate
30: anode
40: light emitting layer
50: cathode
60: hole injection layer
70: hole transport layer
80: hole control layer
90: electronic control layer
100: electron transport layer
110: electron injection layer
120: capping layer

Claims (18)

cathode; anode; And an organic electroluminescent device comprising a light emitting layer provided between the cathode and the anode, further comprising an organic material layer provided between the anode and the light emitting layer and comprising a compound of Formula 1, wherein the light emitting layer is of Formula 2 An organic electroluminescent device comprising a compound:
[Formula 1]

In Formula 1,
Ar1 is a substituted or unsubstituted aryl group having 5 to 50 carbon atoms; a substituted or unsubstituted heteroaryl group having 1 to 50 carbon atoms; Or a substituted or unsubstituted amine group,
Ar2 and Ar3 are the same as or different from each other and each independently a substituted or unsubstituted C5 to C50 aryl group; or a substituted or unsubstituted heteroaryl group having 1 to 50 carbon atoms, which are bonded to each other directly or through CRR', O, S or NR, or one of Ar2 and Ar3 is directly or CRR', O, S or CRR', O, S or may be bound through NR;
Ar4 and Ar5 are the same as or different from each other and each independently a substituted or unsubstituted C5 to C50 aryl group; or a substituted or unsubstituted C1 to C50 heteroaryl group, which is bonded to each other directly or through CRR', O, S or NR, or one of Ar4 and Ar5 is directly or CRR', O, S or CRR', O, S or may be bound through NR;
L1 to L3 are the same as or different from each other and each independently a substituted or unsubstituted C5 to C50 arylene group; Or a substituted or unsubstituted C 1 to C 50 heteroarylene group,
a to e are each an integer of 0 to 3,
X is CR11R12, O, S or NR13, p is 0 or 1, when p is 0, two benzenes bonded to X are directly bonded,
R, R', R11 to R13, R1 and R2 are the same as or different from each other and each independently represent hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 5 to C 50 aryl group, A substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C 1 to C 50 heteroaryl group, a substituted or unsubstituted amine group, a substituted or unsubstituted C 1 to C 30 alkylsilyl group, substituted or an unsubstituted C 5 to C 30 arylsilyl group, a cyano group, a nitro group, a hydroxyl group and a halogen group,
[Formula 2]

In Formula 2,
At least one of A and B is a substituted or unsubstituted two or more aromatic hydrocarbon rings or a substituted or unsubstituted two or more heterocyclic rings, and the rest is a substituted or unsubstituted aromatic hydrocarbon ring or a substituted or unsubstituted heterocycle; ,
Ra is hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 5 to C 50 aryl group, a substituted or unsubstituted C 3 to C 30 cycloalkyl group, a substituted or unsubstituted C A heteroaryl group of 1 to 50, a substituted or unsubstituted amine group, a substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl group having 5 to 30 carbon atoms, a cyano group, a nitro group, selected from the group consisting of a hydroxyl group and a halogen group,
La is a substituted or unsubstituted arylene group having 5 to 50 carbon atoms; Or a substituted or unsubstituted C 1 to C 50 heteroarylene group,
r and u are each an integer from 1 to 9, q is an integer from 0 to 5,
However, the compound of Formula 2 includes at least one deuterium. The organic electroluminescent device according to claim 1, wherein Chemical Formula 1 is represented by the following Chemical Formula 11:
[Formula 11]

Definitions of the substituents of Chemical Formula 11 are the same as in Chemical Formula 1. The organic electroluminescent device according to claim 1, wherein at least one deuterium directly bonded to anthracene of Formula 2 is included. The method according to claim 1, wherein the anthracene of Formula 2

An organic electroluminescent device in which one or more deuterium is bonded to each. The organic electroluminescent device according to claim 1, wherein the light emitting layer further comprises one or more dopants. The organic electroluminescent device according to claim 1, wherein the light emitting layer includes two or more hosts, and at least one of the hosts is a compound represented by Formula 2 above. The organic electroluminescent device according to claim 1, wherein the emission spectrum of the emission layer comprising the compound of Formula 2 has λmax within 400 nm to 470 nm. The organic electroluminescent device of claim 5, wherein the dopant is a fluorescent dopant. The organic electroluminescent device according to claim 5, wherein the dopant includes a pyrene-based compound. The organic electroluminescent device according to claim 5, wherein the dopant includes a non-pyrene-based compound. The organic electroluminescent device of claim 10, wherein the non-pyrene-based compound includes a boron-based compound. The organic electroluminescent device according to claim 1, wherein the organic material layer comprising the compound of Formula 1 is a hole transport layer. The organic electroluminescent device according to claim 1, further comprising a hole control layer provided between the light emitting layer and the organic material layer including the compound of Formula 1. The organic electroluminescent device according to claim 1, wherein the organic material layer including the compound of Formula 1 is in contact with the anode. The organic electroluminescent device according to claim 12, wherein the hole transport layer has a thickness of 50 nm to 200 nm. The organic electroluminescent device of claim 13, wherein the hole control layer has a thickness of 10 nm to 150 nm. The organic electroluminescent device according to claim 1, further comprising an organic material layer provided between the light emitting layer and the cathode, the organic material layer including a compound of Formula 3 below:
[Formula 3]

In Formula 3,
X1 to X3 are CR21R22 or N, and at least one of X1 to X3 is N,
Ara to Arc, R21 and R22 are the same or different from each other, and each independently represents hydrogen, deuterium, a substituted or unsubstituted C 1 to C 30 alkyl group, a substituted or unsubstituted C 5 to C 50 aryl group, substituted or unsubstituted an alkenyl group having 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl group having 3 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 1 to 50 carbon atoms, substituted or an unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C5 to C30 aryloxy group, a substituted or unsubstituted C1 to C30 alkylthioxy group, a substituted or unsubstituted C5 to C30 It is selected from an arylthioxy group, a substituted or unsubstituted C1-C30 alkylsilyl group, a substituted or unsubstituted C5-C30 arylsilyl group, a cyano group, a nitro group, a hydroxyl group, and a halogen group. The organic electroluminescent device according to claim 17, wherein the organic layer comprising the compound of Formula 3 further comprises an organic alkali metal complex.

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