KR20230073098A - Compound, Organic EL Device and Display Device - Google Patents

Abstract

According to the present invention, a compound applicable to a hole transport region of an organic electroluminescent device, the organic electroluminescent device using such the compound, and a display apparatus including such the organic electroluminescent device are provided. In particular, when the novel compound represented by chemical formula 1 of the present invention is used as a material for the hole transport region, the organic electroluminescent device with excellent luminous performance, low driving voltage, high efficiency, and long lifespan compared to conventional materials can be manufactured, and furthermore, it is possible to manufacture a full-color display panel with greatly improved performance and lifespan.

Description

Compound, organic electroluminescent device and display device {Compound, Organic EL Device and Display Device}

The present invention relates to a novel organic compound that can be used as a material for an organic light emitting device, an organic light emitting device including the same, and a display device.

Recently, as a full-color flat panel display, a display using an organic electroluminescent device has been attracting attention, and is used in display devices such as smart phones, TVs, automobiles, and VR (Virtual Reality) head-mounted devices.

An organic electroluminescent element has a structure composed of a pair of electrodes composed of an anode and a cathode, and a single layer or a plurality of layers disposed between the pair of electrodes and containing an organic compound. Layers containing organic compounds include a light emitting layer and a charge transport/injection layer that transports or injects charges such as holes and electrons. Various organic materials suitable for these layers have been developed.

In order to further broaden the application fields of displays using organic electroluminescent elements, reduction of power consumption (lower voltage, improvement of external quantum efficiency) and longer lifespan of the elements are required.

As a hole injection material or a hole transport material, an organic material having an electron donating property, that is, an organic material that is easily oxidized and has an electrochemically stable state upon oxidation is mainly used (Patent Documents 1 and 2).

However, in the case of such a conventional hole transport layer material, further improvement is required in terms of luminous efficiency, driving voltage, and lifetime.

In particular, when the hole transport layer has a low T1 value, excitons generated in the light emitting layer pass over to the hole transport layer and emit light at the hole transport layer interface, resulting in charge unbalance in the light emitting layer. When light is emitted from the interface of the hole transport layer, the color purity and efficiency of the organic light emitting device are lowered and the lifetime is shortened.

Korean Patent Publication No. 2012-112277 Korean Patent Publication No. 2018-092270

An object of the present invention is to provide a novel amine derivative compound, an organic electroluminescent device having high efficiency, low driving voltage and long lifespan by employing such a compound, and a display device using the same.

In order to achieve the above object, the present invention provides a compound represented by Formula 1 below.

In Formula 1,

L ₁ to L ₃ are the same as or different from each other, and each independently represents a single bond, a substituted or unsubstituted C ₁ -C ₁₀ alkylene group, a substituted or unsubstituted C ₃ -C ₃₀ arylene group, or a substituted or unsubstituted C 1 -C 10 alkylene group. selected from the group consisting of a C ₂ -C ₃₀ heteroarylene group, a substituted or unsubstituted C ₃ -C ₂₀ cycloalkylene group, and a substituted or unsubstituted C ₂ -C ₂₀ heterocycloalkylene group,

X ₁ and X ₂ are the same as or different from each other, and are each independently selected from the group consisting of a single bond, CR ₃ R ₄ , O, S or NR ₅ , X ₁ and X ₂ cannot be a single bond at the same time, ,

R ₁ to R ₅ are the same as or different from each other, and are each independently hydrogen, heavy hydrogen, a trifluoromethyl group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl group, substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, substituted or unsubstituted C ₁ -C ₂₀ heteroalkyl group , a substituted or unsubstituted C ₃ -C ₂₀ aralkyl group, a substituted or unsubstituted C ₃ -C ₃₀ aryl group, a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group, a substituted or unsubstituted C ₃ -C ₂₀ heteroaralkyl group, substituted or unsubstituted C ₁ -C ₃₀ alkylsilyl group, substituted or unsubstituted C ₃ -C ₃₀ arylsilyl group, and substituted or unsubstituted C ₃ -C ₃₀ It is selected from the group consisting of a heteroarylsilyl group, R ₁ to R ₅ may combine with adjacent groups to form a substituted or unsubstituted ring,

m is an integer from 0 to 4;

n is an integer from 0 to 3;

Ar ₁ and Ar ₂ are the same as or different from each other, and each independently represents a substituted or unsubstituted C ₅ -C ₃₀ aryl group, a substituted or unsubstituted C 3 -C 30 heteroaryl group, or a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group. ₁ -C ₂₀ alkyl group, substituted or unsubstituted C ₁ -C ₂₀ alkenyl group, substituted or unsubstituted C ₁ -C ₂₀ alkynyl group, substituted or unsubstituted C ₃ -C ₂₀ cycloalkyl group, substituted Or an unsubstituted C ₁ -C ₂₀ heteroalkyl group, a substituted or unsubstituted C ₃ -C ₂₀ heterocycloalkyl group, a substituted or unsubstituted C ₅ -C ₃₀ aralkyl group, a substituted or unsubstituted C ₃ - C ₃₀ heteroaralkyl group, substituted or unsubstituted C ₃ -C ₂₀ cycloalkenyl group, substituted or unsubstituted C ₁ -C ₂₀ heteroalkenyl group, substituted or unsubstituted C ₆ -C ₄₀ arylamine group, and a substituted or unsubstituted C ₅ -C ₄₀ selected from the group consisting of a heteroarylamine group,

At least one hydrogen in the formula (1) may be substituted with deuterium.

In addition, the present invention provides an organic electroluminescent device including the compound represented by Chemical Formula 1 in an organic material layer and a display device including the organic electroluminescent device.

In particular, when the novel compound represented by Formula 1 of the present invention is used as a material for the hole transport region, an organic electroluminescent device having excellent light emitting performance, low driving voltage, high efficiency and long lifespan can be prepared compared to conventional materials, Furthermore, it is possible to manufacture a full color display panel with significantly improved performance and lifespan.

1 is a schematic cross-sectional view of an organic electroluminescent device according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. In describing the present invention, if it is determined that a detailed description of a related known configuration or function may obscure the gist of the present invention, the detailed description will be omitted.

<Description of the compound of the present invention>

The compound according to the present invention is a compound represented by the following formula (1).

In Formula 1,

L ₁ to L ₃ are the same as or different from each other, and each independently represents a single bond, a substituted or unsubstituted C ₁ -C ₁₀ alkylene group, a substituted or unsubstituted C ₃ -C ₃₀ arylene group, or a substituted or unsubstituted C 1 -C 10 alkylene group. selected from the group consisting of a C ₂ -C ₃₀ heteroarylene group, a substituted or unsubstituted C ₃ -C ₂₀ cycloalkylene group, and a substituted or unsubstituted C ₂ -C ₂₀ heterocycloalkylene group,

X ₁ and X ₂ are the same as or different from each other, and are each independently selected from the group consisting of a single bond, CR ₃ R ₄ , O, S or NR ₅ , X ₁ and X ₂ cannot be a single bond at the same time, ,

R ₁ to R ₅ are the same as or different from each other, and are each independently hydrogen, heavy hydrogen, a trifluoromethyl group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl group, substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, substituted or unsubstituted C ₁ -C ₂₀ heteroalkyl group , a substituted or unsubstituted C ₃ -C ₂₀ aralkyl group, a substituted or unsubstituted C ₃ -C ₃₀ aryl group, a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group, a substituted or unsubstituted C ₃ -C ₂₀ heteroaralkyl group, substituted or unsubstituted C ₁ -C ₃₀ alkylsilyl group, substituted or unsubstituted C ₃ -C ₃₀ arylsilyl group, and substituted or unsubstituted C ₃ -C ₃₀ It is selected from the group consisting of a heteroarylsilyl group, R ₁ to R ₅ may combine with adjacent groups to form a substituted or unsubstituted ring,

m is an integer from 0 to 4;

n is an integer from 0 to 3;

Ar ₁ and Ar ₂ are the same as or different from each other, and each independently represents a substituted or unsubstituted C ₅ -C ₃₀ aryl group, a substituted or unsubstituted C 3 -C 30 heteroaryl group, or a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group. ₁ -C ₂₀ alkyl group, substituted or unsubstituted C ₁ -C ₂₀ alkenyl group, substituted or unsubstituted C ₁ -C ₂₀ alkynyl group, substituted or unsubstituted C ₃ -C ₂₀ cycloalkyl group, substituted Or an unsubstituted C ₁ -C ₂₀ heteroalkyl group, a substituted or unsubstituted C ₃ -C ₂₀ heterocycloalkyl group, a substituted or unsubstituted C ₅ -C ₃₀ aralkyl group, a substituted or unsubstituted C ₃ - C ₃₀ heteroaralkyl group, substituted or unsubstituted C ₃ -C ₂₀ cycloalkenyl group, substituted or unsubstituted C ₁ -C ₂₀ heteroalkenyl group, substituted or unsubstituted C ₆ -C ₄₀ arylamine group, and a substituted or unsubstituted C ₅ -C ₄₀ selected from the group consisting of a heteroarylamine group,

At least one hydrogen in the formula (1) may be substituted with deuterium.

As in the compound represented by Formula 1 of the present invention, by using an amine derivative having a condensed substituent of an alicyclic hydrocarbon ring and an aromatic hydrocarbon ring as a material for the hole transport region, excellent light emitting performance and low driving voltage compared to conventional materials , It is possible to manufacture an organic electroluminescent device having high efficiency and long lifespan, and furthermore, a full color display panel with greatly improved performance and lifespan can be manufactured.

Hereinafter, the substituent in this invention is demonstrated in detail.

A position where a substituent is not bonded to the compounds described herein may be hydrogen or deuterium may be bonded thereto.

In this specification, 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 to a position where a hydrogen atom is substituted, that is, a position where the substituent is substituted, 2 In the case of over-substitution, two or more substituents may be the same as or different from each other.

In this specification, the term "substituted or unsubstituted" means deuterium; nitro group; halogen group; hydroxy group; cyano group; phosphine oxide group; an alkyl group; alkenyl group; cycloalkyl group; aryl group; heterocyclic group; aralkyl group; Aralkenyl group; Alkyl aryl group; alkenyl aryl group; alkoxy group; aryloxy group; Arylphosphine oxide group; silyl group; Alkylamine group; Aralkylamine group; Arylamine group; an alkyl arylamine group; and heteroarylamine groups. It means substituted or unsubstituted with one or more substituents selected from the group consisting of, or substituted or unsubstituted with substituents in which two or more substituents among the substituents exemplified above are connected. For example, "a substituent in which two or more substituents are connected" may be a biphenyl group. That is, the biphenyl group may be an aryl group, and may be interpreted as a substituent in which two phenyl groups are connected.

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

In the present specification, the alkyl group may be straight-chain or branched-chain, and the number of carbon atoms is not particularly limited, but is preferably 1 to 50. 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, but is not limited thereto.

In the present specification, the alkenyl group is a monovalent substituent derived from a straight-chain or branched-chain unsaturated hydrocarbon having one or more carbon-carbon double bonds, and the number of carbon atoms is not particularly limited, but is preferably 2 to 50. 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, stilbenyl group, styrenyl group, etc., but is not limited thereto.

In the present specification, the alkynyl group is a monovalent substituent derived from a straight-chain or branched unsaturated hydrocarbon having at least one carbon-carbon triple bond, and the number of carbon atoms is not particularly limited, but preferably has 2 to 20 carbon atoms. Specific examples include, but are not limited to, an ethynyl group, 2-propynyl, and the like.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 60 carbon atoms, specifically cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, etc., but are not limited thereto. don't

In the present specification, the aryl group may be a monocyclic aryl group or a polycyclic aryl group. When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 60 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. The polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

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

,

,

및

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

,

,

and

etc. However, it is not limited thereto.

In the present specification, an aralkyl group refers to an aryl-alkyl group in which a bond to a parent moiety is formed by an alkyl, and specific examples include, but are not limited to, benzyl, 2-phenethyl, and naphthalenylmethyl.

In the present specification, an alkylaryl group means an alkyl-substituted aryl group.

In the present specification, examples of the arylphosphine oxide group include a substituted or unsubstituted monoarylphosphine oxide group, a substituted or unsubstituted diarylphosphine oxide group, or a substituted or unsubstituted triarylphosphine oxide group. . The aryl group in the arylphosphine oxide group may be a monocyclic aryl group or a polycyclic aryl group. The aryl phosphine oxide 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.

In the present specification, the silyl group may be represented by a chemical formula of -SiR _a R _b R _c , wherein R _a , R _b and R _c are each hydrogen; A substituted or unsubstituted alkyl group; Or it may be a substituted or unsubstituted aryl group. The silyl group specifically includes a trimethylsilyl group, a triethylsilyl group, a t-butyldimethylsilyl group, a vinyldimethylsilyl group, a propyldimethylsilyl group, a triphenylsilyl group, a diphenylsilyl group, a phenylsilyl group, and the like, but is not limited thereto. don't

In the present specification, the heterocyclic group is an aromatic or aliphatic heterocyclic group containing one or more of O, N, and S as heterogeneous elements, and the number of carbon atoms is not particularly limited, but preferably has 2 to 60 carbon atoms. Examples of the heterocyclic group include a thiophene group, a furan group, a pyrrole group, an imidazole group, a thiazole group, an oxazole group, an oxadiazole group, a triazole group, a pyridine group, a bipyridine group, a pyrimidine group, a triazine group, a triazole group, Acridine group, pyridazine group, pyrazine group, quinoline group, quinazoline group, quinoxaline group, phthalazine group, pyridopyrimidinyl group, pyridopyrazinyl group, pyrazinopyrazinyl group, isoquinoline group, indole group , carbazole group, carboline group, benzooxazole group, benzoimidazole group, benzothiazole group, benzocarbazole group, benzothiophene group, dibenzothiophene group, benzofuranyl group, phenanthroline group, thiazolyl group , An isoxazolyl group, an oxadiazolyl group, a thiadiazolyl group, a benzothiazolyl group, a phenothiazinyl group, and a dibenzofuranyl group, but are not limited thereto.

In the present specification, the description of the aromatic heterocyclic group among heterocyclic groups may be applied to the heteroaryl group. The heteroaryl group may include the structure below.

In the present specification, the alkoxy group may be straight chain, branched chain or cyclic chain. The number of carbon atoms in the alkoxy group is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, the alkoxy group is methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyl Oxy, isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy etc., but is not limited thereto.

In the present specification, the aryl group in the aryloxy group is the same as the example of the above-mentioned aryl group. Specifically, aryloxy groups include phenoxy, p-toryloxy, m-toryloxy, 3,5-dimethyl-phenoxy, 2,4,6-trimethylphenoxy, p-tert-butylphenoxy, 3-biphenyl Oxy, 4-biphenyloxy, 1-naphthyloxy, 2-naphthyloxy, 4-methyl-1-naphthyloxy, 5-methyl-2-naphthyloxy, 1-anthryloxy, 2-anthryl oxy, 9-anthryloxy, 1-phenanthryloxy, 3-phenanthryloxy, 9-phenanthryloxy, etc., and arylthioxy groups include phenylthioxyl group, 2-methylphenylthioxy group, 4-tert-butylphenyl Thioxy group and the like, but are not limited thereto.

In the present specification, the alkylamine group, the aralkylamine group, the arylamine group, the alkylarylamine group, and the heteroarylamine group are amine groups each substituted with an alkyl group, an aralkyl group, an aryl group, an alkylaryl group, and a heteroaryl group, Here, the description of the above-described alkyl group and the aryl group may be applied to alkyl and aryl, and the description of the aromatic heterocyclic group among the above-described heterocyclic groups may be applied to the heteroaryl group. Specific examples of the amine group include methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 3-methyl-phenylamine, 4 -Methyl-naphthylamine, 2-methyl-biphenylamine, 9-methyl-anthracenylamine, diphenylamine, phenylnaphthylamine, ditolylamine, phenyltolylamine, triphenylamine, etc. There are, but are not limited to these.

In the present specification, the heteroaralkyl group refers to an alkyl group substituted with a heteroaryl group (e.g., a C1-C4 alkyl group), wherein the heteroaryl group and the alkyl group are each described in relation to the aromatic heterocyclic group among the above-mentioned heterocyclic groups and to the alkyl group. explanation may apply.

In the present specification, the alkylene group may be selected from examples of the above-mentioned alkyl groups, except for divalent groups.

In the present specification, the cycloalkylene group may be selected from examples of the above-described cycloalkyl groups, except for divalent groups.

In the present specification, the heterocycloalkylene group means a heterocycloalkyl group having two binding sites, that is, a divalent group. The description of an aliphatic heterocyclic group can be applied except that each is a divalent group.

In the present specification, the arylene group means that the aryl group has two binding sites, that is, a divalent group. The description of the aryl group described above can be applied except that each is a divalent group.

In the present specification, the heteroarylene group means that the heteroaryl group has two binding sites, that is, a divalent group. The above description of the aromatic heterocyclic group may be applied except that each is a divalent group.

In the present specification, "to form a ring by bonding with adjacent groups" means a substituted or unsubstituted aliphatic hydrocarbon ring by bonding with adjacent groups; A substituted or unsubstituted aromatic hydrocarbon ring; A substituted or unsubstituted aliphatic heterocycle; A substituted or unsubstituted aromatic heterocycle; or to form a condensed ring thereof.

In this specification, "adjacent group" refers to a substituent substituted on an atom directly connected to the atom on which the substituent is substituted, a substituent located sterically closest to the substituent, or another substituent substituted on the atom on which the substituent is substituted. can mean For example, two substituents substituted at ortho positions in a benzene ring and two substituents substituted at the same carbon in an aliphatic ring may be interpreted as "adjacent groups" to each other.

In the present specification, an aliphatic hydrocarbon ring is a non-aromatic ring and refers to a ring composed of only carbon and hydrogen atoms.

In the present specification, examples of the aromatic hydrocarbon ring include, but are not limited to, a phenyl group, a naphthyl group, an anthracenyl group, and the like.

In the present specification, an aliphatic heterocycle means an aliphatic ring containing at least one of N, O or S atoms as a heteroatom.

In the present specification, the aromatic heterocycle means an aromatic ring containing at least one of N, O or S atoms as a heteroatom.

In the present specification, the aliphatic ring, aromatic ring, aliphatic heterocyclic ring and aromatic heterocyclic ring may be monocyclic or polycyclic.

According to one embodiment of the present invention, Ar ₁ and Ar ₂ of Formula 1 Any one of them is represented by Formula 2 or Formula 3 below.

In Formula 2 and Formula 3,

X ₃ to X ₅ are the same as or different from each other, and are each independently selected from the group consisting of a single bond, CR _a R _b , O, S or NR _c , X ₃ and X ₄ cannot be a single bond at the same time, ,

X ₆ is NR _c ;

R ₆ to R ₉ and Ra to Rc are the same as or different from each other, and each independently represents hydrogen, heavy hydrogen, a trifluoromethyl group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, or a substituted group. Or an unsubstituted C ₃ -C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, a substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, a substituted or unsubstituted C ₁ -C ₂₀ heteroalkyl group, substituted or unsubstituted C ₃ -C ₂₀ aralkyl group, substituted or unsubstituted C ₃ -C ₃₀ aryl group, substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group, substituted or An unsubstituted C ₃ -C ₂₀ heteroaralkyl group, a substituted or unsubstituted C ₁ -C ₃₀ alkylsilyl group, a substituted or unsubstituted C ₃ -C ₃₀ arylsilyl group, and a substituted or unsubstituted C ₃ -C ₃₀ It is selected from the group consisting of a heteroarylsilyl group, R ₆ ~ R ₉ and Ra ~ Rc may combine with adjacent groups to form a substituted or unsubstituted ring,

o is an integer from 0 to 3;

p, q and r are integers from 0 to 4;

* is Ar ₁ and Ar ₂ Any one of them is a position at which the compound represented by Formula 1 is bonded.

According to one embodiment of the present invention, Ar ₁ and Ar ₂ The other one is a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group.

According to one embodiment of the present invention, both X ₁ and X ₂ in Formula 1 are CR ₃ R ₄ .

According to an embodiment of the present invention, in CR ₃ R ₄ of X ₁ and X ₂ in Formula 1, R ₃ and R ₄ are the same as or different from each other, and each independently a substituted or unsubstituted C ₁ -C ₂₀ alkyl group. am.

According to one embodiment of the present invention, the compound represented by Formula 1 is any one of the following compounds.

<Structure of organic electroluminescent device>

Hereinafter, an organic electroluminescent device according to an embodiment of the present invention will be described in detail based on the drawings. 1 is a schematic cross-sectional view showing an organic electroluminescent device according to an embodiment of the present invention.

The organic electroluminescent device 1 shown in FIG. 1 includes an anode 110 (first electrode) provided on a substrate 100, a hole injection layer 120 provided on the anode 110, and a hole injection layer 120 ) The hole transport layer 130 provided on the hole transport layer 130, the light emitting layer 140 provided on the hole transport layer 130, the electron transport layer 150 provided on the light emitting layer 140, and the electron injection layer provided on the electron transport layer 150 (160) and a cathode (170, second electrode) provided on the electron injection layer (160). Here, layers between the anode 110 and the cathode 170 constitute an organic material layer.

In addition, the organic electroluminescent element 1 has a laminated structure reversed (a so-called inverted element), for example, a cathode provided on the substrate 100, an electron injection layer provided on the cathode, and an electron injection layer provided on the substrate 100. It may be configured to include an electron transport layer provided on the electron transport layer, a light emitting layer provided on the electron transport layer, a hole transport layer provided on the light emitting layer, a hole injection layer provided on the hole transport layer, and an anode provided on the hole injection layer.

In the organic electroluminescent device 1 of the present invention, all of the above layers are not essential, and the minimum structural unit is composed of an anode 110, a light emitting layer 140, and a cathode 170, and the hole injection layer 120 ), at least one of the hole transport layer 130, the electron transport layer 150, and the electron injection layer 160 may be omitted.

For example, in addition to the structure of the above-described "anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode", the laminated structure of the organic electroluminescent device is "anode/hole transport layer/light emitting layer/electron transport layer/electron injection layer" layer/cathode”, “anode/hole injection layer/emission layer/electron transport layer/electron injection layer/cathode”, “anode/hole injection layer/hole transport layer/emission layer/electron injection layer/cathode”, “anode/hole injection layer/cathode” Hole transport layer/emission layer/electron transport layer/cathode", "anode/emission layer/electron transport layer/electron injection layer/cathode", "anode/hole transport layer/emission layer/electron injection layer/cathode", "anode/hole transport layer/emission layer/electron Transport Layer/Cathode”, “Anode/Hole Injection Layer/Emission Layer/Electron Injection Layer/Cathode”, “Anode/Hole Injection Layer/Emission Layer/Electron Transport Layer/Cathode”, “Anode/Emission Layer/Electron Transport Layer/Cathode”, “Anode/ light emitting layer/electron injection layer/cathode'.

In addition, for the purpose of balancing the concentration of holes and electrons in the light emitting layer 140, the area between the anode 110 and the light emitting layer 140 (hole transport area) and between the light emitting layer 140 and the cathode 170 A separate layer (for example, a hole blocking layer and/or an electron blocking layer, etc.) may be added to the region of (electron transport region).

In this case, the organic electroluminescent device 1 is "anode/hole injection layer/hole transport layer/electron blocking layer/emission layer/electron transport layer/electron injection layer/cathode", "anode/hole injection layer/hole transport layer/emission layer/ It may have a laminated structure such as "hole blocking layer/electron transport layer/electron injection layer/cathode", "anode/hole injection layer/hole transport layer/electron blocking layer/emission layer/hole blocking layer/electron transport layer/electron injection layer/cathode", etc. there is.

Moreover, each said layer may consist of a single layer, respectively, and may consist of multiple layers.

Hereinafter, the substrate 10 used for manufacturing the organic electroluminescent device 1 and each layer constituting the organic electroluminescent device 1 will be described in detail.

The substrate 100 is a support for supporting the organic electroluminescent element 1, and glass, metal, polymer, semiconductor (silicon), or the like is usually used. The substrate 100 is formed in the shape of a plate, film or sheet depending on the purpose, and for example, a glass plate, metal plate, metal foil, polymer film, polymer sheet or the like is used. Among them, glass plates and plates made of transparent synthetic resins such as polyester, polymethacrylate, polycarbonate, and polysulfone are preferred. In the case of manufacturing a flexible display, a polymeric material (eg, polyimide) having high thermal stability and flexibility applied on a glass plate (also referred to as a carrier glass) may be used as the substrate 100 . If it is a glass substrate, soda-lime glass, non-alkali glass, etc. are used, and since thickness should just have enough thickness to maintain mechanical strength, it should just be 0.2 mm or more, for example. As an upper limit of thickness, it is 2 mm or less, for example, Preferably it is 1 mm or less. Regarding the material of the glass, alkali-free glass is preferable since fewer ions eluted from the glass are preferred, but soda-lime glass coated with a barrier coating of SiO ₂ or the like is also commercially available and can be used. In addition, a gas barrier film such as a dense silicon oxide film may be provided on at least one side of the substrate 100 in order to improve gas barrier properties. In particular, when a polymer plate, film or sheet having low gas barrier properties is used as the substrate 100 It is preferable to provide a gas barrier film.

The anode 110 is an electrode for injecting holes, and a material having a high work function is preferable so that holes can be smoothly injected into the organic material layer.

Examples of materials forming the anode 110 include inorganic compounds and organic compounds. Examples of the inorganic compound include metals (aluminum, gold, silver, nickel, palladium, chromium, vanadium, copper, zinc, etc.) or alloys thereof, metal oxides (indium oxide, tin oxide, indium-tin oxide ( ITO), indium-zinc oxide (IZO, etc.), combinations of metals and oxides such as ZnO:Al or SNO ₂ :Sb, metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass or Nessa glass, etc. can Examples of the organic compound include polythiophene such as poly(3-methylthiophene) and poly[3,4-(ethylene-1,2-dioxy)thiophene] (PEDOT), polypyrrole, and polyaniline. A conductive polymer etc. are mentioned. In addition, it can be used suitably selected from materials used as an anode of an organic electroluminescent element.

The hole injection layer 120 serves to efficiently inject holes moving from the anode 110 into the light emitting layer 140 or into the hole transport layer 130 . The hole transport layer 130 serves to efficiently transport holes injected from the anode 110 or holes injected from the anode 110 through the hole injection layer 120 to the light emitting layer 140 . The hole injection layer 120 and the hole transport layer 130 are formed by laminating or mixing one or more hole injection/transport materials, or a mixture of a hole injection/transport material and a polymeric binder, respectively. Alternatively, a layer may be formed by adding an inorganic salt such as iron chloride (²) to the hole injecting/transporting material.

As the hole injecting/transporting substance, one having high hole injection efficiency and efficiently transporting the injected holes is preferable. For this purpose, it is preferable to use a material that has low ionization potential, high hole mobility, excellent stability, and is unlikely to generate trap impurities during production and use.

As the material forming the hole injection layer 120 and the hole transport layer 130, in the photoconductive material, a compound conventionally used as a hole charge transport material, a p-type semiconductor, a hole injection layer of an organic electroluminescent device, and Any compound can be selected and used from known compounds used in the hole transport layer. These specific examples include carbazole derivatives (such as N-phenylcarbazole and polyvinylcarbazole), biscarbazole derivatives such as bis(N-arylcarbazole) or bis(N-alkylcarbazole), and triarylamine derivatives. (Polymer having aromatic tertiary amino in main chain or side chain, 1,1-bis(4-di-p-tolylaminophenyl)cyclohexane, N,N'-diphenyl-N,N'-di(3- Methylphenyl) -4,4'-diaminobiphenyl, N,N'-diphenyl-N,N'-dinaphthyl-4,4'-diaminobiphenyl, N,N'-diphenyl-N, N'-di(3-methylphenyl)-4,4'-diphenyl-1,1'-diamine, N,N'-dinaphthyl-N,N'-diphenyl-4,4'-diphenyl- 1,1′-diamine, N ⁴ ,N ^{4 ′} -diphenyl-N ⁴ ,N ^{4 ′} -bis(9-phenyl-9H-carbazol-3-yl)-[1,1′-biphenyl]- 4,4'-diamine, N ⁴ ,N ⁴ ,N ^{4 '} ,N ^4' -tetra[1,1'-biphenyl]-4-yl)-[1,1'-biphenyl]-4,4 Triphenylamine derivatives such as '-diamine, 4,4',4"-tris(3-methylphenyl(phenyl)amino)triphenylamine, starburst amine derivatives, etc.), stilbene derivatives, phthalocyanine derivatives (metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone-based compounds, benzofuran derivatives, thiophene derivatives, oxadiazole derivatives, quinoxaline derivatives (e.g., 1,4,5,8,9,12-hexaazatriphenylene -2,3,6,7,10,11-hexacarbonitrile, etc.), heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. In the polymer system, polycarbonates having the above monomers in their side chains, styrene derivatives, and polyvinylcar Bazole and polysilane are preferred, but it is not particularly limited as long as it is a compound capable of forming a thin film necessary for manufacturing a light emitting device, injecting holes from an anode, and transporting holes. As a material, a compound represented by formula (1) can be used.

It is also known that the conductivity of an organic semiconductor is strongly influenced by its doping. Such an organic semiconductor matrix material is composed of a compound having good electron-donating property or a compound having good electron-accepting property. For doping of electron donor materials, strong electron acceptors such as tetracyanoquinonedimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinonedimethane (F4TCNQ) are used. known (see, for example, M. Pfeiffer, A. Beyer, T. Fritz, K. Leo, Appl. Phys. Lett., 73(22), 3202-3204 (1998) and J. Blochwitz , M. Pheiffer, T. Fritz, K. Leo, Appl. Phys. Lett., 73(6), 729-731 (1998)). These generate so-called holes by an electron transfer process in an electron donating base material (hole transport material). Depending on the number and mobility of holes, the conductivity of the base material varies considerably. As matrix materials having hole transport properties, for example, benzidine derivatives (TPD, etc.) or starburst amine derivatives (TDATA, etc.), or specific metal phthalocyanines (particularly, zinc phthalocyanine (ZnPc), etc.) are known (Japanese Patent Laid-Open 2005 -167175).

A hole buffer layer may be additionally provided between the hole injection layer 120 and the hole transport layer 130, and may include a hole injection or transport material known in the art.

The light emitting layer 140 is a layer that emits light by recombination of holes injected from the anode 110 and electrons injected from the cathode 170 between electrodes to which an electric field is applied. The material for forming the light-emitting layer 140 may be a compound that is excited by recombination of holes and electrons and emits light (luminescent compound), which can form a stable thin film shape and exhibits strong light emission (fluorescence) efficiency in a solid state. It is preferable that it is a visible compound.

The light emitting mechanism of the light emitting layer 140 is divided into fluorescence and phosphorescence. Fluorescence is a mechanism in which excitons in a singlet state, among excitons generated by the combination of holes and electrons, emit light while descending to the ground state, and phosphorescence is a mechanism in which excitons in a triplet state emit light while descending to the ground state. 25% of singlet excitons and 75% of triplet excitons are generated by the combination of holes and electrons, unlike fluorescence in which only 25% of singlet excitons contribute to light emission, in the case of phosphorescence, 75% of triplet excitons and 75% of triplet excitons Since all 25% of singlet excitons that can be converted into triplet excitons through intersystematic transition contribute to light emission, it is theoretically possible to achieve 100% internal quantum efficiency.

The light emitting layer 140 may be a single layer or a plurality of layers, and may contain a host and a dopant to improve color purity and quantum efficiency. In the light emitting layer 140 having such a structure, excitons generated in the host are transferred to dopants to emit light. The host material and the dopant material may be of one type or a combination of a plurality thereof. The dopant material may be included entirely or partially in the host material. As the doping method, it can be formed by co-evaporation with the host material, but it may be deposited simultaneously after mixing with the host material in advance, or may be formed by a wet film forming method after mixing with the host material in advance with an organic solvent.

The amount of host material used varies depending on the type of host material, and may be determined according to the characteristics of the host material. The standard for the amount of host material used is preferably 50 to 99.999% by weight, more preferably 80 to 99.95% by weight, still more preferably 90 to 99.9% by weight of the total light emitting layer material.

The usage amount of the dopant material varies depending on the type of the dopant material, and may be determined according to the characteristics of the dopant material. The standard for the amount of dopant material used is preferably 0.001 to 50% by weight, more preferably 0.05 to 20% by weight, still more preferably 0.1 to 10% by weight of the total light emitting layer material. The above range is preferable in that, for example, the concentration quenching phenomenon can be prevented.

Examples of the host material include condensed aromatic ring derivatives and heterocyclic compound. Specifically, condensed aromatic ring derivatives include anthracene derivatives, pyrene derivatives, naphthalene derivatives, pentacene derivatives, phenanthrene compounds, fluoranthene compounds, etc., and heterocyclic-containing compounds include carbazole derivatives, dibenzofuran derivatives, ladder type furan compounds, pyrimidine derivatives, etc., but are not limited thereto.

When the light emitting layer emits red light, PIQIr (acac) (bis (1-phenylisoquinoline) acetylacetonateiridium), PQIr (acac) (bis (1-phenylquinoline) acetylacetonate iridium), PQIr (tris (1-phenylquinoline) iridium) are used as dopants. , A phosphorescent material such as octaethylporphyrin platinum (PtOEP) or a fluorescent material such as tris(8-hydroxyquinolino)aluminum (Alq3) may be used, but is not limited thereto. When the light emitting layer emits green light, a phosphorescent material such as Ir(ppy)3 (fac tris(2-phenylpyridine)iridium) or a fluorescent material such as Alq3 (tris(8-hydroxyquinolino)aluminum) may be used as a dopant. , but is not limited to this. When the light emitting layer emits blue light, as the light emitting dopant, a phosphorescent material such as (4,6-F2ppy)2Irpic, spiro-DPVBi, spiro-6P, distylbenzene (DSB), distryarylene (DSA), or PFO A fluorescent material such as a polymer-based polymer or a PPV-based polymer may be used, but is not limited thereto.

For example, a polyaromatic compound represented by the following formula (BD-YX2) or a multimer of a polycyclic aromatic compound having a plurality of structures represented by the following formula (BD-YX2) may be used as the blue light emitting dopant.

In the formula (BD-YX2), ring A, ring B and ring C are each independently an aryl ring or a heteroaryl ring, and at least one hydrogen in these rings may be substituted;

Y1 is B, P, P=O, P=S, Al, Ga, As, Si-R or Ge-R, R of Si-R and Ge-R is aryl, alkyl or cycloalkyl,

X1 and X2 are each independently >O, >NR, >C(-R) ₂ , >S or >Se, wherein R in >NR is optionally substituted aryl, optionally substituted heteroaryl, or substituted optionally substituted alkyl or optionally substituted cycloalkyl, wherein R in >C(-R) ₂ is hydrogen, optionally substituted aryl, optionally substituted alkyl or optionally substituted cycloalkyl, and also the above >NR At least one of R in and R in >C(-R) ₂ may be bonded to at least one of the A ring, B ring and C ring by a linking group or a single bond;

At least one hydrogen in the compound or structure represented by formula (BD-YX2) may be substituted with deuterium, cyano or halogen,

In the compound or structure represented by formula (BD-YX2), at least one of ring A, ring B, ring C, aryl and heteroaryl may be condensed with at least one cycloalkane, and in the cycloalkane At least one hydrogen may be substituted, and at least one -CH2- in the cycloalkane may be substituted with -O-.

In particular, the aryl ring or heteroaryl ring as ring A, ring B, and ring C in the above formula (BD-YX2) is a 5-membered ring or a 5-membered ring that shares a bond with the condensed bicyclic structure in the center of the above formula composed of Y1, X1 and X2. It is preferable that it is a 6-membered ring.

The electron injection layer 160 serves to efficiently inject electrons moving from the cathode 170 into the light emitting layer 140 or into the electron transport layer 150 .

The electron transport layer 150 serves to efficiently transport electrons injected from the cathode 170 or electrons injected from the cathode 170 through the electron injection layer 160 to the light emitting layer 140 .

As a material for the electron transport layer 150, a compound having electron acceptor characteristics and high electron mobility is suitable. In addition, it should have a LUMO (Lowest Unoccupied Molecular Orbital) energy level suitable for injecting electrons into the light emitting layer 140, and to prevent holes from passing from the light emitting layer 140 to the electron transport layer 150, the HOMO of the light emitting layer 140 (Highest Occupied Molecular Orbital) It is preferable that the energy level and the difference are large.

The electron transport layer 150 and the electron injection layer 160 are formed by laminating and mixing one type or two or more types of electron transport/injection materials, respectively.

The electron injection/transport layer is a layer responsible for injecting electrons from the cathode and transporting the electrons, and preferably has high electron injection efficiency and efficiently transports the injected electrons. For this purpose, it is preferable to use a material that has high electron affinity, high electron mobility, excellent stability, and hardly generates trap impurities during production and use. The electron injection/transport layer in this embodiment may have the function of a layer capable of effectively blocking the movement of holes. As the material forming the electron transport layer 150 or the electron injection layer 160, a compound conventionally used as an electron transport compound in a photoconductive material, or a known material used for an electron injection layer and an electron transport layer of an organic electroluminescent device. It can be used by selecting it arbitrarily from a compound.

In general, as materials used for the electron transport layer or the electron injection layer, compounds comprising an aromatic ring or heteroaromatic ring composed of at least one atom selected from carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus, pyrrole derivatives, and condensates thereof It is preferable to contain at least one selected from ring derivatives and metal complexes having electron-accepting nitrogen. Specifically, condensed ring aromatic ring derivatives such as naphthalene and anthracene, styryl aromatic ring derivatives represented by 4,4'-bis(diphenylethenyl)biphenyl, perinone derivatives, coumarin derivatives, and naphthalimide derivatives , quinone derivatives such as anthraquinone and diphenoquinone, phosphorus oxide derivatives, carbazole derivatives, and indole derivatives. Examples of the metal complex having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, flavonol metal complexes, and benzoquinoline metal complexes. Although these materials are used alone, you may mix and use them with other materials.

In addition, as specific examples of other electron transfer compounds, pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, diphenylquinone Derivatives, perylene derivatives, oxadiazole derivatives (1,3-bis[(4-t-butylphenyl)1,3,4-oxadiazolyl]phenylene, etc.), thiophene derivatives, triazole derivatives (N- naphthyl-2,5-diphenyl-1,3,4-triazole, etc.), thiadiazole derivatives, metal complexes of auxin derivatives, quinolinol-based metal complexes, quinoxaline derivatives, polymers of quinoxaline derivatives, benzazoles compounds, gallium complexes, pyrazole derivatives, perfluorinated phenylene derivatives, triazine derivatives, pyrazine derivatives, benzoquinoline derivatives (2,2'-bis(benzo[h]quinolin-2-yl)-9,9' -spirobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzoimidazole derivatives (tris(N-phenylbenzoimidazol-2-yl)benzene, etc.), benzoxazole derivatives, benzothiazole derivatives, quinoline derivatives , Oligopyridine derivatives such as terpyridine, bipyridine derivatives, terpyridine derivatives (1,3-bis (4'-(2,2': 6'2"-terpyridinyl)) benzene, etc.), naphthyridine derivatives ( bis(1-naphthyl)-4-(1,8-naphthyridin-2-yl)phenylphosphine oxide, etc.), aldazine derivatives, carbazole derivatives, indole derivatives, inoxide derivatives, bisstyryl derivatives, etc. can be heard

In addition, metal complexes having electron-accepting nitrogen can also be used, for example, quinolinol-based metal complexes, hydroxyazole complexes such as hydroxyphenyloxazole complexes, azomethine complexes, tropolone metal complexes, and flavonol metal complexes. and benzoquinoline metal complexes.

Although the above materials are used alone, they may be used in combination with other materials.

Among the above materials, borane derivatives, pyridine derivatives, fluoranthene derivatives, BO derivatives, anthracene derivatives, benzofluorene derivatives, phosphine oxide derivatives, pyrimidine derivatives, carbazole derivatives, triazine derivatives, benzoimidazole derivatives, Phenanthroline derivatives and quinolinol-based metal complexes are preferred.

The cathode 170 serves to inject electrons into the light emitting layer 140 through the electron injection layer 160 and the electron transport layer 150 .

A material forming the cathode 170 is preferably a material having a low work function so that electrons can be efficiently injected into the organic material layer. Specific examples of the negative electrode material include metals such as tin, indium, calcium, aluminum, silver, lithium, sodium, potassium, titanium, yttrium, gadolinium, lead, cesium, and magnesium, or alloys thereof (magnesium-silver alloy, magnesium-indium alloy , aluminum-lithium alloys such as lithium fluoride/aluminum, etc.) and the like are preferable. In order to improve device characteristics by increasing the electron injection efficiency, lithium, sodium, potassium, cesium, calcium, magnesium or alloys containing these low work function metals are effective. However, these low work function metals are generally unstable in air in many cases. In order to improve this point, for example, a method of doping the organic material layer with a small amount of lithium, cesium or magnesium to use a highly stable electrode is known. As other dopants, inorganic salts such as lithium fluoride, cesium fluoride, lithium oxide and cesium oxide can also be used. However, it is not limited to these.

The organic material layer may further include an electron blocking layer between the hole transport layer 130 and the light emitting layer 140, and may further include a hole blocking layer between the electron transport layer 150 and the light emitting layer 140.

In the electron blocking layer and the hole blocking layer, excitons generated in the light emitting layer 140 diffuse to the electron transport layer 150 or hole transport layer 130 adjacent to the light emitting layer 140, or are not recombinated in the light emitting layer 140, and the hole transport layer ( 130) or a layer that prevents electrons or holes from passing over to the electron transport layer 150. As a result, the number of excitons contributing to light emission in the light emitting layer is increased, so that the light emitting efficiency of the device is improved and the driving voltage may be lowered. In addition, by preventing an irreversible decomposition reaction due to oxidation due to diffusion of holes into the electron transport layer 150 that moves electrons by reduction (electron acceptor), the durability and stability of the device are improved and the life of the device is efficiently improved. can be increased

Materials known in the art may be used as the electron blocking layer or the hole blocking layer. The organic material layer may further include a light emitting auxiliary layer (not shown) between the electron blocking layer and the light emitting layer 140 . The light emitting auxiliary layer may play a role of transporting holes to the light emitting layer 140 and adjusting the thickness of the organic layer. The light emitting auxiliary layer may use a material known in the art as a hole transport material. In the present invention, the compound represented by Formula 1 can be used as a material for the electron blocking layer or the light emitting auxiliary layer.

The materials used for the above hole injection layer, hole transport layer, light emitting layer, electron transport layer and electron injection layer can form each layer independently, but as a polymer binder, polyvinyl chloride, polycarbonate, polystyrene, poly(N-vinylcar Bazol), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate resin, ABS Used after being dispersed in solvent-soluble resins such as resins and polyurethane resins, or curable resins such as phenol resins, xylene resins, petroleum resins, urea resins, melamine resins, unsaturated polyester resins, alkyd resins, epoxy resins, and silicone resins. It is also possible to do

<Method of manufacturing organic electroluminescent device>

For each layer constituting the organic electroluminescent device, the material that should constitute each layer is deposited by a method such as evaporation, resistance heating evaporation, electron beam evaporation, sputtering, molecular lamination, printing, spin coating, casting, or coating. It can be formed by making it into a thin film.

The film thickness of each layer formed in this way is not particularly limited and can be set appropriately depending on the nature of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured with a crystal oscillation type film thickness measuring device or the like.

In the case of forming a thin film using a vapor deposition method, the deposition conditions vary depending on the type of material, the crystal structure and association structure of the film, and the like. Deposition conditions are generally heating temperature of the deposition crucible +50 to +400°C, vacuum degree 10 ^-6 to 10 ^-3 Pa, deposition rate 0.01 to 50nm/sec, substrate temperature -150 to +300°C film thickness 2nm to 5 It is preferable to set appropriately in the range of micrometers.

Next, as an example of a method for manufacturing an organic electroluminescent device, a method for manufacturing an organic electroluminescent device composed of an anode/a hole injection layer/a hole transport layer/a light emitting layer composed of a host material and a dopant material/an electron transport layer/an electron injection layer/cathode is provided. explain about

After fabricating an anode by forming a thin film of anode material on a suitable substrate by vapor deposition or the like, thin films of a hole injection layer and a hole transport layer are formed on the anode. A thin film is formed by codepositioning a host material and a dopant material thereon to form a light emitting layer, an electron transporting layer and an electron injecting layer are formed on the light emitting layer, and a thin film made of a cathode material is formed by a vapor deposition method or the like to form a cathode. By doing so, a desired organic electroluminescent device is obtained. Further, in the fabrication of the organic electroluminescent device described above, it is also possible to reverse the fabrication order and fabricate the cathode, electron injection layer, electron transport layer, light emitting layer, hole transport layer, hole injection layer, and anode in this order.

<Application example of organic electroluminescence device>

In addition, the present invention can be applied to a display device provided with an organic electroluminescent device or a lighting device provided with an organic electroluminescent device.

A display device or lighting device having an organic electroluminescent element is manufactured by a known method such as connecting such an organic electroluminescent element and a known driving device (e.g., a drain electrode or a source electrode of a thin film transistor) in this embodiment. It can be driven by appropriately using known driving methods such as direct current driving, pulse driving, and alternating current driving.

Examples of the display device include panel displays such as color flat panel displays, flexible displays such as flexible color organic electroluminescent (EL) displays, and the like (eg, Japanese Unexamined Patent Publication No. 10-335066, Japanese Unexamined Patent Publication No. 2003-321546, Japanese Unexamined Patent Publication No. 2004-281706, etc.). In addition, as a display method of a display, a matrix method and/or a segment method etc. are mentioned, for example. Also, the matrix display and the segment display may coexist in the same panel.

In the matrix, pixels for display are two-dimensionally arranged in a lattice or mosaic form, and characters or images are displayed by a set of pixels. The shape or size of the pixel is determined according to the purpose. For example, for image and character display on PCs, monitors, and televisions, square pixels with sides of 300 μm or less are usually used, and in the case of large displays such as display panels, pixels on the order of mm are used. do. In the case of monochrome display, pixels of the same color may be arranged, but in the case of color display, pixels of red, green, and blue are arranged and displayed. In this case, there are typically a delta type and a stripe type. Incidentally, as a driving method for this matrix, either a line-sequential driving method or an active matrix is used. Although the line-sequential drive has the advantage of having a simple structure, when operating characteristics are considered, the active matrix may be superior, so it is necessary to use this differently depending on the purpose.

In the segment method (type), a pattern is formed to display predetermined information, and a predetermined area is illuminated. For example, the time or temperature display in a digital watch or thermometer, the operation state display of an audio device or electric cooker, and the panel display of a car etc. are mentioned.

Examples of the lighting device include lighting devices such as indoor lighting, backlights of liquid crystal display devices, and the like (for example, Japanese Patent Laid-Open No. 2003-257621, Japanese Patent Laid-Open No. 2003-277741, Japanese Patent). Publication No. 2004-119211, etc.). Backlights are mainly used for the purpose of improving the visibility of display devices that do not emit self-luminescence, and are used for liquid crystal display devices, clocks, audio devices, automobile panels, display panels, and signs. In particular, as a backlight for a liquid crystal display device, especially a PC where thinning is a problem, considering that it is difficult to reduce the thickness because the conventional method consists of a fluorescent lamp or a light guide plate, the backlight using the light emitting element according to the present embodiment is thin. , light weight is characterized.

<Example>

The present invention will be described more specifically by way of examples below, but the present invention is not limited thereto.

[Synthesis Example 1] Compound P1

In a 1000 ml round bottom flask, 30 g (112.27 mmol) of 6-Bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene, 25.85 g of 9,9-Dimethyl-9H-fluoren-2-amine ( 123.50 mmol), Pd ₂ (dba) ₃ 3.08 g (3.37 mmol), P(t-Bu) 1.36 g (6.74 mmol), and NaOtBu 35.61 g (370.50 mmol) were added. Put 500ml of toluene as a solvent and stir at 50 ^o C. After confirming the reaction by TLC, when the reaction is complete, the temperature is cooled to room temperature. After adding water to the reaction solution and stirring, the organic layer and the water layer are separated. The organic layer was filtered through silica gel and concentrated. After concentration, column chromatography was performed to obtain 32.40 g (73.0%) of Compound A.

In a 500ml round bottom flask, compound A 15 g (37.92 mmol), 1-Bromodibenzo[b,d]furan 9.37 g (37.92 mmol), Pd ₂ (dba) ₃ 1.04 g (1.14 mmol), P(t-Bu) 0.46 g (2.28 mmol) and 10.93 g (113.75 mmol) of NaOtBu were added. Put 200ml of toluene as a solvent and stir at 90 ^° C. After confirming the reaction by TLC, when the reaction is complete, the temperature is cooled to room temperature. After adding water to the reaction solution and stirring, the organic layer and the water layer are separated. The organic layer was filtered through silica gel and concentrated. After concentration, recrystallization was performed to obtain 16.70 g (78.4%) of compound P1.

[Synthesis Example 2] Compound P30

In a 1000 ml round bottom flask, 30 g (112.27 mmol) of 6-Bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene, 25.85 g of 9,9-dimethyl-9H-fluoren-1-amine ( 123.50 mmol), Pd ₂ (dba) ₃ 3.08 g (3.37 mmol), P(t-Bu) 1.36 g (6.74 mmol), and NaOtBu 35.61 g (370.50 mmol) were prepared in the same manner as in Compound A to obtain compound B 32.40 g (69.3%) was obtained.

In a 500 ml round bottom flask, compound B 15 g (37.92 mmol), 2-bromodibenzo[b,d]thiophene 9.98 g (37.92 mmol), Pd ₂ (dba) ₃ 1.04 g (1.14 mmol), P(t-Bu) ₃ 0.46 g (2.28mmol), NaOtBu 10.93g (113.75 mmol) was carried out in the same manner as in the compound P1 to obtain 15.80g (72.11%) of compound P30.

[Synthesis Example 3] Compound P78

In a 1000 ml round bottom flask, 30 g (112.27 mmol) of 6-Bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene, 37.43 g of 9,9-diphenyl-9H-fluoren-2-amine ( 123.50 mmol), Pd ₂ (dba) ₃ 3.08g (3.37 mmol), P(t-Bu) 1.36g (6.74mmol), NaOtBu 35.61g (370.50 mmol) was carried out in the same manner as in Compound A to obtain compound C 43.00 g (73.69%) was obtained.

In a 500 ml round bottom flask, 15 g (28.86 mmol) of compound C, 12.39 g (28.86 mmol) of 3-bromo-9,9-diphenyl-9H-thioxanthene, 0.79 g (0.87 mmol) of Pd ₂ (dba) ₃ , P(t- Bu) ₃ 0.35g (1.73mmol) and NaOtBu 8.32g (86.58mmol) were carried out in the same manner as in Compound P1 to obtain 21.40g (85.41%) of Compound P78.

[Synthesis Example 4] Compound P84

In a 1000 ml round bottom flask, 6-Bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene 30 g (112.27 mmol), 9,9-diphenyl-9H-fluoren-2-amine 41.18 g ( 123.50 mmol), Pd ₂ (dba) ₃ 3.08g (3.37 mmol), P(t-Bu) 1.36g (6.74mmol), NaOtBu 35.61g (370.50 mmol) was carried out in the same manner as in Compound A to obtain compound D 42.30 g (72.49%) was obtained.

In a 1000 ml round bottom flask, 50 g (261.17 mmol) of 1-Bromo-3-chlorobenzene, 39.30 g (235.05 mmol) of 9H-carbazole, 7.17 g (7.84 mmol) of Pd ₂ (dba) ₃ , 3.17 g of P (t-Bu) ( 15.67 mmol) and NaOtBu 67.77 g (705.15 mmol) were added. Put 500ml of toluene as a solvent and stir at 110 ^o C. After confirming the reaction by TLC, when the reaction is complete, the temperature is cooled to room temperature. After adding water to the reaction solution and stirring, the organic layer and the water layer are separated. The organic layer was filtered through silica gel and concentrated. After concentration, column chromatography was performed to obtain 43.60 g (60.11%) of Compound E.

In a 500 ml round bottom flask, 15 g (28.86 mmol) of Compound D, 8.02 g (28.86 mmol) of Compound E, _0.79 g (0.87 mmol) of Pd ₂ (dba) _3, 0.35 g (1.73 mmol) of P(t-Bu) 3, NaOtBu 8.32g (86.58 mmol) was carried out in the same manner as in compound P1 to obtain 17.50g (79.68%) of compound P84.

[Synthesis Example 5] Compound P106

In a 1000 ml round bottom flask, 6-Bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene 30 g (112.27 mmol), 9,9'-spirobi[fluoren]-2-amine 40.93 g ( 123.50 mmol), Pd ₂ (dba) ₃ 3.08 g (3.37 mmol), P(t-Bu) 1.36 g (6.74 mmol), NaOtBu 35.61 g (370.50 mmol) was carried out in the same manner as in Compound A to obtain compound F 43.60 g (75.01%) was obtained.

In a 500 ml round bottom flask, compound F 15 g (28.86 mmol), 3'-bromospiro[fluorene-9,9'-xanthene 11.87 g (28.86 mmol), Pd ₂ (dba) ₃ 0.79 g (0.87 mmol), P(t- Bu) ₃ 0.35g (1.73mmol) and NaOtBu 8.32g (86.58mmol) were carried out in the same manner as in Compound P1 to obtain 20.20g (82.53%) of Compound P106.

[Synthesis Example 6] Compound P123

In a 1000 ml round bottom flask, 30 g (112.27 mmol) of 6-Bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene, 24.61 g (123.50 mmol) of dibenzo[b,d]thiophen-1-amine ), Pd ₂ (dba) ₃ 3.08 g (3.37 mmol), P (t-Bu) 1.36 g (6.74 mmol), NaOtBu 35.61 g (370.50 mmol) was carried out in the same manner as in Compound A to obtain compound G 32.70 g ( 75.54%) was obtained.

In a 1000 ml round bottom flask, 2-Bromo-9,9-dimethyl-9H-fluorene 30g (109.82 mmol), (9-chlorodibenzo[b,d]furan-2-yl)boronic acid 28.42g (115.31mmol), Pd( Add 3.81 g (3.30 mmol) of PPh ₃ ) ₄ and 45.54 g (329.47 mmol) of K ₂ CO ₃ . 400ml of toluene, 100ml of ethanol, and 200ml of H ₂ O were added as solvents and stirred at 90 ^° C. After confirming the reaction by TLC, when the reaction is complete, the temperature is cooled to room temperature. After adding water to the reaction solution and stirring, the organic layer and the water layer are separated. The organic layer was filtered through silica gel and concentrated. After concentration, column chromatography was performed to obtain 28.30 g (65.25%) of compound H.

In a 500 ml round bottom flask, 15 g (38.90 mmol) of compound G, 15.36 g (38.90 mmol) of compound H, _1.07 g (1.17 mmol) of Pd ₂ (dba) _3, 0.47 g (2.33 mmol) of P(t-Bu) 3, NaOtBu 11.22 g (116.71 mmol) was carried out in the same manner as in compound P1 to obtain 22.40 g (77.39%) of compound P123.

[Synthesis Example 7] Compound P143

In a 1000 ml round bottom flask, 30 g (75.89 mmol) of 4-Bromo-9,9'-spirobi[fluorene], 16.64 g (83.48 mmol) of dibenzo[b,d]thiophen-2-amine, 2.08 g of Pd ₂ (dba) ₃ (2.28 mmol), P(t-Bu) ₃ 0.92g (4.55mmol), and NaOtBu 24.07g (250.44 mmol) were carried out in the same manner as in Compound A to obtain 32.00g (82.09%) of Compound I.

6-Bromo-1,1,4,4-tetramethyl-1,2,3,4-tetrahydronaphthalene 50 g (187.12 mmol), (4-chlorophenyl)boronic acid 28.67 g (183.38 mmol), Pd( Add 6.49 g (5.61 mmol) of PPh ₃ ) ₄ and 77.59 g (561.36 mmol) of K ₂ CO ₃ . 400ml of toluene, 100ml of ethanol, and 200ml of H ₂ O were added as solvents and stirred at 90 ^° C. After confirming the reaction by TLC, when the reaction is complete, the temperature is cooled to room temperature. After adding water to the reaction solution and stirring, the organic layer and the water layer are separated. The organic layer was filtered through silica gel and concentrated. After concentration, column chromatography was performed to obtain 37.10 g (66.34%) of compound H.

In a 500 ml round bottom flask, 15 g (29.20 mmol) of compound I, 8.73 g (29.20 mmol) of compound J, _0.80 g (0.88 mmol) of Pd ₂ (dba) _3, 0.35 g (1.75 mmol) of P(t-Bu) 3, NaOtBu 8.42g (87.61 mmol) was carried out in the same manner as in compound P1 to obtain 18.30g (80.75%) of compound P143.

Other compounds of the present invention can be synthesized by a method according to the synthesis example described above by appropriately changing the starting compound.

<Example of device application>

[Example 1]

두께로 박막 코팅된 유리 기판을 증류수 초음파로 세척하였다. 증류수 세척이 끝난 후, 용제(이소프로필 알코올, 아세톤, 메탄올 등)로 초음파 세척을 하고, 건조시켰다. 이렇게 준비된 ITO 투명 전극 위에 HI를 40nm의 두께로 열 진공 증착하여 제1 정공주입층을 형성하였다. 제1 정공 주입층 상에 HAT-CN을 5nm의 두께로 열 진공증착 하여 제2 정공주입층을 형성하고, 제2 정공주입층상에 화합물 P1을 20nm의 두께로 진공 증착하여 정공수송층을 형성하였다. 이어서 정공수송층 위에 호스트 BH와 도판트 BD(중량기준 95:5)을 20nm의 두께로 진공 증착하여 발광층을 형성하였다. 발광층 위에 ET2를 10nm의 두께로 증착하여 정공저지층을 형성하였고, 정공저지층상에 ETL을 20nm 두께로 형성하여 전자수송층을 형성하였다. 전자수송층 위에 순차적으로 1nm 두께의 리튬 플루오라이드(LiF)를 증착하고 1,000

두께의 알루미늄을 증착하여 음극을 형성함으로써, 유기 전계 발광 소자를 제조하였다.ITO (Indium tin oxide) is 1000

A thin film coated glass substrate was washed with ultrasonic waves in distilled water. After washing with distilled water, ultrasonic cleaning was performed with a solvent (isopropyl alcohol, acetone, methanol, etc.) and dried. HI was thermally vacuum deposited to a thickness of 40 nm on the prepared ITO transparent electrode to form a first hole injection layer. HAT-CN was thermally vacuum deposited on the first hole injection layer to a thickness of 5 nm to form a second hole injection layer, and compound P1 was vacuum deposited on the second hole injection layer to a thickness of 20 nm to form a hole transport layer. Subsequently, a light emitting layer was formed by vacuum depositing host BH and dopant BD (95:5 by weight) to a thickness of 20 nm on the hole transport layer. ET2 was deposited on the emission layer to a thickness of 10 nm to form a hole blocking layer, and ETL was formed to a thickness of 20 nm on the hole blocking layer to form an electron transport layer. On the electron transport layer, 1 nm thick lithium fluoride (LiF) was sequentially deposited, and 1,000

An organic electroluminescent device was manufactured by depositing a thick layer of aluminum to form a cathode.

[Examples 2 to 10]

An organic electroluminescent device was manufactured in the same manner as in Example 1, except that the compound of the present invention shown in Table 1 was used instead of Compound P1 as the hole transport layer in Example 1.

[Comparative Examples 1 and 2]

Experiments were performed in the same manner as in Example 1, except that NPB and Comparative Compound A were used instead of Compound P1 as the hole transport layer.

[Comparative Compound A]

As in Examples 1 to 10 and Comparative Examples 1 to 2, the results of measuring the characteristics of organic electroluminescent devices prepared using each compound as a hole transport layer material are shown in Table 1.

As can be seen from the results of Table 1, when a blue organic light emitting device was produced using the material for an organic light emitting device of the present invention as a hole transport layer material, the organic light emitting device was higher than the comparative example using NPB or Comparative Compound A It is possible to improve the driving voltage, luminous efficiency and lifetime of the.

100 substrate
110 anode (first electrode)
120 hole injection layer
130 hole transport layer
140 light emitting layer
150 electron transport layer
160 electron injection layer
170 cathode (second electrode)

Claims (10)

A compound represented by Formula 1 below:

In Formula 1,
L ₁ to L ₃ are the same as or different from each other, and each independently represents a single bond, a substituted or unsubstituted C ₁ -C ₁₀ alkylene group, a substituted or unsubstituted C ₃ -C ₃₀ arylene group, or a substituted or unsubstituted C 1 -C 10 alkylene group. selected from the group consisting of a C ₂ -C ₃₀ heteroarylene group, a substituted or unsubstituted C ₃ -C ₂₀ cycloalkylene group, and a substituted or unsubstituted C ₂ -C ₂₀ heterocycloalkylene group,
X ₁ and X ₂ are the same as or different from each other, and are each independently selected from the group consisting of a single bond, CR ₃ R ₄ , O, S or NR ₅ , X ₁ and X ₂ cannot be a single bond at the same time, ,
R ₁ to R ₅ are the same as or different from each other, and are each independently hydrogen, heavy hydrogen, a trifluoromethyl group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, a substituted or unsubstituted C ₃ -C ₃₀ cycloalkyl group, substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, substituted or unsubstituted C ₁ -C ₂₀ heteroalkyl group , a substituted or unsubstituted C ₃ -C ₂₀ aralkyl group, a substituted or unsubstituted C ₃ -C ₃₀ aryl group, a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group, a substituted or unsubstituted C ₃ -C ₂₀ heteroaralkyl group, substituted or unsubstituted C ₁ -C ₃₀ alkylsilyl group, substituted or unsubstituted C ₃ -C ₃₀ arylsilyl group, and substituted or unsubstituted C ₃ -C ₃₀ It is selected from the group consisting of a heteroarylsilyl group, R ₁ to R ₅ may combine with adjacent groups to form a substituted or unsubstituted ring,
m is an integer from 0 to 4;
n is an integer from 0 to 3;
Ar ₁ and Ar ₂ are the same as or different from each other, and each independently represents a substituted or unsubstituted C ₅ -C ₃₀ aryl group, a substituted or unsubstituted C 3 -C 30 heteroaryl group, or a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group. ₁ -C ₂₀ alkyl group, substituted or unsubstituted C ₁ -C ₂₀ alkenyl group, substituted or unsubstituted C ₁ -C ₂₀ alkynyl group, substituted or unsubstituted C ₃ -C ₂₀ cycloalkyl group, substituted Or an unsubstituted C ₁ -C ₂₀ heteroalkyl group, a substituted or unsubstituted C ₃ -C ₂₀ heterocycloalkyl group, a substituted or unsubstituted C ₅ -C ₃₀ aralkyl group, a substituted or unsubstituted C ₃ - C ₃₀ heteroaralkyl group, substituted or unsubstituted C ₃ -C ₂₀ cycloalkenyl group, substituted or unsubstituted C ₁ -C ₂₀ heteroalkenyl group, substituted or unsubstituted C ₆ -C ₄₀ arylamine group, and a substituted or unsubstituted C ₅ -C ₄₀ selected from the group consisting of a heteroarylamine group;
At least one hydrogen in the formula (1) may be substituted with deuterium. According to claim 1,
Ar ₁ and Ar ₂ Any one of which is a compound represented by Formula 2 or Formula 3:

In Formula 2 and Formula 3,
X ₃ to X ₅ are the same as or different from each other, and are each independently selected from the group consisting of a single bond, CR _a R _b , O, S or NR _c , X ₃ and X ₄ cannot be a single bond at the same time, ,
X ₆ is NR _c ;
R ₆ to R ₉ and Ra to Rc are the same as or different from each other, and each independently represents hydrogen, heavy hydrogen, a trifluoromethyl group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted C ₁ -C ₂₀ alkyl group, or a substituted group. Or an unsubstituted C ₃ -C ₃₀ cycloalkyl group, a substituted or unsubstituted C ₂ -C ₃₀ alkenyl group, a substituted or unsubstituted C ₂ -C ₂₀ alkynyl group, a substituted or unsubstituted C ₁ -C ₂₀ heteroalkyl group, substituted or unsubstituted C ₃ -C ₂₀ aralkyl group, substituted or unsubstituted C ₃ -C ₃₀ aryl group, substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group, substituted or An unsubstituted C ₃ -C ₂₀ heteroaralkyl group, a substituted or unsubstituted C ₁ -C ₃₀ alkylsilyl group, a substituted or unsubstituted C ₃ -C ₃₀ arylsilyl group, and a substituted or unsubstituted C ₃ -C ₃₀ It is selected from the group consisting of a heteroarylsilyl group, R ₆ ~ R ₉ and Ra ~ Rc may combine with adjacent groups to form a substituted or unsubstituted ring,
o is an integer from 0 to 3;
p, q and r are integers from 0 to 4;
* is Ar ₁ and Ar ₂ Any one of them is a position at which the compound represented by Formula 1 is bonded. According to claim 2,
Ar ₁ and Ar ₂ The other one is a substituted or unsubstituted C ₃ -C ₃₀ heteroaryl group, a compound. According to claim 1,
X ₁ and X ₂ are both CR ₃ R ₄ (wherein R3 and R4 are as defined in claim 1). According to claim 4,
In CR ₃ R ₄ of X ₁ and X ₂ , R ₃ and R ₄ are the same as or different from each other, and each independently represents a substituted or unsubstituted C ₁ -C ₂₀ alkyl group. a first electrode;
a second electrode facing the first electrode;
An organic material layer interposed between the first electrode and the second electrode,
An organic electroluminescent device in which the organic material layer includes the compound of claim 1 . According to claim 6,
The first electrode is an anode,
The second electrode is a cathode,
The organic material layer,
i) a light emitting layer;
ii) a hole transport region interposed between the first electrode and the light emitting layer and including at least one of a hole injection layer, a hole transport layer, an electron blocking layer, and a light emitting auxiliary layer; and
iii) an electron transport region interposed between the light emitting layer and the second electrode and including at least one of a hole blocking layer, an electron transport layer, and an electron injection layer;
wherein the hole transport region comprises the compound of claim 1,
organic electroluminescent device. According to claim 7,
An organic electroluminescent device, wherein the hole transport layer comprises the compound of claim 1. According to claim 7,
An organic electroluminescent device, wherein the electron blocking layer or the light emitting auxiliary layer contains the compound of claim 1. A display device comprising the organic electroluminescent device of claim 6, wherein a first electrode of the organic electroluminescent device is electrically connected to a source electrode or a drain electrode of a thin film transistor.

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