KR102656634B1 - Organometallic compound and organic light-emitting device comprising the same - Google Patents

Abstract

The present invention relates to an organometallic compound and an organic electroluminescent device containing the same. Due to the steric hindrance effect of the organometallic compound, when used as a phosphorescent dopant material in an organic electroluminescent device, the low half width and dopant concentration quenching phenomenon can be controlled. .
In addition, it is possible to provide an organic electroluminescent device that has a low driving voltage and can exhibit high efficiency and long lifespan characteristics.

Description

Organic metal compound and organic electroluminescent device comprising the same {ORGANOMETALLIC COMPOUND AND ORGANIC LIGHT-EMITTING DEVICE COMPRISING THE SAME}

The present invention relates to novel organometallic compounds and organic electroluminescent devices containing the same.

Conventionally, display devices using electroluminescent light-emitting elements have been studied in various ways because they can reduce power consumption and be thinner, and organic electroluminescent elements made of organic materials have been actively studied because they can easily be made lighter or larger. In particular, the development of organic materials with luminescent properties including blue, one of the three primary colors of light, and the development of organic materials with charge transport capabilities such as holes and electrons (which have the potential to become semiconductors or superconductors) are related to polymer compounds. , regardless of low molecular weight compounds, have been actively studied so far.

An organic electroluminescent element has a structure consisting of a pair of electrodes consisting of an anode and a cathode, and one or more 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 are being developed.

As materials for the emitting layer, for example, benzofluorene-based compounds and chrysene-based compounds are being developed (International Publication No. 2004/061047 or International Publication No. 2008/147721).

In addition, as hole transport materials, for example, triphenylamine-based compounds and carbazole-based compounds are being developed (Japanese Patent Application Laid-open No. 2001-172232, Japanese Patent Application Laid-Open No. 2006-199679, Japanese Patent Application Laid-Open No. 2001-172232, 2005-268199, Japanese Patent Publication No. 2007-088433, International Publication No. 2003/078541, International Publication No. 2003/080760).

In addition, as electron transport materials, for example, anthracene-based compounds and compounds whose central skeleton is made of bianthracene, binaphthalene, or a combination of naphthalene and anthracene, etc. are being developed (Japanese Patent Application Laid-Open No. 2005-170911, Japanese Patent Application Laid-Open). Patent Publication No. 2003-146951, Japanese Patent Application Publication No. 08-12600, Japanese Patent Application Publication No. 2003-123983, Japanese Patent Application Publication No. 11-297473).

In addition, polycyclic aromatic hydrocarbons (PAHs) have recently been attracting attention as materials used in organic electronics, pigments, sensors, and liquid displays, and examples of the synthesis of dibenzochrysene-based compounds with B-N bonding sites have also been reported (J. Am . Chem. Soc., 2011, 133, 18614-18617).

The purpose of the present invention is to provide an organometallic compound and an organic electroluminescent device containing the same.

Another object of the present invention is to provide a novel organometallic compound whose low half width and dopant concentration quenching phenomenon can be controlled when used as a phosphorescent dopant material in an organic electroluminescent device due to the steric hindrance effect of the organometallic compound.

Another object of the present invention is to provide an organic electroluminescent device that has low driving voltage and can exhibit high efficiency and long lifespan characteristics.

In order to achieve the other objects of the present invention, the present invention provides an organometallic compound represented by the following formula (1):

[Formula 1]

M(L ₁ ) _3-n (L ₂ ) _n

[Formula 2]

here,

* refers to the part combined with M,

M is Ir,

L ₁ is a ligand represented by Formula 2 above,

n is 0 to 2,

X is selected from the group consisting of N(R ₁ ), O, S and C(R ₂ )(R ₃ ),

Y ₁ to Y ₃ are the same or different from each other, and are each independently C(R ₄ ) or N,

Ring A and Ring B are the same or different from each other, and each independently represents a substituted or unsubstituted aryl having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl having 1 to 30 carbon atoms, or a substituted or unsubstituted cycle having 3 to 30 carbon atoms. It is selected from the group consisting of alkyl and substituted or unsubstituted heterocycloalkyl having 1 to 30 carbon atoms,

At least one of the A ring and the B ring contains substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms,

R ₁ to R ₄ are the same or different from each other, and each independently represents hydrogen, a cyano group, a nitro group, a carbonyl group, a carboxyl group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, or a substituted or unsubstituted carbon number. Alkyl group of 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group of 3 to 20 carbon atoms, substituted or unsubstituted alkenyl group of 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group of 2 to 24 carbon atoms, substituted or unsubstituted alkynyl group of 7 to 30 carbon atoms aralkyl group, a substituted or unsubstituted aryl group with 5 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group with 5 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group with 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylalkyl group with 1 to 30 carbon atoms, an alkoxy group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkylamino group having 2 to 24 carbon atoms. Hetero arylamino group, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted carbon number 1 A straight-chain or branched alkylsulfanyl group having 1 to 14 carbon atoms, a substituted or unsubstituted organic sulfanyl group having 3 to 14 carbon atoms, a substituted or unsubstituted straight-chain or branched alkanesulfonyl group having 1 to 14 carbon atoms, substituted or unsubstituted An organic sulfonyl group having 3 to 14 carbon atoms having a ringed alicyclic skeleton, a substituted or unsubstituted dialkylphosphino group having 2 to 30 carbon atoms, a substituted or unsubstituted diarylphosphino group having 12 to 30 carbon atoms, and It is selected from the group consisting of substituted or unsubstituted alkylarylphosphino groups having 7 to 30 carbon atoms, and can be combined with adjacent groups to form a substituted or unsubstituted ring,

L ₂ is a monodentate ligand or a bidentate ligand.

In addition, the present invention includes a first electrode; a second electrode opposite the first electrode; It relates to an organic electroluminescent device comprising at least one organic material layer interposed between the first electrode and the second electrode, wherein the at least one organic material layer includes at least one compound represented by Formula 1 above.

In the present invention, “hydrogen” refers to hydrogen, light hydrogen, deuterium, or tritium, unless otherwise specified.

In the present invention, the “halogen group” is fluorine, chlorine, bromine, or iodine.

In the present invention, “alkyl” is a monovalent substituent derived from a straight-chain or branched saturated hydrocarbon having 1 to 40 carbon atoms, examples of which include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, etc. Examples include, but are not limited to.

In the present invention, “alkenyl” is a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms having one or more carbon-carbon double bonds, examples of which include vinyl, allyl ( allyl), isopropenyl, 2-butenyl, etc., but is not limited thereto.

In the present invention, “alkynyl” is a monovalent substituent derived from a straight or branched chain unsaturated hydrocarbon having 2 to 40 carbon atoms with one or more carbon-carbon triple bonds, examples of which include ethynyl, 2 -Propanyl (2-propynyl), etc. may be mentioned, but it is not limited thereto.

In the present invention, “alkylthio” may be the alkyl group described above bonded through a sulfur linkage (-S-).

In the present invention, “aryl” is a monovalent substituent derived from an aromatic hydrocarbon having 6 to 60 carbon atoms, either a single ring or a combination of two or more rings, and may also include a form in which two or more rings are simply attached to each other (pendant) or condensed. Examples of such aryl include phenyl, naphthyl, phenanthryl, anthryl, fluonyl, dimethylfluorenyl, etc., but are not limited thereto.

In the present invention, “heteroaryl” is a monovalent substituent derived from a monoheterocyclic or polyheterocyclic aromatic hydrocarbon having 6 to 30 carbon atoms, and at least one carbon in the ring, preferably 1 to 3 carbons, is N, O , is substituted with a heteroatom such as S or Se. In addition, a form in which two or more rings are simply pendant or condensed with each other may be included, and a condensed form with an aryl group may also be included. Examples of such heteroaryls include 6-membered monocyclic rings such as pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, and triazinyl, phenoxathienyl, indolizinyl, and indolyl ( Polycyclic rings such as indolyl, purinyl, quinolyl, benzothiazole, carbazolyl, and 2-furanyl, N-imidazolyl, 2-isoxazolyl , 2-pyridinyl, 2-pyrimidinyl, etc., but are not limited thereto.

In the present invention, “aryloxy” is a monovalent substituent represented by RO-, where R is aryl having 6 to 60 carbon atoms, and examples of aryloxy include phenyloxy, naphthyloxy, diphenyloxy, etc. , but is not limited to this.

In the present invention, “alkyloxy” is a monovalent substituent represented by R'O-, where R' is alkyl having 1 to 40 carbon atoms and includes a linear, branched, or cyclic structure. can do. Examples of alkyloxy include, but are not limited to, methoxy, ethoxy, n-propoxy, 1-propoxy, t-butoxy, n-butoxy, and pentoxy.

In the present invention, “alkoxy” may be a straight chain, branched chain, or ring chain. The number of carbon atoms of alkoxy is not particularly limited, but is preferably 1 to 20 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. It may be possible, but it is not limited to this.

In the present invention, “aralkyl” refers to an aryl-alkyl group where aryl and alkyl are as described above, and the aralkyl may include a lower alkyl group. The aralkyl group may be, for example, benzyl, 2-phenethyl, naphthalenylmethyl, etc., but is not limited thereto. Bonding to the parent moiety may be via an alkyl.

In the present invention, the “arylamino group” may be an amine substituted with an aryl group having 6 to 30 carbon atoms.

In the present invention, the “alkylamino group” may be an amine substituted with an alkyl group having 1 to 30 carbon atoms.

In the present invention, the “aralkyl amino group” may be an amine substituted with an aryl-alkyl group having 6 to 30 carbon atoms.

In the present invention, “heteroarylamino group” refers to an amine group substituted with an aryl group or heterocyclic group having 6 to 30 carbon atoms.

In the present invention, “heteroaralkyl group” refers to an aryl-alkyl group substituted with a heterocyclic group.

In the present invention, “cycloalkyl” refers to a monovalent substituent derived from a monocyclic or polycyclic non-aromatic hydrocarbon having 3 to 40 carbon atoms. Examples of the cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantine.

In the present invention, “heterocycloalkyl” refers to a monovalent substituent derived from a non-aromatic hydrocarbon having 3 to 40 carbon atoms, and at least one carbon in the ring, preferably 1 to 3 carbons, is N, O, S or Se. It may be substituted with a hetero atom such as . Examples of such heterocycloalkyl include, but are not limited to, morpholine and piperazine.

In the present invention, “alkylsilyl” refers to silyl substituted with alkyl having 1 to 40 carbon atoms, and “arylsilyl” refers to silyl substituted with aryl having 6 to 60 carbon atoms.

In the present invention, “condensed ring” means a condensed aliphatic ring, a condensed aromatic ring, a condensed heteroaliphatic ring, a condensed heteroaromatic ring, or a combination thereof.

In the present invention, "forming a ring by bonding with adjacent groups" means a substituted or unsubstituted aliphatic hydrocarbon ring by bonding with adjacent groups; Substituted or unsubstituted aromatic hydrocarbon ring; Substituted or unsubstituted aliphatic heterocycle; Substituted or unsubstituted aromatic heterocycle; Or it means forming a condensation ring thereof.

In the present invention, examples of “aromatic hydrocarbon rings” include phenyl groups, naphthyl groups, and anthracenyl groups, but are not limited to these.

In the present invention, “aliphatic heterocycle” refers to an aliphatic ring containing one or more heteroatoms.

In the present invention, “aromatic heterocycle” refers to an aromatic ring containing one or more heteroatoms.

In the present invention, “linear or branched alkylsulfanyl group” includes, for example, methylsulfanyl group, ethylsulfanyl group, n-propylsulfanyl group, i-propylsulfanyl group, n-butylsulfanyl group, and 2-methylpropylsulfanyl group. , 1-methylpropylsulfanyl group, t-butylsulfanyl group, n-pentylsulfanyl group, n-hexylsulfanyl group, n-heptylsulfanyl group, n-octylsulfanyl group, n-nonylsulfanyl group, n-decylsulfanyl group, n -It may be undecylsulfanyl group, n-dodecylsulfanyl group, n-tridecylsulfanyl group, n-tetradecylsulfanyl group, etc.

In the present invention, “organic sulfanyl group having an alicyclic skeleton” includes, for example, cycloalkylsulfanyl groups such as cyclopropylsulfanyl group, cyclobutylsulfanyl group, cyclopentylsulfanyl group, and cyclohexylsulfanyl group; (bicyclo[2.2.1]heptan2-yl)sulfanyl group, (bicyclo[2.2.2]octan-2-yl)sulfanyl group, (tetracyclo[4.2.0.1 2.5.1 7.10]dodecane-3- an organic sulfanyl group in which an alicyclic ring derived from a bridged alicyclic hydrocarbon such as a 1)sulfanyl group or (adamantane-2-yl)sulfanyl group is directly bonded to a sulfur atom; From cycloalkanes such as cyclopropane, cyclobutane, cyclopentane, and cyclohexane, and bridged alicyclic hydrocarbons such as norbornane, bicyclo [2.2.2] octane, tricyclodecane, tetracyclododecane, and adamantane. An organic sulfanyl group having a methylene group or an alkylene group having 2 to 8 carbon atoms (e.g., ethylene group, propylene group, etc.) bonded to the derived alicyclic ring (provided that the methylene group or the alkylene group is bonded to a sulfur atom) ), etc.

In the present invention, “linear or branched alkanesulfonyl group” includes, for example, methanesulfonyl group, ethanesulfonyl group, n-propanesulfonyl group, n-propane-2-sulfonyl group, n-butanesulfonyl group, 2-methyl Propane-1-sulfonyl group, 1-methylpropane-1-sulfonyl group, 2-methylpropane-2-sulfonyl group, n-pentanesulfonyl group, n-hexanesulfonyl group, n-heptanesulfonyl group, n-octane sulfo It may be a nyl group, n-nonanesulfonyl group, n-decanesulfonyl group, n-undecanesulfonyl group, n-dodecanesulfonyl group, n-tridecanesulfonyl group, n-tetradecanesulfonyl group, etc.

In the present invention, the "organic sulfonyl group having an alicyclic skeleton" includes, for example, cycloalkanesulfonyl groups such as cyclopropanesulfonyl group, cyclobutanesulfonyl group, cyclopentanesulfonyl group, and cyclohexanesulfonyl group; Bicyclo[2.2.1]heptane-2-sulfonyl group, bicyclo[2.2.2]octane-2-sulfonyl group, tetracyclo[4.2.0.1 2.5 .1 7.10]dodecane-3-sulfonyl group, adaman Organic sulfonyl groups in which an alicyclic ring derived from bridged alicyclic hydrocarbons, such as a tan-2-sulfonyl group, is directly bonded to a sulfur atom; Cycloalkanes such as cyclopropane, cyclobutane, cyclopentane, and cyclohexane, and bridged alicyclic hydrocarbons such as norbornane, bicyclo[2.2.2]octane, tricyclorodecane, tetracyclododecane, and adamantane. An organic sulfonyl group having a methylene group or an alkylene group having 2 to 8 carbon atoms (for example, an ethylene group, a propylene group, etc.) bonded to an alicyclic ring derived from (provided that the methylene group or the alkylene group is bonded to a sulfur atom and Yes), etc.

In the present invention, "phosphino group" is R ₂ P-, for example, a dialkylphosphino group having 2 to 30 carbon atoms, a substituted or unsubstituted diarylphosphino group having 12 to 30 carbon atoms, and a substituted or unsubstituted phosphino group. It may be a ringed alkylarylphosphino group having 7 to 30 carbon atoms.

In the present invention, "substitution" means changing a hydrogen atom bonded to a carbon atom of a compound to another substituent. The position to be substituted is not limited as long as it is the position where the hydrogen atom is substituted, that is, a position where the substituent can be substituted, and if two or more substituents are substituted. , two or more substituents may be the same or different from each other. The substituents include hydrogen, cyano group, nitro group, carbonyl group, carboxyl group, halogen group, hydroxy group, alkylthio group with 1 to 4 carbon atoms, alkyl group with 1 to 30 carbon atoms, cycloalkyl group with 3 to 20 carbon atoms, and alke group with 2 to 30 carbon atoms. Nyl group, alkynyl group with 2 to 24 carbon atoms, aralkyl group with 7 to 30 carbon atoms, aryl group with 5 to 30 carbon atoms, heteroaryl group with 5 to 60 carbon atoms, heteroarylalkyl group with 6 to 30 carbon atoms, alkoxy with 1 to 30 carbon atoms group, alkylamino group with 1 to 30 carbon atoms, arylamino group with 6 to 30 carbon atoms, aralkylamino group with 6 to 30 carbon atoms, hetero arylamino group with 2 to 24 carbon atoms, alkylsilyl group with 1 to 30 carbon atoms, 6 to 30 carbon atoms Arylsilyl group, aryloxy group with 6 to 30 carbon atoms, straight or branched alkylsulfanyl group with 1 to 14 carbon atoms, organic sulfanyl group with 3 to 14 carbon atoms, straight or branched alkane sulfo with 1 to 14 carbon atoms Nyl group, organic sulfonyl group with 3 to 14 carbon atoms having an alicyclic skeleton, dialkylphosphino group with 2 to 30 carbon atoms, diarylphosphino group with 12 to 30 carbon atoms, and alkylarylphosphino group with 7 to 30 carbon atoms. It may be substituted with one or more substituents selected from the group consisting of groups, but is not limited to the above examples.

In the present invention, due to the steric hindrance effect of the organometallic compound, when used as a phosphorescent dopant material in an organic electroluminescent device, the low half width and dopant concentration quenching phenomenon can be controlled.

In addition, it is possible to provide an organic electroluminescent device that has a low driving voltage and can exhibit high efficiency and long lifespan characteristics.

1 shows NMR data for a new organic compound according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement it. However, the present invention may be implemented in many different forms and is not limited to the embodiments described herein.

The present invention relates to a novel organometallic compound, which can control low half width and dopant concentration quenching phenomenon when used as a phosphorescent dopant material in an organic electroluminescent device due to the steric hindrance effect.

Using the novel organometallic compound, it is possible to exhibit low driving voltage, high efficiency, and long lifespan characteristics.

Specifically, the novel organometallic compound may be a compound represented by the following formula (1):

[Formula 1]

M(L ₁ ) _3-n (L ₂ ) _n

[Formula 2]

here,

* refers to the part combined with M,

M is Ir,

L ₁ is a ligand represented by Formula 2 above,

n is 0 to 2,

X is selected from the group consisting of N(R ₁ ), O, S and C(R ₂ )(R ₃ ),

Y ₁ to Y ₃ are the same or different from each other, and are each independently C(R ₄ ) or N,

Ring A and Ring B are the same or different from each other, and each independently represents a substituted or unsubstituted aryl having 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl having 1 to 30 carbon atoms, or a substituted or unsubstituted cycle having 3 to 30 carbon atoms. It is selected from the group consisting of alkyl and substituted or unsubstituted heterocycloalkyl having 1 to 30 carbon atoms,

At least one of the A ring and the B ring contains substituted or unsubstituted cycloalkyl having 3 to 30 carbon atoms,

R ₁ to R ₄ are the same or different from each other, and each independently represents hydrogen, a cyano group, a nitro group, a carbonyl group, a carboxyl group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, or a substituted or unsubstituted carbon number. Alkyl group of 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group of 3 to 20 carbon atoms, substituted or unsubstituted alkenyl group of 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group of 2 to 24 carbon atoms, substituted or unsubstituted alkynyl group of 7 to 30 carbon atoms aralkyl group, a substituted or unsubstituted aryl group with 5 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group with 5 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group with 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylalkyl group with 1 to 30 carbon atoms, an alkoxy group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkylamino group having 2 to 24 carbon atoms. Hetero arylamino group, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted carbon number 1 A straight-chain or branched alkylsulfanyl group having 1 to 14 carbon atoms, a substituted or unsubstituted organic sulfanyl group having 3 to 14 carbon atoms, a substituted or unsubstituted straight-chain or branched alkanesulfonyl group having 1 to 14 carbon atoms, substituted or unsubstituted An organic sulfonyl group having 3 to 14 carbon atoms having a ringed alicyclic skeleton, a substituted or unsubstituted dialkylphosphino group having 2 to 30 carbon atoms, a substituted or unsubstituted diarylphosphino group having 12 to 30 carbon atoms, and It is selected from the group consisting of substituted or unsubstituted alkylarylphosphino groups having 7 to 30 carbon atoms, and can be combined with adjacent groups to form a substituted or unsubstituted ring,

L ₂ is a monodentate ligand or a bidentate ligand.

The A ring may be a compound represented by the following formula (3):

[Formula 3]

here,

* refers to the part combined with M,

*' refers to the combined part,

m is an integer from 0 to 4,

R ₅ is each independently hydrogen, cyano group, nitro group, carbonyl group, carboxyl group, halogen group, hydroxy group, substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, substituted or unsubstituted alkyl group having 1 to 30 carbon atoms, substituted or unsubstituted Cycloalkyl group with 3 to 20 carbon atoms in the ring, substituted or unsubstituted alkenyl group with 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group with 2 to 24 carbon atoms, substituted or unsubstituted aralkyl group with 7 to 30 carbon atoms, substituted or unsubstituted carbon atoms Aryl group with 5 to 30 carbon atoms, substituted or unsubstituted heteroaryl group with 5 to 60 carbon atoms, substituted or unsubstituted heteroarylalkyl group with 6 to 30 carbon atoms, substituted or unsubstituted alkoxy group with 1 to 30 carbon atoms, substituted or unsubstituted carbon atoms Alkylamino group with 1 to 30 carbon atoms, substituted or unsubstituted arylamino group with 6 to 30 carbon atoms, substituted or unsubstituted aralkylamino group with 6 to 30 carbon atoms, substituted or unsubstituted heteroarylamino group with 2 to 24 carbon atoms, substituted or unsubstituted carbon atoms Alkylsilyl group with 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl group with 6 to 30 carbon atoms, substituted or unsubstituted aryloxy group with 6 to 30 carbon atoms, straight or branched alkylsulfanyl group with 1 to 14 carbon atoms, carbon number Organic sulfanyl group of 3 to 14 carbon atoms, linear or branched alkanesulfonyl group of 1 to 14 carbon atoms, organic sulfonyl group of 3 to 14 carbon atoms with an alicyclic skeleton, substituted or unsubstituted dialkyl group of 2 to 30 carbon atoms It is selected from the group consisting of a phosphino group, a substituted or unsubstituted diarylphosphino group having 12 to 30 carbon atoms, and a substituted or unsubstituted alkylarylphosphino group having 7 to 30 carbon atoms, and is substituted by bonding with an adjacent group. Alternatively, it may form an unsubstituted ring.

The compound represented by Formula 1 may be a compound represented by Formula 4 or Formula 5 below:

[Formula 4]

[Formula 5]

here,

*, m, Y ₁ , Y ₂ , Y ₃ , X and R ₅ are as defined in paragraph 1 or 2,

o is an integer from 0 to 4,

p is an integer from 1 to 10,

Z1 to Z2 are the same or different from each other and are each independently C(R ₇ )(R ₈ ) or N(R ₉ ),

R ₆ to R ₉ are the same or different from each other, and each independently represents hydrogen, a cyano group, a nitro group, a carbonyl group, a carboxyl group, a halogen group, a hydroxy group, a substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, or a substituted or unsubstituted carbon number. Alkyl group of 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group of 3 to 20 carbon atoms, substituted or unsubstituted alkenyl group of 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group of 2 to 24 carbon atoms, substituted or unsubstituted alkynyl group of 7 to 30 carbon atoms aralkyl group, a substituted or unsubstituted aryl group with 5 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group with 5 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group with 6 to 30 carbon atoms, a substituted or unsubstituted heteroarylalkyl group with 1 to 30 carbon atoms, an alkoxy group, a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms, a substituted or unsubstituted aralkylamino group having 6 to 30 carbon atoms, or a substituted or unsubstituted aralkylamino group having 2 to 24 carbon atoms. Hetero arylamino group, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms, substituted or unsubstituted carbon number 1 A straight-chain or branched alkylsulfanyl group having 1 to 14 carbon atoms, a substituted or unsubstituted organic sulfanyl group having 3 to 14 carbon atoms, a substituted or unsubstituted straight-chain or branched alkanesulfonyl group having 1 to 14 carbon atoms, substituted or unsubstituted An organic sulfonyl group having 3 to 14 carbon atoms having a ringed alicyclic skeleton, a substituted or unsubstituted dialkylphosphino group having 2 to 30 carbon atoms, a substituted or unsubstituted diarylphosphino group having 12 to 30 carbon atoms, and It is selected from the group consisting of substituted or unsubstituted alkylarylphosphino groups having 7 to 30 carbon atoms, and may be combined with adjacent groups to form a substituted or unsubstituted ring.

Any one or more of R ₅ to R ₉ may include deuterium.

The p is preferably 2, and Z ₁ and Z ₂ may be C(R ₇ )(R ₈ ).

The L ₂ may be a compound represented by Formula 6 or Formula 7 below:

[Formula 6]

[Formula 7]

here,

* refers to the part combined with M,

q and r are integers from 0 to 4,

R ₁₀ and R ₁₁ are the same or different from each other, and are each independently hydrogen, cyano group, nitro group, carbonyl group, carboxyl group, halogen group, hydroxy group, substituted or unsubstituted alkylthio group having 1 to 4 carbon atoms, substituted or Unsubstituted alkyl group with 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group with 3 to 20 carbon atoms, substituted or unsubstituted alkenyl group with 2 to 30 carbon atoms, substituted or unsubstituted alkynyl group with 2 to 24 carbon atoms, substituted or unsubstituted carbon atoms 7 to 30 aralkyl group, substituted or unsubstituted aryl group with 5 to 30 carbon atoms, substituted or unsubstituted heteroaryl group with 5 to 60 carbon atoms, substituted or unsubstituted heteroarylalkyl group with 6 to 30 carbon atoms, substituted or unsubstituted carbon number Alkoxy group of 1 to 30 carbon atoms, substituted or unsubstituted alkylamino group of 1 to 30 carbon atoms, substituted or unsubstituted arylamino group of 6 to 30 carbon atoms, substituted or unsubstituted aralkylamino group of 6 to 30 carbon atoms, substituted or unsubstituted carbon number of 2 heteroarylamino group of 24 to 24 carbon atoms, substituted or unsubstituted alkylsilyl group of 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl group of 6 to 30 carbon atoms, substituted or unsubstituted aryloxy group of 6 to 30 carbon atoms, substituted or unsubstituted a linear or branched alkylsulfanyl group having 1 to 14 carbon atoms, a substituted or unsubstituted organic sulfanyl group having 3 to 14 carbon atoms, a substituted or unsubstituted linear or branched alkanesulfonyl group having 1 to 14 carbon atoms, Organic sulfonyl group having 3 to 14 carbon atoms having a substituted or unsubstituted alicyclic skeleton, dialkylphosphino group having 2 to 30 carbon atoms being substituted or unsubstituted, diarylphos having 12 to 30 carbon atoms being substituted or unsubstituted It is selected from the group consisting of a pino group and a substituted or unsubstituted alkylarylphosphino group having 7 to 30 carbon atoms, and can be combined with adjacent groups to form a substituted or unsubstituted ring,

R ₁₂ to R ₁₄ are the same or different from each other, and each independently represents hydrogen, a substituted or unsubstituted alkyl group with 1 to 30 carbon atoms, a substituted or unsubstituted aralkyl group with 7 to 30 carbon atoms, or a substituted or unsubstituted aryl group with 6 to 30 carbon atoms. It may be selected from the group consisting of a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 2 to 30 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms.

Any one or more of R ₁₀ to R ₁₄ may include deuterium.

The compound represented by Formula 1 may be a compound selected from the group consisting of the following compounds:

An organic electroluminescent device according to another embodiment of the present invention includes a first electrode; a second electrode opposite the first electrode; It may include one or more organic layers interposed between the first electrode and the second electrode.

The organic material layer may be a hole injection layer, a hole transport layer, a light emitting layer, an electron transport layer, an electron injection layer, etc.

Specifically, the organic electroluminescent device includes a substrate, an anode formed on the substrate, a hole injection layer formed on the anode, a hole transport layer formed on the hole injection layer, a light-emitting layer formed on the hole transport layer, and an electron transport layer formed on the light-emitting layer. and an electron injection layer formed on the electron transport layer, and a cathode formed on the electron injection layer.

In addition, the organic electroluminescent device has the manufacturing order reversed, for example, a substrate, a cathode formed on the substrate, an electron injection layer formed on the cathode, an electron transport layer formed on the electron injection layer, and on the electron transport layer. It may be configured to have a light-emitting layer formed, a hole transport layer formed on the light-emitting layer, a hole injection layer formed on the hole transport layer, and an anode formed on the hole injection layer.

All of the above layers are not necessary, and the minimum structural unit is composed of an anode, a light-emitting layer, an electron transport layer, and/or an electron injection layer and a cathode, and the hole injection layer and the hole transport layer are arbitrarily formed layers. Additionally, each of the above layers may be composed of a single layer or may be composed of multiple layers.

As aspects of the layers constituting the organic electroluminescent element, in addition to the above-described aspects of “substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode”, “substrate/anode/hole” Transport layer/light emitting layer/electron transport layer/electron injection layer/cathode”, “substrate/anode/hole injection layer/light emitting layer/electron transport layer/electron injection layer/cathode”, “substrate/anode/hole injection layer/hole transport layer/light emitting layer/electron” Injection layer/cathode”, “substrate/anode/hole injection layer/hole transport layer/light-emitting layer/electron transport layer/cathode”, “substrate/anode/light-emitting layer/electron transport layer/electron injection layer/cathode”, “substrate/anode/hole” “Transport layer/light-emitting layer/electron injection layer/cathode”, “substrate/anode/hole transport layer/light-emitting layer/electron transport layer/cathode”, “substrate/anode/hole injection layer/light-emitting layer/electron injection layer/cathode”, “substrate/anode/ Hole injection layer/light-emitting layer/electron transport layer/cathode”, “substrate/anode/light-emitting layer/electron transport layer/cathode”, “substrate/anode/light-emitting layer/electron injection layer/cathode”, “substrate/anode/hole injection layer/hole transport layer” /electron blocking layer/light-emitting layer/electron blocking layer/electron transport layer/electron injection layer/cathode” may be used.

The substrate 101 serves as a support for the organic electroluminescent element, and quartz, glass, metal, plastic, etc. are typically used. The substrate is formed in the form of a plate, film, or sheet depending on the purpose, and for example, a glass plate, a metal plate, a metal foil, a plastic film, a plastic sheet, etc. are used. Among them, glass plates and plates made of transparent synthetic resins such as polyester, polymethacrylate, polycarbonate, and polysulfone are preferable. If it is a glass substrate, soda lime glass, alkali-free glass, etc. are used, and the thickness may be sufficient to maintain mechanical strength, so for example, it may be 0.2 mm or more. The upper limit of thickness is, for example, 2 mm or less, and preferably 1 mm or less. Regarding the material of glass, alkali-free glass is preferable since it is better to have fewer ions eluted from the glass. However, soda lime glass coated with a barrier coat such as SiO ₂ is also commercially available and can be used. In addition, in order to increase the gas barrier property, a gas barrier film such as a dense silicon oxide film may be formed on at least one side of the substrate. In particular, when a plate, film or sheet made of synthetic resin with a low gas barrier property is used as the substrate, the gas barrier film may be formed on at least one side of the substrate. It is desirable to form a barrier film.

The anode serves to inject holes into the light emitting layer. Additionally, when a hole injection layer and/or a hole transport layer are formed between the anode and the light-emitting layer, holes are injected into the light-emitting layer through these.

Materials that form the anode include inorganic compounds and organic compounds. Inorganic compounds include, for example, metals (aluminum, gold, silver, nickel, palladium, chromium, etc.), metal oxides (indium oxide, tin oxide, indium-tin oxide (ITO), indium-zinc oxide ( IZO), metal halides (copper iodide, etc.), copper sulfide, carbon black, ITO glass, and Nesa glass. Examples of organic compounds include polythiophenes such as poly(3-methylthiophene), and conductive polymers such as polypyrrole and polyaniline. In addition, the material can be appropriately selected and used as an anode for organic electroluminescent devices.

The resistance of the transparent electrode is not limited as long as it can supply sufficient current for light emission of the light-emitting element, but it is preferable to have low resistance from the viewpoint of power consumption of the light-emitting element. For example, 300 Ω/ The following ITO substrates function as element electrodes, but currently, 10 Ω/ Since it is possible to supply substrates with an accuracy of, for example, 100 to 5 Ω/ , preferably 50 to 5 Ω/ It is particularly desirable to use a low-resistance product. The thickness of ITO can be arbitrarily selected according to the resistance value, but is usually between 50 and 200 nm.

The hole injection layer serves to efficiently inject holes moving from the anode into the light emitting layer or into the hole transport layer. The hole transport layer serves to efficiently transport holes injected from the anode or holes injected from the anode via the hole injection layer to the light emitting layer. The hole injection layer and the hole transport layer are formed by laminating or mixing one or two or more types of hole injection/transport materials, or a mixture of a hole injection/transport material and a polymer binder, respectively. Additionally, the layer may be formed by adding an inorganic salt such as iron (III) chloride to the hole injection/transport material.

As a hole injection/transport material, it is necessary to efficiently inject and transport holes from the positive electrode between electrodes to which an electric field is applied, and it is desirable to have high hole injection efficiency and efficiently transport the injected holes. To achieve this, it is desirable to use a material that has a small ionization potential, high hole mobility, excellent stability, and is unlikely to generate trapping impurities during manufacture and use.

Materials forming the hole injection layer or hole transport layer (hole layer materials) include compounds conventionally used as hole charge transport materials in photoconductive materials, p-type semiconductors, hole injection layers and hole transport materials in organic electroluminescent devices. Any of the known ones used in the transport layer can be selected and used. Specific examples thereof include carbazole derivatives (N-phenylcarbazole, polyvinylcarbazole, etc.), biscarbazole derivatives such as bis(N-arylcarbazole) or bis(N-alkylcarbazole), and triarylamine derivatives. (Polymer having an aromatic tertiary amino group in the 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'-dinaphthylN,N'-diphenyl-4,4'-diphenyl -1,1'-diamine, 4,4',4"-tris(3-methylphenyl(phenyl)amino)triphenylamine derivatives such as triphenylamine, starburstamine derivatives, etc.), stilbene derivatives, phthalocyanine derivatives ( metal-free, copper phthalocyanine, etc.), pyrazoline derivatives, hydrazone-based compounds, benzofuran derivatives, thiophene derivatives, oxadiazole derivatives, heterocyclic compounds such as porphyrin derivatives, polysilanes, etc. In polymer systems, the above monomers are measured. Polycarbonate, styrene derivatives, polyvinylcarbazole, and polysilane having a chain are preferred, but any compound is capable of forming a thin film necessary for manufacturing a light-emitting device, injecting holes from the anode, and transporting holes. There is no particular limitation.

Additionally, it is 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 with good electron donating properties or a compound with good electron accepting properties. For doping of electron-donating materials, strong electron acceptors such as tetracyanoquinonedimethane (TCNQ) or 2,3,5,6-tetrafluorotetracyano-1,4-benzoquinonedimethane (F4TCNQ) are used. is known (e.g., 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 through 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 changes significantly. As matrix materials with hole transport properties, for example, benzidine derivatives (TPD, etc.) or starburst amine derivatives (TDATA, etc.), or specific metal phthalocyanines (especially zinc phthalocyanine ZnPc, etc.) are known (Japanese Patent Publication 2005) -No. 167175).

The light-emitting layer is between electrodes to which an electric field is applied, and emits light by recombining holes injected from the anode and electrons injected from the cathode. The material forming the light-emitting layer can be any compound (luminescent compound) that is excited and emits light by recombination of holes and electrons, can form a stable thin film shape, and has strong luminescence (fluorescence and/or phosphorescence) efficiency in the solid state. It is preferable that it is a compound representing . The light-emitting material of the light-emitting device according to an embodiment of the present invention may be fluorescent or phosphorescent.

The light-emitting layer may be a single layer or a plurality of layers, and is formed of a light-emitting material (host material, dopant material). The host material and the dopant material may be one type, a combination of multiple types, or any of them. The dopant material may be contained entirely, partially, or contained in the host material. As a doping method, it can be formed by co-deposition with a host material, but may be deposited simultaneously after mixing with the host material in advance.

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

The amount of dopant material used varies depending on the type of dopant material, and can be determined according to the characteristics of the dopant material. The standard for the amount of dopant used is preferably 0.001 to 50% by weight of the total light emitting material, more preferably 0.05 to 20% by weight, and still more preferably 0.1 to 10% by weight.

The organometallic compound represented by Formula 1 can be used as a dopant material. In particular, it can be used as a phosphorescent dopant material, and the organometallic compound represented by Formula 1 is used by mixing with the host material, and is 1 to 50% by weight, preferably 1 to 20% by weight, based on the host material. More preferably, it may be included in 1 to 10% by weight.

The host material is not particularly limited, but includes triarylamine, carbazole derivatives, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazole, silane, boron, triazine, dibenzofuran, and dibenzothiophene derivatives. It may include two or more host materials selected from the group consisting of mixtures thereof.

Additionally, the host material is not limited to the above examples, and any compounds commonly used as host materials can be used without limitation.

Other dopant materials are not particularly limited, and already known compounds can be used, and various materials can be selected depending on the desired emission color. Specifically, for example, condensed ring derivatives such as phenanthrene, anthracene, pyrene, tetracene, pentacene, perylene, naphthopyrene, dibenzopyrene, rubrene, and chrysene, benzoxazole derivatives, and benzthiazole. Derivatives, benzimidazole derivatives, benztriazole derivatives, oxazole derivatives, oxadiazole derivatives, thiazole derivatives, imidazole derivatives, thiadiazole derivatives, triazole derivatives, pyrazoline derivatives, stilbene derivatives, thiophene derivatives, Tetraphenylbutadiene derivatives, cyclopentadiene derivatives, bistyryl derivatives such as bistyryl anthracene derivatives and distyrylbenzene derivatives (Japanese Patent Application Laid-Open No. 1-245087), bistyrylarylene derivatives (Japanese Patent Application Publication No. 1-245087) No. 2-247278), diazindacene derivatives, furan derivatives, benzofuran derivatives, phenylisobenzofuran, dimethylisobenzofuran, di(2-methylphenyl)isobenzofuran, di(2-trifluoromethylphenyl)iso Isobenzofuran derivatives such as benzofuran and phenylisobenzofuran, dibenzofuran derivatives, 7-dialkylaminocoumarin derivatives, 7-piperidinocoumarin derivatives, 7-hydroxycoumarin derivatives, 7-methoxycoumarin derivatives, Coumarin derivatives such as 7-acetoxycoumarin derivatives, 3-benzthiazolylcoumarin derivatives, 3-benzimidazolylcoumarin derivatives, and 3-benzoxazolylcoumarin derivatives, dicyanomethylenepyran derivatives, dicyanomethylenethiopyran derivatives, poly Methine derivatives, cyanine derivatives, oxobenzanthracene derivatives, xanthene derivatives, rhodamine derivatives, fluorescein derivatives, pyrylium derivatives, carbostyryl derivatives, acridine derivatives, oxazine derivatives, phenylene oxide derivatives, quinacridone Derivatives, quinazoline derivatives, pyrrolopyridine derivatives, furopyridine derivatives, 1,2,5-thiadiazolopyrene derivatives, pyromethene derivatives, perinone derivatives, pyrrolopyrrole derivatives, squaryllium derivatives, biolanthrone derivatives , phenazine derivatives, acridone derivatives, deazaflavine derivatives, fluorene derivatives, and benzofluorene derivatives.

The electron injection layer serves to efficiently inject electrons moving from the cathode into the light emitting layer or into the electron transport layer. The electron transport layer serves to efficiently transport electrons injected from the cathode or electrons injected from the cathode via the electron injection layer to the light emitting layer. The electron transport layer and the electron injection layer are each formed by laminating or mixing one or two or more types of electron transport/injection material, or by a mixture of an electron transport/injection material and a polymer binder.

The electron injection/transport layer is a layer that injects electrons from the cathode and is responsible for transporting the electrons. It is desirable that the electron injection efficiency is high and the injected electrons are transported efficiently. To this end, it is desirable to use a material that has high electron affinity, high electron mobility, excellent stability, and is unlikely to generate trapping impurities during manufacture and use. However, considering the transport balance between holes and electrons, if the role is mainly to efficiently prevent holes from the anode from flowing to the cathode without recombining, the luminous efficiency can be improved even if the electron transport capacity is not very high. The improving effect is equivalent to that of materials with high electron transport ability. Therefore, the electron injection/transport layer in the present embodiment may also include a function of a layer that can efficiently prevent the movement of holes.

The material forming the electron transport layer or electron injection layer is arbitrarily selected from compounds conventionally used as electron transport compounds in photoconductive materials and known compounds used in the electron injection layer and electron transport layer of organic electroluminescent devices. You can use it.

Materials used in the electron transport layer or electron injection layer include compounds consisting of an aromatic ring or heteroaromatic ring composed of one or more atoms selected from carbon, hydrogen, oxygen, sulfur, silicon, and phosphorus, pyrrole derivatives, and condensed ring derivatives thereof. and a metal complex having electron-accepting nitrogen. Specifically, condensed ring-based aromatic ring derivatives such as naphthalene and anthracene, styryl-based aromatic ring derivatives such as 4,4'-bis(diphenylethenyl)biphenyl, perinone derivatives, coumarin derivatives, and naphthalimide. Derivatives include quinone derivatives such as anthraquinone and diphenoquinone, phosphorus derivatives, carbazole derivatives, and indole derivatives. Examples of metal complexes having electron-accepting nitrogen include hydroxyazole complexes such as hydroxyphenyloxazole complex, azomethine complex, tropolone metal complex, flavonol metal complex, and benzoquinoline metal complex. . These materials can be used alone, but may be used in combination with different materials. Among them, anthracene derivatives such as 9,10-bis(2-naphthyl)anthracene, styryl-based aromatic ring derivatives such as 4,4'-bis(diphenylethenyl)biphenyl, and 4,4'-bis(N Carbazole derivatives such as -carbazolyl)biphenyl and 1,3,5-tris(N-carbazolyl)benzene are preferably used from the viewpoint of durability.

Additionally, specific examples of other electron transfer compounds include pyridine derivatives, naphthalene derivatives, anthracene derivatives, phenanthroline derivatives, perinone derivatives, coumarin derivatives, naphthalimide derivatives, anthraquinone derivatives, diphenoquinone derivatives, and 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 complex, pyrazole derivative, perfluorinated phenylene derivative, triazine derivative, pyrazine derivative, benzoquinoline derivative (2,2'-bis(benzo [h]quinolin-2-yl)-9,9' -spirobifluorene, etc.), imidazopyridine derivatives, borane derivatives, benzimidazole derivatives (tris(N-phenylbenzimidazol-2-yl)benzene, etc.), benzoxazole derivatives, benzthiazole 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, phosphorus oxide derivatives, bistyryl derivatives, etc. I can hear it.

Additionally, a metal complex having an electron-accepting nitrogen can also be used, for example, a quinolinol-based metal complex, a hydroxyazole complex such as a hydroxyphenyloxazole complex, an azomethine complex, a tropolone metal complex, or a flavonol metal complex. and benzoquinoline metal complexes.

The materials described above can be used alone, but may be used in combination with different materials.

Among the materials described above, quinolinol-based metal complexes, bipyridine derivatives, phenanthroline derivatives, borane derivatives, or benzimidazole derivatives are preferred.

The electron transport layer or electron injection layer may further contain a substance capable of reducing the material forming the electron transport layer or electron injection layer. Various reducing substances are used as long as they have a certain reducing property, for example, alkali metals, alkaline earth metals, rare earth metals, oxides of alkali metals, halides of alkali metals, oxides of alkaline earth metals, halides of alkaline earth metals, At least one selected from the group consisting of oxides of rare earth metals, halides of rare earth metals, organic complexes of alkali metals, organic complexes of alkaline earth metals, and organic complexes of rare earth metals can be preferably used.

Preferred reducing substances include alkali metals such as Na (work function 2.36 eV), K (2.28 eV), Rb (2.16 eV), or Cs (1.95 eV), Ca (2.9 eV), and Sr (2.9 eV). 2.0 to 2.5 eV) or alkaline earth metals such as Ba (copper, 2.52 eV), and those with a work function of 2.9 eV or less are particularly preferable. Among these, more preferable reducing substances are alkali metals of K, Rb or Cs, more preferably Rb or Cs, and most preferable is Cs. These alkali metals have a particularly high reducing ability, and by adding a relatively small amount to the material forming the electron transport layer or electron injection layer, the luminance of the organic EL device can be improved and its lifespan can be improved. In addition, as a reducing material with a work function of 2.9 eV or less, a combination of two or more alkali metals is also preferred, especially a combination containing Cs, for example, Cs and Na, Cs and K, Cs and Rb, or Cs. A combination of Na and K is preferred. By containing Cs, the reducing ability can be efficiently exerted, and by adding it to the material forming the electron transport layer or the electron injection layer, the luminance of the organic EL device can be improved and its lifespan can be improved.

The cathode serves to inject electrons into the light-emitting layer through the electron injection layer and the electron transport layer.

The material forming the cathode is not particularly limited as long as it is a material that can efficiently inject electrons into the organic layer, but the same material as the material forming the anode can be used. Among them, metals such as tin, indium, calcium, aluminum, silver, copper, nickel, chromium, gold, platinum, iron, zinc, lithium, sodium, potassium, cesium and magnesium or their alloys (magnesium-silver alloy, magnesium-silver alloy) Indium alloys, aluminum-lithium alloys such as lithium fluoride/aluminum, etc.) are preferable. In order to improve device characteristics by increasing 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 the atmosphere. To improve this point, there is a known method of using a highly stable electrode by doping a trace amount of lithium, cesium or magnesium into the organic layer, for example. 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.

In addition, to protect the electrode, metals such as platinum, gold, silver, copper, iron, tin, aluminum and indium, or alloys using these metals, inorganic substances such as silica, titania and silicon nitride, polyvinyl alcohol, vinyl chloride, and hydrocarbons. A preferable example is laminating a polymer compound or the like. The manufacturing method of these electrodes is not particularly limited as long as it can achieve conduction, such as resistance heating, electron beam beam, sputtering, ion plating, and coating.

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 individually, but may be used as a polymer binder such as polyvinyl chloride, polycarbonate, polystyrene, or poly(N-vinylcarboxylic acid). Bazole), polymethyl methacrylate, polybutyl methacrylate, polyester, polysulfone, polyphenylene oxide, polybutadiene, hydrocarbon resin, ketone resin, phenoxy resin, polyamide, ethyl cellulose, vinyl acetate resin, ABS It is dispersed in solvent-soluble resins such as resins and polyurethane resins, and 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 use

Each layer that makes up an organic electroluminescent device is made by turning the materials that make up each layer into a thin film using methods such as deposition, resistance heating deposition, electron beam deposition, sputtering, molecular stacking, printing, spin coating, casting, or coating. It can be formed by doing. There is no particular limitation on the film thickness of each layer formed in this way, and it can be set appropriately depending on the properties of the material, but is usually in the range of 2 nm to 5000 nm. The film thickness can usually be measured using a crystal oscillation type film thickness measuring device or the like. When thinning a film using a vapor deposition method, the deposition conditions vary depending on the type of material, the target crystal structure and association structure of the film, etc. Deposition conditions generally range from boat heating temperature of 50 to 400°C, vacuum degree of 10 ^-6 to 10 ^-3 Pa, deposition rate of 0.01 to 50 nm/sec, substrate temperature of -150 to +300°C, and film thickness of 2 nm to 5 ㎛. It is desirable to set it appropriately.

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/hole injection layer/hole transport layer/host material and a light emitting layer/electron transport layer/electron injection layer/cathode made of a dopant material is included. Explain. An anode is manufactured by forming a thin film of an anode material on a suitable substrate by a vapor deposition method or the like, and then thin films of a hole injection layer and a hole transport layer are formed on the anode. A thin film is formed by co-depositing a host material and a dopant material on this to form a light-emitting layer, an electron transport layer and an electron injection layer are formed on this light-emitting layer, and a thin film made of a cathode material is formed by a vapor deposition method, etc. to serve as a cathode. The target organic electroluminescent device is obtained. In addition, in manufacturing the organic electroluminescent device described above, the manufacturing order can be reversed and the cathode, electron injection layer, electron transport layer, light emitting layer, hole transport layer, hole injection layer, and anode can be manufactured in that order.

When applying a direct current voltage to the organic electroluminescent device obtained in this way, it can be applied with the anode as + and the cathode as -, and when a voltage of about 2 to 40 V is applied, the transparent or translucent electrode side (anode) Alternatively, light emission can be observed from the cathode and both sides. Additionally, the organic electroluminescent device emits light even when pulse current or alternating current is applied. Additionally, the waveform of the applied alternating current may be arbitrary.

Synthesis Example 1

L1-1 (0.86 g, 2.43 mmol) and iridium trichloride (0.035 g, 1.0 mmol) were added, and then dissolved in 2-ethoxyethanol (90 mL) and distilled water (30 mL). Next, it was stirred for 24 hours at 110°C under nitrogen conditions. After cooling to room temperature, 500 mL of distilled water was added, and the filtered solid was sufficiently washed to obtain L2-1.

Next, L2-1, acetylacetone (0.5 mL, 5.0 mmol), and sodium carbonate (0.53 g, 0.50 mmol) obtained above were dissolved in 2-ethoxyethanol (100 mL) and incubated at 60°C for 24 hours under nitrogen conditions. It was stirred. After cooling to room temperature, extraction and concentration with water and dichloromethane, column chromatography was performed under the condition of dichloromethane:hexane = 30:70 to obtain Compound 1 (0.6 g, 60%).

MS: [M+H] ⁺ = 1001.38

Synthesis Example 2

Compound 2 (1.35 g, 54%) was obtained under the same conditions as Synthesis Example 1, except that L1-2 (0.90 g, 2.43 mmol) was used instead of L1-1.

MS: [M+H] ⁺ = 1030.42

Synthesis Example 3

Compound 3 (0.48 g, 48%) was obtained under the same conditions as Synthesis Example 1, except that L1-3 (0.90 g, 2.43 mmol) was used instead of L1-1.

MS: [M+H] ⁺ = 1030.42

Synthesis Example 4

Compound 4 (0.50 g, 46%) was obtained under the same conditions as Synthesis Example 1, except that L1-4 (0.97 g, 2.43 mmol) was used instead of L1-1.

MS: [M+H] ⁺ = 1094.47

Synthesis Example 5

Compound 5 (0.59 g, 54%) was obtained under the same conditions as Synthesis Example 1, except that L1-5 (0.97 g, 2.43 mmol) was used instead of L1-1.

MS: [M+H] ⁺ = 1085.47

Synthesis Example 6

Compound 6 (0.60 g, 58%) was obtained under the same conditions as Synthesis Example 1, except that L1-6 (0.90 g, 2.43 mmol) was used instead of L1-1.

MS: [M+H] ⁺ = 1035.44

Synthesis Example 7

Compound 7 (0.44g, 40%) was obtained under the same conditions as Synthesis Example 1, except that L1-7 (1.00 g, 2.43 mmol) was used instead of L1-1.

MS: [M+H] ⁺ = 1098.48

Synthesis example 8

Compound 8 (0.44g, 42%) was obtained under the same conditions as Synthesis Example 1, except that L1-8 (0.93 g, 2.43 mmol) was used instead of L1-1.

MS: [M+H] ⁺ = 1057.44

Synthesis Example 9

Compound 9 (0.44g, 46%) was obtained under the same conditions as Synthesis Example 1, except that L1-9 (1.00 g, 2.43 mmol) was used instead of L1-1.

MS: [M+H] ⁺ = 1113.5

Synthesis Example 10

Compound 10 (0.54 g, 52%) was obtained under the same conditions as Synthesis Example 1, except that L1-10 (0.91 g, 2.43 mmol) was used instead of L1-1.

MS: [M+H] ⁺ = 1037.36

Synthesis Example 11

L1-1 (0.86 g, 2.43 mmol) and iridium trichloride (0.035 g, 1.0 mmol) were added, and then dissolved in 2-ethoxyethanol (90 mL) and distilled water (30 mL). Next, it was stirred for 24 hours at 110°C under nitrogen conditions. After cooling to room temperature, 500 mL of distilled water was added, and the filtered solid was sufficiently washed to obtain L2-1.

Next, L2-1, 2,2,6,6-tetramethyl-3,5-heptanedione (1.0 mL, 5.0 mmol) and sodium carbonate (0.53 g, 0.50 mmol) obtained above were mixed with 2-ethoxyethanol ( 100 mL) and stirred at 60°C under nitrogen conditions for 24 hours. After cooling to room temperature, extraction and concentration with water and dichloromethane, column chromatography was performed under the condition of dichloromethane:hexane = 30:70 to obtain Compound 11 (0.6 g, 56%).

MS: [M+H] ⁺ = 1086.48

Synthesis Example 12

Compound 12 (0.44 g, 40%) was obtained under the same conditions as Synthesis Example 11, except that L1-2 was used instead of L1-1 and L2-2 was used instead of L2-1.

MS: [M+H] ⁺ = 1114.52

Synthesis Example 13

Compound 13 (0.49 g, 42%) was obtained under the same conditions as Synthesis Example 11, except that L1-4 was used instead of L1-1 and L2-4 was used instead of L2-1.

MS: [M+H] ⁺ = 1170.58

Synthesis Example 14

Compound 14 (0.54 g, 48%) was obtained under the same conditions as Synthesis Example 11, except that L1-6 was used instead of L1-1 and L2-6 was used instead of L2-1.

MS: [M+H] ⁺ = 1120.55

Synthesis Example 15

Compound 15 (0.57g, 50%) was obtained under the same conditions as Synthesis Example 11, except that L1-8 was used instead of L1-1 and L2-8 was used instead of L2-1.

MS: [M+H] ⁺ = 1142.55

Synthesis Example 16

Compound 16 (0.53 g, 44%) was obtained under the same conditions as Synthesis Example 11, except that L1-9 was used instead of L1-1 and L2-9 was used instead of L2-1.

MS: [M+H] ⁺ = 1198.61

Synthesis Example 17

Compound 17 (0.52g, 46%) was obtained under the same conditions as Synthesis Example 11, except that L1-10 was used instead of L1-1 and L2-10 was used instead of L2-1.

MS: [M+H] ⁺ = 1122.47

Synthesis Example 18

L2-1 (0.71 g, 0.38 mmol) was dissolved in 100 mL of dichloromethane, and silver trifluoromethanesulfonate (0.21 g, 0.83 mmol) and 30 mL of isopropanol were added. Next, it was stirred at room temperature for 12 hours, filtered, and concentrated.

Next, the concentrated compound and 2-phenylpyridine (0.059 g, 0.38 mmol) were dissolved in 200 mL of ethanol, and the reaction was carried out by refluxing and stirring for 18 hours, and then the temperature was lowered. The resulting mixture was filtered, the obtained solid was washed with ethanol and hexane, and column chromatography was performed under the condition of dichloromethane:hexane = 30:70 to obtain compound 18 (0.16 g, 40%).

MS: [M+H] ⁺ = 1056.40

Synthesis Example 19

Compound 19 (0.21 g, 52%) was obtained under the same conditions as Synthesis Example 18, except that d9-phenyl pyridine was used instead of 2-phenylpyridine.

MS: [M+H] ⁺ = 1064.45

Synthesis Example 20

Compound 20 (0.24 g, 60%) was obtained under the same conditions as Synthesis Example 18, except that 5-CD3-2-phenylpyridine was used instead of 2-phenylpyridine.

MS: [M+H] ⁺ = 1073.43

Synthesis Example 21

Compound 20 (0.24 g, 56%) was obtained under the same conditions as Synthesis Example 18, except that L2-6 was used instead of L2-1 and 4-CD3-2-phenylpyridine was used instead of 2-phenylpyridine.

MS: [M+H] ⁺ = 1108.51

Synthesis Example 22

Compound under the same conditions as Synthesis Example 18, except that L2-6 was used instead of L2-1, and 5-(methyl- d 3)-2-[4-(methyl- d 3)phenyl]pyridine was used instead of 2-phenylpyridine. 22 (0.24g, 56%) was obtained.

MS: [M+H] ⁺ = 1124.53

Synthesis Example 23

Compound 23 (0.20 g, 46%) was obtained under the same conditions as Synthesis Example 18, except that L2-6 was used instead of L2-1 and 5-(tert-butyl)-2-phenylpyridine was used instead of 2-phenylpyridine. .

MS: [M+H] ⁺ = 1146.53

Synthesis Example 24

Same conditions as Synthesis Example 18, except that L2-2 was used instead of L2-1, and 4,5-Di(methyl- d 3)-2-[4-(methyl- d 3)phenylpyridine was used instead of 2-phenylpyridine. Compound 24 (0.19g, 44%) was obtained.

MS: [M+H] ⁺ = 1135.54

Synthesis Example 25

2-Phenylpyridine (0.38 g, 2.43 mmol) and iridium trichloride (0.035 g, 1.0 mmol) were added, and then dissolved in 2-ethoxyethanol (90 mL) and distilled water (30 mL). Next, it was stirred for 24 hours at 110°C under nitrogen conditions. After cooling to room temperature, 500 mL of distilled water was added, and the filtered solid was sufficiently washed to obtain L2-11.

L2-11 (0.41 g, 0.38 mmol) was dissolved in 100 mL of dichloromethane, and silver trifluoromethanesulfonate (0.21 g, 0.83 mmol) and 30 mL of isopropanol were added. Next, it was stirred at room temperature for 12 hours, filtered, and concentrated.

Next, the concentrated compound and 2-(7,7,10,10-tetramethyl-7,8,9,10-tetrahydronaphtho[2,3-b]benzofuran-4-yl)pyridine (0.135 g, 0.38 mmol) was dissolved in 200 mL of ethanol, the reaction was carried out by refluxing and stirring for 18 hours, and then the temperature was lowered. The resulting mixture was filtered, the obtained solid was washed with ethanol and hexane, and column chromatography was performed under the condition of dichloromethane:hexane = 30:70 to obtain compound 25 (0.12 g, 38%).

MS: [M+H] ⁺ = 857.28

Synthesis Example 26

Synthesis example except that 4-methyl-2-phenylpyridine (0.41 g, 2.43 mmol) was used instead of 2-phenylpyridine (0.38 g, 2.43 mmol), and L2-12 was used instead of L2-11 (0.41 g, 0.38 mmol). Compound 26 (0.12g, 36%) was obtained under the same conditions as 25.

MS: [M+H] ⁺ = 885.32

Synthesis Example 27

Except that 5-methyl-2-(p-tolyl)pyridine (0.45 g, 2.43 mmol) was used instead of 2-phenylpyridine (0.38 g, 2.43 mmol) and L2-13 was used instead of L2-11 (0.41 g, 0.38 mmol). Then, Compound 27 (0.127g, 34%) was obtained under the same conditions as Synthesis Example 25.

MS: [M+H] ⁺ = 913.35

Synthesis Example 28

5-(methyl- d 3)-2-[4-(methyl- d 3)phenyl]pyridine (0.46 g, 2.43 mmol) instead of 2-phenylpyridine (0.38 g, 2.43 mmol), L2-11 (0.41 g, Compound 28 (0.119 g, 34%) was obtained under the same conditions as Synthesis Example 25, except that L2-14 was used instead of 0.38 mmol).

MS: [M+H] ⁺ = 925.42

Synthesis Example 29

5-(methyl- d 3)-2-[4-(methyl- d 3)phenyl]pyridine (0.46 g, 2.43 mmol) instead of 2-phenylpyridine (0.38 g, 2.43 mmol), L2-11 (0.41 g, 0.38 mmol) instead of L2-14, 2-(7,7,10,10-tetramethyl-7,8,9,10-tetrahydronaphtho[2,3-b]benzofuran-4-yl)pyridine ( 0.135 g, 0.38 mmol) instead of 5-methyl-2-(7,7,10,10-tetramethyl-7,8,9,10-tetrahydronaphtho[2,3-b]benzofuran-4-yl ) Compound 29 (0.143g, 40%) was obtained under the same conditions as Synthesis Example 25, except that pyridine (0.140g, 0.38 mmol) was used.

MS: [M+H] ⁺ = 939.44

Synthesis Example 30

5-(methyl- d 3)-2-[4-(methyl- d 3)phenyl]pyridine (0.46 g, 2.43 mmol) instead of 2-phenylpyridine (0.38 g, 2.43 mmol), L2-11 (0.41 g, 0.38 mmol) instead of L2-14, 2-(7,7,10,10-tetramethyl-7,8,9,10-tetrahydronaphtho[2,3-b]benzofuran-4-yl)pyridine ( 0.135 g, 0.38 mmol) instead of 4-methyl-2-(7,7,10,10-tetramethyl-7,8,9,10-tetrahydronaphtho[2,3-b]benzofuran-4-yl ) Compound 30 (0.157g, 44%) was obtained under the same conditions as Synthesis Example 25, except that pyridine (0.140g, 0.38 mmol) was used.

MS: [M+H] ⁺ = 939.44

Synthesis Example 31

5-(methyl- d 3)-2-[4-(methyl- d 3)phenyl]pyridine (0.46 g, 2.43 mmol) instead of 2-phenylpyridine (0.38 g, 2.43 mmol), L2-11 (0.41 g, 0.38 mmol) instead of L2-14, 2-(7,7,10,10-tetramethyl-7,8,9,10-tetrahydronaphtho[2,3-b]benzofuran-4-yl)pyridine ( 0.135g, 0.38 mmol) instead of 4-isopropyl-2-(7,7,10,10-tetramethyl-7,8,9,10-tetrahydronaphtho[2,3-b]benzofuran-4- Compound 30 (0.169g, 46%) was obtained under the same conditions as Synthesis Example 25, except that yl)pyridine (0.151g, 0.38 mmol) was used.

MS: [M+H] ⁺ = 967.47

Synthesis Example 32

5-(methyl- d 3)-2-[4-(methyl- d 3)phenyl]pyridine (0.46 g, 2.43 mmol) instead of 2-phenylpyridine (0.38 g, 2.43 mmol), L2-11 (0.41 g, 0.38 mmol) instead of L2-14, 2-(7,7,10,10-tetramethyl-7,8,9,10-tetrahydronaphtho[2,3-b]benzofuran-4-yl)pyridine ( 0.135 g, 0.38 mmol) instead of 4-(methyl- d 3)-2-(7,7,10,10-tetramethyl-7,8,9,10-tetrahydronaphtho[2,3-b]benzo Compound 30 (0.143g, 40%) was obtained under the same conditions as Synthesis Example 25, except that furan-4-yl)pyridine (0.141g, 0.38 mmol) was used.

MS: [M+H] ⁺ = 942.46

Synthesis Example 33

4,5-Di(methyl- d 3)-2-[4-(methyl- d 3)phenyl]pyridine (0.50 g, 2.43 mmol) instead of 2-phenylpyridine (0.38 g, 2.43 mmol), L2-11 ( Compound 33 (0.175 g, 48%) was obtained under the same conditions as Synthesis Example 25, except that L2-15 was used instead of 0.41 g, 0.38 mmol).

MS: [M+H] ⁺ = 959.49

Synthesis Example 34

4-methyl-2-(5,5,8,8-tetramethyl-5,6,7,8-tetrahydronaphthalen-2-yl)pyridine (0.69 g) instead of 2-phenylpyridine (0.38 g, 2.43 mmol) , 2.43 mmol), L2-16 instead of L2-11 (0.41 g, 0.38 mmol), 2-(7,7,10,10-tetramethyl-7,8,9,10-tetrahydronaphtho[2,3 -b]benzofuran-4-yl)pyridine (0.135g, 0.38 mmol) instead of 4-(methyl- d 3)-2-(7,7,10,10-tetramethyl-7,8,9,10- Compound 34 (0.180g, 42%) was obtained under the same conditions as Synthesis Example 25, except that tetrahydronaphtho[2,3-b]benzofuran-4-yl)pyridine (0.141g, 0.38 mmol) was used. did.

MS: [M+H] ⁺ = 1128.61

Synthesis Example 35

Compound 35 (0.64 g, 62%) was obtained under the same conditions as Synthesis Example 1, except that L1-11 (0.90 g, 2.43 mmol) was used instead of L1-1.

MS: [M+H] ⁺ = 1034.34

Synthesis Example 36

Compound 36 (0.23 g, 56%) was obtained under the same conditions as Synthesis Example 18, except that L2-17 was used instead of L2-1.

MS: [M+H] ⁺ = 1089.36

Synthesis Example 37

4-methyl-2-phenylpyridine (0.41 g, 2.43 mmol) instead of 2-phenylpyridine (0.38 g, 2.43 mmol), L2-12 instead of L2-11 (0.41 g, 0.38 mmol), 2-(7,7, 10,10-tetramethyl-7,8,9,10-tetrahydronaphtho[2,3-b]benzofuran-4-yl)pyridine (0.135g, 0.38 mmol) instead of 2-(7,7,10 , except that 10-tetramethyl-7,8,9,10-tetrahydrobenzo[b]naphtho[2,3-d]thiophen-4-yl)pyridine (0.141g, 0.38 mmol) was used. Compound 37 (0.171 g, 50%) was obtained under the same conditions as Synthesis Example 25.

MS: [M+H] ⁺ = 901.3

Synthesis Example 38

4-methyl-2-phenylpyridine (0.41 g, 2.43 mmol) instead of 2-phenylpyridine (0.38 g, 2.43 mmol), L2-12 instead of L2-11 (0.41 g, 0.38 mmol), 2-(7,7, 10,10-tetramethyl-7,8,9,10-tetrahydronaphtho[2,3-b]benzofuran-4-yl)pyridine (0.135g, 0.38 mmol) instead of 4-methyl-2-(7 ,7,10,10-tetramethyl-7,8,9,10-tetrahydrobenzo[b]naphtho[2,3-d]thiophen-4-yl)pyridine (0.147g, 0.38 mmol) Compound 38 (0.171 g, 50%) was obtained under the same conditions as Synthesis Example 25 except that.

MS: [M+H] ⁺ = 915.32

Experimental Example 1

A glass substrate coated with a thin film of ITO (Indium Tin Oxide) with a thickness of 1,400 Å was placed in distilled water dissolved in detergent and washed ultrasonically. At this time, Decon™ CON705 from Fischer Co. was used as detergent, and distilled water that was filtered a second time through a 0.22 ㎛ sterilizing filter from Millipore Co. was used as distilled water. After washing the ITO for 30 minutes, ultrasonic cleaning was repeated twice with distilled water for 10 minutes. After washing with distilled water, it was ultrasonic washed with solvents of isopropyl alcohol, acetone, and methanol for 10 minutes each, dried, and then transported to a plasma cleaner. Additionally, after cleaning the substrate for 5 minutes using oxygen plasma, the substrate was transported to a vacuum evaporator.

Next, a mixture of 95% by weight of the HT-A compound below and 5% by weight of the P-DOPANT compound below was thermally vacuum deposited on the ITO transparent electrode to a thickness of 100Å, and then only the HT-A compound below was deposited to a thickness of 1150Å to form a hole transport layer. was formed. On the hole transport layer, the following HT-B compound was thermally vacuum deposited to a thickness of 450 Å to form an electron blocking layer. On the electron blocking layer, a mixture of the following GH1 compound as the first host, the following GH2 compound as the second host, and the previously prepared compound 1 as a dopant in a weight ratio of 47:47:6 was vacuum deposited to a thickness of 400 Å to form an emitting layer. . On the light emitting layer, the following ET-A compound was vacuum deposited to a thickness of 50 Å to form a hole blocking layer. Next, on the hole blocking layer, the following ET-B compound and Liq compound were mixed at a weight ratio of 2:1 and thermally vacuum deposited to a thickness of 250 Å to form an electron transport layer, and then LiF and magnesium were mixed at a weight ratio of 1:1. They were mixed and vacuum deposited to a thickness of 30Å to form an electron injection layer. An organic light-emitting device was manufactured by mixing magnesium and silver at a weight ratio of 1:4 on the electron injection layer and depositing them to a thickness of 160 Å to form a cathode.

Experimental Examples 2 to 16

Organic light-emitting devices of Examples 2 to 16 were manufactured in the same manner as Experimental Example 1, except that when forming the light-emitting layer, instead of Compound 3, the compounds and weight ratios shown in Table 1 below were used as the phosphorescent dopant. In Table 1 below, when the weight ratio is 10, it means that a mixture of the first host, second host, and dopant in a weight ratio of 45:45:10 is used, respectively.

Comparative Experiment Example 1

The organic light-emitting devices of Comparative Experiment Example 1 were manufactured in the same manner as Experiment 1, except that the compounds and weight ratios shown in Table 1 below were used as the phosphorescent dopant instead of Compound 1 when forming the light-emitting layer. In Table 1 below, when the weight ratio is 10, it means that a mixture of the first host, second host, and dopant in a weight ratio of 45:45:10 is used, respectively.

[Comparative Compound 1]

dopant material weight ratio half width max
(nm) Voltage (V) (@10mA/cm ² ) Efficiency (cd/A) (@10mA/cm ² ) life span
(T95, hr) (@50mA/cm ² ) Experimental Example 1 Compound 1 6 45 531 4.26 60.14 160 Compound 1 10 46 532 4.32 59.74 170 Experimental Example 2 Compound 2 6 46 528 4.30 70.91 190 Compound 2 10 47 530 4.32 70.58 198 Experimental Example 3 Compound 3 6 46 528 4.32 69.40 157 Compound 3 10 48 531 4.34 69.02 167 Experimental Example 4 Compound 4 6 44 529 4.35 71.24 180 Compound 4 10 46 531 4.36 71.04 184 Experimental Example 5 Compound 6 6 48 528 4.40 73.00 180 Compound 6 10 49 530 4.41 71.60 186 Experimental Example 6 Compound 9 6 48 533 4.44 73.08 174 Compound 9 10 49 534 4.46 71.74 179 Experimental Example 7 Compound 12 6 46 534 4.41 69.98 170 Compound 12 10 48 535 4.43 68.04 180 Experimental Example 8 Compound 13 6 46 534 4.46 70.01 168 Compound 13 10 48 535 4.49 69.80 186 Comparative Example 1 Comparative compound 1 6 57 530 4.35 51.87 74 Comparative compound 1 10 59 532 4.36 51.06 82

Looking at the chemical structure according to the present invention, two of the three ligands connected to iridium contain dibenzofuran with cycloalkyl condensation, and the hydrogen of the weakest bond among the C-H bonds in the cycloalkyl group is all replaced with four methyl groups. This brings stability to the molecule itself.

In addition, the dopant concentration quenching phenomenon is controlled by the steric hindrance effect of the four methyl-substituted cycloalkyl groups, resulting in high efficiency. In particular, when the concentration of dopant is increased, the effect becomes more noticeable. In addition, including ring compounds in which cycloalkyl groups are condensed, the half width is maintained at 50 nm or less. Therefore, as shown in Table 1, when the compound according to the present invention is used as a dopant for the light-emitting layer of an organic light-emitting device, a device with high efficiency and long lifespan can be obtained.

Experimental Examples 9 to 13

Organic light-emitting devices of Experimental Examples 9 to 13 were manufactured in the same manner as Experimental Example 1, except that when forming the light-emitting layer, instead of Compound 1, the compounds and weight ratios shown in Table 2 were used as the phosphorescent dopant. In Table 2 below, if the weight ratio is 10, it means that a mixture of the first host, second host, and dopant in a weight ratio of 45:45:10, respectively, was used.

Comparative Experiment Example 2

The organic light-emitting devices of Comparative Experiment Example 1 were manufactured in the same manner as Experiment 1, except that the compounds and weight ratios shown in Table 2 below were used as the phosphorescent dopant instead of Compound 1 when forming the light-emitting layer. In Table 2 below, if the weight ratio is 10, it means that a mixture of the first host, second host, and dopant in a weight ratio of 45:45:10, respectively, was used.

[Comparative Compound 2]

dopant material weight ratio half width max (nm) Voltage (V) (@10mA/cm ² ) Efficiency (cd/A) (@10mA/cm ² ) Lifespan (T95, hr) (@50mA/cm ² ) Experimental Example 9 Compound 18 10 46 534 4.26 59.88 172 Experimental Example 10 Compound 20 10 46 533 4.32 62.74 196 Experimental Example 11 Compound 21 10 46 533 4.30 69.91 210 Experimental Example 12 Compound 22 10 47 534 4.34 72.34 248 Experimental Example 13 Compound 23 10 46 534 4.42 70.40 180 Comparative example 2 Comparative compound 2 10 59 532 4.36 50.28 105

Looking at the chemical structure according to the present invention, two of the three ligands connected to iridium include dibenzofuran in which cycloalkyl is condensed, and the hydrogen of the weakest bond among the C-H bonds in the cycloalkyl group is all replaced with four methyl groups. This brings stability to the molecule itself. In addition, the dopant concentration quenching phenomenon is controlled by the steric hindrance effect of the four methyl-substituted cycloalkyl groups, resulting in high efficiency. In particular, in compounds 20 to 23, the C-H bond of the alkyl substituent located in the ligand is replaced with a C-D bond. The hydrogen of the weakest bond among the C-H bonds is replaced with deuterium, resulting in higher molecular stability. Therefore, high luminous efficiency and long lifespan can be achieved. In addition, including ring compounds in which cycloalkyl groups are condensed, the half width is maintained at 50 nm or less. Therefore, as shown in Table 2, when the compound according to the present invention is used as a dopant for the light-emitting layer of an organic light-emitting device, a device with high efficiency and long lifespan can be obtained.

Experimental Examples 14 to 19

Organic light-emitting devices of Examples 22 to 26 were manufactured in the same manner as Experimental Example 1, except that the compounds and weight ratios shown in Table 3 below were used as the phosphorescent dopant instead of Compound 1 when forming the light-emitting layer. In Table 1 below, when the weight ratio is 10, it means that a mixture of the first host, second host, and dopant in a weight ratio of 45:45:10 is used, respectively.

Comparative Experiment Example 3

The organic light-emitting devices of Comparative Experiment Example 1 were manufactured in the same manner as Experiment 1, except that the compounds and weight ratios shown in Table 3 below were used as the phosphorescent dopant instead of Compound 1 when forming the light-emitting layer. In Table 3 below, if the weight ratio is 10, it means that a mixture of the first host, second host, and dopant in a weight ratio of 45:45:10, respectively, was used.

[Comparative Compound 3]

dopant material weight ratio half width max (nm) Voltage (V) (@10mA/cm ² ) Efficiency (cd/A) (@10mA/cm ² ) Lifespan (T95, hr) (@50mA/cm ² ) Experimental Example 14 Compound 25 10 48 533 4.30 58.12 180 Experimental Example 15 Compound 26 10 47 535 4.34 58.94 184 Experimental Example 16 Compound 33 10 46 535 4.38 60.02 222 Experimental Example 17 Compound 34 10 48 535 4.32 76.28 178 Experimental Example 18 Compound 37 10 46 534 4.48 70.40 180 Experimental Example 19 Compound 38 10 48 534 4.36 70.82 190 Comparative example 3 Comparative compound 3 10 58 532 4.32 49.98 110

Looking at the chemical structure according to the present invention, one of the three ligands linked to iridium includes dibenzofuran to which cycloalkyl is fused. As shown in Tables 1 and 2, high luminous efficiency and long lifespan can be achieved. In addition, since it contains a structure in which cycloalkyl groups are condensed, the half width was maintained at 50 nm or less. Therefore, as shown in Table 3 above, the compound according to the present invention, when used as a dopant for the emitting layer of an organic light-emitting device, provides a device with high efficiency and long life. You can get it.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements made by those skilled in the art using the basic concept of the present invention defined in the following claims are also possible. falls within the scope of rights.

Claims (10)

Compound represented by Formula 1:
[Formula 1]
M(L ₁ ) _{3- n} (L ₂ ) _n
[Formula 5]

[Formula 6]

[Formula 7]

here,
* refers to the part combined with M,
M is Ir,
L ₁ is a ligand represented by Formula 5 above,
L ₂ is a ligand represented by Formula 6 or Formula 7 above,
n is an integer of 1 or 2,
m is an integer from 0 to 4,
p is an integer from 1 to 10,
q and r are integers from 0 to 4,
Z ₁ to Z ₂ are C(R ₇ )(R ₈ ),
X is O or S,
Y ₁ to Y ₃ are C(R ₄ ),
R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ and R ₁₁ are the same or different from each other, and each independently represents hydrogen, cyano group, nitro group, carbonyl group, carboxyl group, halogen group, hydroxy group, substituted or unsubstituted carbon number of 1 Alkylthio group of 4 to 4 carbon atoms, substituted or unsubstituted alkyl group of 1 to 30 carbon atoms, substituted or unsubstituted cycloalkyl group of 3 to 20 carbon atoms, substituted or unsubstituted alkenyl group of 2 to 30 carbon atoms, substituted or unsubstituted alkenyl group of 2 to 24 carbon atoms alkynyl group, a substituted or unsubstituted aralkyl group having 7 to 30 carbon atoms, a substituted or unsubstituted aryl group having 5 to 30 carbon atoms, a substituted or unsubstituted heteroaryl group having 5 to 60 carbon atoms, or a substituted or unsubstituted aralkyl group having 6 to 30 carbon atoms. Heteroarylalkyl group, substituted or unsubstituted alkoxy group with 1 to 30 carbon atoms, substituted or unsubstituted alkylamino group with 1 to 30 carbon atoms, substituted or unsubstituted arylamino group with 6 to 30 carbon atoms, substituted or unsubstituted alkoxy group with 6 to 30 carbon atoms Alkylamino group, substituted or unsubstituted heteroarylamino group having 2 to 24 carbon atoms, substituted or unsubstituted alkylsilyl group having 1 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms, substituted or unsubstituted arylsilyl group having 6 to 30 carbon atoms Aryloxy group, substituted or unsubstituted linear or branched alkylsulfanyl group having 1 to 14 carbon atoms, substituted or unsubstituted organic sulfanyl group having 3 to 14 carbon atoms, substituted or unsubstituted straight chain having 1 to 14 carbon atoms Chain or branched alkanesulfonyl group, organic sulfonyl group having 3 to 14 carbon atoms having a substituted or unsubstituted alicyclic skeleton, substituted or unsubstituted dialkylphosphino group having 2 to 30 carbon atoms, substituted or unsubstituted It is selected from the group consisting of a diarylphosphino group having 12 to 30 carbon atoms and a substituted or unsubstituted alkylarylphosphino group having 7 to 30 carbon atoms, and can be combined with adjacent groups to form a substituted or unsubstituted ring. ,
R ₁₂ to R ₁₄ are the same or different from each other, and each independently represents hydrogen, a substituted or unsubstituted alkyl group with 1 to 30 carbon atoms, a substituted or unsubstituted aralkyl group with 7 to 30 carbon atoms, or a substituted or unsubstituted aryl group with 6 to 30 carbon atoms. selected from the group consisting of a substituted or unsubstituted heteroaryl group having 1 to 60 carbon atoms, a substituted or unsubstituted heteroarylalkyl group having 2 to 30 carbon atoms, and a substituted or unsubstituted cycloalkyl group having 3 to 20 carbon atoms,
When R ₄ , R ₅ , R ₇ , R ₈ , R ₁₀ to R ₁₄ are substituted, hydrogen, cyano group, nitro group, carbonyl group, carboxyl group, halogen group, hydroxy group, alkylthio group having 1 to 4 carbon atoms, carbon number Alkyl group of 1 to 30 carbon atoms, cycloalkyl group of 3 to 20 carbon atoms, alkenyl group of 2 to 30 carbon atoms, alkynyl group of 2 to 24 carbon atoms, aralkyl group of 7 to 30 carbon atoms, aryl group of 5 to 30 carbon atoms, 5 to 60 carbon atoms. heteroaryl group, heteroarylalkyl group of 6 to 30 carbon atoms, alkoxy group of 1 to 30 carbon atoms, alkylamino group of 1 to 30 carbon atoms, arylamino group of 6 to 30 carbon atoms, aralkylamino group of 6 to 30 carbon atoms, 2 to 2 carbon atoms Hetero arylamino group of 24, alkylsilyl group of 1 to 30 carbon atoms, arylsilyl group of 6 to 30 carbon atoms, aryloxy group of 6 to 30 carbon atoms, straight or branched alkylsulfanyl group of 1 to 14 carbon atoms, 3 carbon atoms. Organic sulfanyl group of 1 to 14 carbon atoms, linear or branched alkanesulfonyl group of 1 to 14 carbon atoms, organic sulfonyl group of 3 to 14 carbon atoms with an alicyclic skeleton, dialkylphosphino group of 2 to 30 carbon atoms, 12 carbon atoms It is substituted with a substituent selected from the group consisting of a diarylphosphino group having to 30 carbon atoms and an alkylarylphosphino group having 7 to 30 carbon atoms, and when substituted with a plurality of substituents, they are the same or different from each other. delete delete delete According to paragraph 1,
The compound represented by Formula 1 is selected from the group consisting of the following compounds:

first electrode; a second electrode opposite the first electrode; It includes one or more organic layers interposed between the first electrode and the second electrode,
The one or more organic layers include one or more compounds according to claim 1.
Organic electroluminescent device. According to clause 6,
The organic material layer is a light emitting layer
Organic electroluminescent device. In clause 7,
The light emitting layer further includes a host.
Organic electroluminescent device. According to clause 8,
The host includes two or more host materials selected from the group consisting of triarylamine, azacarbazole, silane, boron, triazine, dibenzofuran, and mixtures thereof.
Organic electroluminescent device. According to clause 6,
The compound has a half width of 50 nm or less.
Organic electroluminescent device.