WO2024080842A1

WO2024080842A1 - Organometallic compound and organic electroluminescent device comprising same

Info

Publication number: WO2024080842A1
Application number: PCT/KR2023/015872
Authority: WO
Inventors: 엄민식; 김환희; 하정환; 박상우; 오대환
Original assignee: 에스케이 주식회사
Priority date: 2022-10-13
Filing date: 2023-10-13
Publication date: 2024-04-18

Abstract

The present invention relates to an organometallic compound and an organic electroluminescent device comprising same. The organometallic compound enables the manufacture of full-color displays and white light organic electroluminescent devices, and is suitable for electroluminescence in the visible region, particularly a blue region, of an electromagnetic spectrum. In addition, the organometallic compound can be used as a mixture with a host compound in an emission layer of an organic electroluminescent device, and can be used as an emitter, a matrix material, or a charge transporting material, particularly a hole transporting material or a charge blocker. By using the organometallic compound, it may be possible to provide an organic electroluminescent device which can have high quantum yield and high stability and exhibit long lifespan characteristics.

Description

[Correction 31.10.2023 by Rule 91] Organometallic compounds and organic electroluminescent devices containing them

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

Conventionally, display devices using light-emitting elements that emit electroluminescence 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 organometallic compounds suitable for electroluminescence in the visible region of the electromagnetic spectrum, especially in the blue region, enabling the production of full-color displays and white light organic electroluminescent devices.

Another object of the present invention is to provide an organometallic compound that can be used as a mixture with a host compound in the light-emitting layer of an organic electroluminescent device.

Another object of the present invention is to provide organometallic compounds that can be used as emitters, matrix materials, charge transport materials, especially hole transport materials or charge blockers.

Another object of the present invention is to provide an organic electroluminescent device using the organometallic compound, which has high quantum yield, high stability, 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]

here,

m, n and o are the same or different from each other and are each independently an integer from 0 to 10,

p is an integer from 0 to 2,

M is beryllium (Be), magnesium (Mg), aluminum (Al), calcium (Ca), titanium (Ti), manganese (Mn), cobalt (Co), copper (Cu), zinc (Zn), gallium (Ga) ), germanium (Ge), zirconium (Zr), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), rhenium (Re), platinum (Pt), or gold (Au),

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

X ₁ to X ₇ are the same or different from each other and are each independently N or C(R ₅ ),

X ₈ is N(R ₆ ) or C(R ₇ )(R ₈ ),

Y ₁ and Y ₂ are the same or different from each other, and each independently represents a single bond, a double bond, N(R ₉ ), B(R ₁₀ ), P(R ₁₁ ), Si(R ₁₂ )(R ₁₃ ), Ge (R ₁₄ )(R ₁₅ ), S, Se, O, C(=O), C(=S), S(=O), S(=O) ₂ , substituted or unsubstituted C ₁ to C ₂₀ selected from the group consisting of an alkylene group, a substituted or unsubstituted C ₂ to C ₃₀ alkenylene group, and a substituted or unsubstituted C ₂ to C ₂₀ alkynylene group,

R ₁ to R ₁₅ are the same or different from each other, and each independently represents hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted C ₁ to C ₄ alkylthio group, or a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, substituted or unsubstituted C ₃ to C ₂₀ cycloalkyl group, substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, substituted or unsubstituted C ₂ to C ₃₀ alkynyl group, substituted or Unsubstituted C ₇ to C ₃₀ aralkyl group, substituted or unsubstituted C ₆ to C ₃₀ aryl group, substituted or unsubstituted C ₁ to C ₃₀ heteroaryl group, substituted or unsubstituted C ₆ to C 30 carbon atoms C ₃₀ heteroarylalkyl group, substituted or unsubstituted C ₁ to C ₃₀ alkoxy group, substituted or unsubstituted C ₁ to C ₃₀ alkylamino group, substituted or unsubstituted C ₆ to C ₃₀ arylamino group, substituted Or an unsubstituted C ₇ to C ₃₀ aralkylamino group, a substituted or unsubstituted C ₁ to C ₃₀ heteroarylamino group, a substituted or unsubstituted C ₁ to C ₃₀ alkylsilyl group, or a substituted or unsubstituted C It is selected from the group consisting of ₆ to C ₃₀ arylsilyl groups and substituted or unsubstituted C ₆ to C ₃₀ aryloxy groups, and may be combined with adjacent groups to form a substituted or unsubstituted ring.

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” refers to a monovalent substituent derived from a C ₁ to C ₄₀ straight or branched chain saturated hydrocarbon. Examples thereof include methyl, ethyl, propyl, isobutyl, sec-butyl, pentyl, iso-amyl, hexyl, etc., but are not limited thereto.

In the present invention, “alkenyl” refers to a monovalent substituent derived from a straight or branched C ₂ to C ₄₀ unsaturated hydrocarbon having one or more carbon-carbon double bonds. Examples thereof include vinyl, allyl, isopropenyl, 2-butenyl, etc., but are not limited thereto.

In the present invention, “alkynyl” refers to a monovalent substituent derived from a straight or branched C ₂ to C ₄₀ unsaturated hydrocarbon having one or more carbon-carbon triple bonds. Examples thereof include ethynyl, 2-propynyl, etc., but are not limited thereto.

In the present invention, “alkylthio” refers to an alkyl group bonded through a sulfur linkage (-S-).

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

In the present invention, “heteroaryl” refers to a monovalent substituent derived from a C ₆ to C ₃₀ monoheterocyclic or polyheterocyclic aromatic hydrocarbon. At this time, at least one carbon in the ring, preferably 1 to 3 carbons, is replaced with a heteroatom such as N, O, 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 refers to aryl of C ₆ to C ₆₀ . Examples of such aryloxy include phenyloxy, naphthyloxy, diphenyloxy, etc., but are not limited thereto.

In the present invention, “alkyloxy” is a monovalent substituent represented by R'O-, where R' refers to C ₁ to C ₄₀ alkyl, and is linear, branched, or cyclic. May contain structures. 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 straight chain, branched chain, or ring chain. The number of carbon atoms of alkoxy is not particularly limited, but is preferably C ₁ to C ₂₀ . 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.

As used herein, “aralkyl” refers to an aryl-alkyl group where aryl and alkyl are defined above. Preferred aralkyl contains lower alkyl groups. Non-limiting examples of suitable aralkyl groups include benzyl, 2-phenethyl, and naphthalenylmethyl. Bonding to the parent moiety is through the alkyl.

In the present invention, “arylamino group” refers to an amine substituted with a C ₆ to C ₃₀ aryl group.

In the present invention, “alkylamino group” means an amine substituted with an alkyl group of C ₁ to C ₃₀ .

In the present invention, “aralkyl amino group” refers to an amine substituted with an aryl-alkyl group of C ₆ to C ₃₀ .

In the present invention, “heteroarylamino group” refers to an amine group substituted with a heteroaryl group.

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 C ₃ to C ₄₀ monocyclic or polycyclic non-aromatic hydrocarbon. Examples of such cycloalkyl include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, norbornyl, and adamantine.

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

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

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, "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, halogen group, hydroxy group, C ₁ to C ₃₀ alkyl group, C ₂ to C ₃₀ alkenyl group, C ₂ to C ₂₄ alkynyl group, and C ₂ to C ₃₀ heteroalkyl group. , C ₆ to C ₃₀ aralkyl group, C ₆ to C ₃₀ aryl group, C ₁ to C _{30 heteroaryl group, C 1 to C 30} _{heteroarylalkyl group, C 1} _{to C 30} _alkoxy _group , C ₁ to C ₃₀ alkylamino group, C ₆ to C ₃₀ arylamino group, C ₇ to C ₃₀ aralkylamino group, C ₁ to C ₂₄ heteroarylamino group, substituted or unsubstituted C ₁ to C ₃₀ alkylsilyl group, It may be substituted with one or more substituents selected from the group consisting of a substituted or unsubstituted C ₆ to C ₃₀ arylsilyl group and a substituted or unsubstituted C ₆ to C ₃₀ aryloxy group, but is not limited to the above examples.

The organometallic compound of the present invention enables the production of full-color displays and white light organic electroluminescent devices, and is suitable for electroluminescence in the visible region of the electromagnetic spectrum, especially in the blue region.

In addition, it can be used as a mixture with a host compound in the emitting layer of an organic electroluminescent device, and can be used as an emitter, matrix material, charge transport material, especially a hole transport material or charge blocker, and can be used as a high quantum material by using the organometallic compound. An organic electroluminescent device with high yield and high stability can be provided.

[Formula 1]

here,

p is an integer from 0 to 2,

X ₈ is N(R ₆ ) or C(R ₇ )(R ₈ ),

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, and when the organometallic compound is used as a phosphorescent dopant material in an organic electroluminescent device, the low half width and dopant concentration quenching phenomenon can be controlled.

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]

here,

p is an integer from 0 to 2,

X ₈ is N(R ₆ ) or C(R ₇ )(R ₈ ),

The compound represented by Formula 1 may be a compound represented by Formula 2 below:

[Formula 2]

here,

n, m, o, p, _M _, ring A _, _ring B _, ring _C , X ₁ _to , X ₁₀ is C.

The compound represented by Formula 1 may be a compound represented by Formula 3 or Formula 4 below:

[Formula 3]

[Formula 4]

here,

m, o, _p , M _, _A ring _, C _ring _, _X ₁ _to

Z is selected from the group consisting of N, P, P=O, C(R ₁₈ ), Si(R ₁₉ ) and Ge(R ₂₀ );

X ₁₁ to X ₁₃ are the same or different from each other, and are each independently N or C(R ₂₁ ),

R ₁₆ to R ₂₁ are the same or different from each other, and each independently represents hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted C ₁ to C ₄ alkylthio group, or a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, substituted or unsubstituted C ₃ to C ₂₀ cycloalkyl group, substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, substituted or unsubstituted C ₂ to C ₃₀ alkynyl group, substituted or Unsubstituted C ₇ to C ₃₀ aralkyl group, substituted or unsubstituted C ₆ to C ₃₀ aryl group, substituted or unsubstituted C ₁ to C ₃₀ heteroaryl group, substituted or unsubstituted C ₆ to C 30 carbon atoms C ₃₀ heteroarylalkyl group, substituted or unsubstituted C ₁ to C ₃₀ alkoxy group, substituted or unsubstituted C ₁ to C ₃₀ alkylamino group, substituted or unsubstituted C ₆ to C ₃₀ arylamino group, substituted Or an unsubstituted C ₇ to C ₃₀ aralkylamino group, a substituted or unsubstituted C ₁ to C ₃₀ heteroarylamino group, a substituted or unsubstituted C ₁ to C ₃₀ alkylsilyl group, or a substituted or unsubstituted C It is selected from the group consisting of ₆ to C ₃₀ arylsilyl groups and substituted or unsubstituted C ₆ to C ₃₀ aryloxy groups, and may be combined with adjacent groups to form a substituted or unsubstituted ring.

The A ring may be a compound selected from the group consisting of the following formulas 5 to 9:

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

here,

* refers to the part combined with M,

*' refers to the combined part,

s is an integer from 0 to 4,

t and v are the same or different from each other and are each independently an integer from 0 to 6,

u is an integer from 0 to 7,

X15 is N(R ₂₈ ) or C(R ₂₉ )(R ₃₀ ),

R ₂₂ to R ₃₀ are the same or different from each other, and each independently represents hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted C ₁ to C ₄ alkylthio group, or a substituted or unsubstituted C ₁ to C ₃₀ alkyl group, substituted or unsubstituted C ₃ to C ₂₀ cycloalkyl group, substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, substituted or unsubstituted C ₂ to C ₃₀ alkynyl group, substituted or Unsubstituted C ₇ to C ₃₀ aralkyl group, substituted or unsubstituted C ₆ to C ₃₀ aryl group, substituted or unsubstituted C ₁ to C ₃₀ heteroaryl group, substituted or unsubstituted C ₆ to C 30 carbon atoms C ₃₀ heteroarylalkyl group, substituted or unsubstituted C ₁ to C ₃₀ alkoxy group, substituted or unsubstituted C ₁ to C ₃₀ alkylamino group, substituted or unsubstituted C ₆ to C ₃₀ arylamino group, substituted Or an unsubstituted C ₇ to C ₃₀ aralkylamino group, a substituted or unsubstituted C ₁ to C ₃₀ heteroarylamino group, a substituted or unsubstituted C ₁ to C ₃₀ alkylsilyl group, or a substituted or unsubstituted C It is selected from the group consisting of ₆ to C ₃₀ arylsilyl groups and substituted or unsubstituted C ₆ to C ₃₀ aryloxy groups, and may be combined with adjacent groups to form a substituted or unsubstituted ring.

Y1 and Y2 are the same or different from each other, and each independently represents a single bond, a double bond, *-N(R ₉ )-*, *-B(R ₁₀ )-*, *-P(R ₁₁ )-*, *-Si(R ₁₂ )(R ₁₃ )-*, *-Ge(R ₁₄ )(R ₁₅ )-*, *-S-*, *-Se-*, *-O-*, *-C( =O)-*, *-C(=S)-*, *-S(=O)-*, *-S(=O) ₂ -*, *-C(R ₃₁ )=*', *= C(R ₃₂ )-*', *-C(R ₃₃ )=C(R ₃₄ )-*', *-C(R ₃₅ )(R ₃₆ )-C(R ₃₇ )(R ₃₈ )-*' , *-C(=S)-*' and *-C≡C-*', where * and *' are each binding sites with neighboring atoms, and R ₃₁ to R ₃₈ are the same or different from each other. and each independently hydrogen, cyano group, nitro group, halogen group, hydroxy group, substituted or unsubstituted C ₁ to C ₄ alkylthio group, substituted or unsubstituted C ₁ to C ₃₀ alkyl group, substituted or unsubstituted C ₃ to C ₂₀ cycloalkyl group, substituted or unsubstituted C ₂ to C ₃₀ alkenyl group, substituted or unsubstituted C ₂ to C ₃₀ alkynyl group, substituted or unsubstituted C ₇ to C ₃₀ ar Alkyl group, substituted or unsubstituted C ₆ to C ₃₀ aryl group, substituted or unsubstituted C ₁ to C ₃₀ heteroaryl group, substituted or unsubstituted C ₆ to C ₃₀ heteroarylalkyl group, substituted or unsubstituted Substituted C ₁ to C ₃₀ alkoxy group, substituted or unsubstituted C ₁ to C ₃₀ alkylamino group, substituted or unsubstituted C ₆ to C ₃₀ arylamino group, substituted or unsubstituted C ₇ to C ₃₀ Aralkylamino group, substituted or unsubstituted C ₁ to C ₃₀ heteroarylamino group, substituted or unsubstituted C ₁ to C ₃₀ alkylsilyl group, substituted or unsubstituted C ₆ to C ₃₀ arylsilyl group and substituted or an unsubstituted C ₆ to C ₃₀ aryloxy group, and may be combined with adjacent groups to form a substituted or unsubstituted ring.

The M may be platinum (Pt), but is not limited to the above example.

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 is manufactured by reversing the manufacturing order, 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 an electron transport layer 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. In addition, 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-mentioned “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 gas barrier properties, 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 low gas barrier properties is used as the substrate, gas barrier films such as a dense silicon oxide film may be formed on at least one side. 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 forming 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 enough 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, an ITO substrate of 300 Ω/□ or less functions as an element electrode, but since it is currently possible to supply a substrate of about 10 Ω/□, for example, 100 to 5 Ω/□ is preferred. It is particularly desirable to use a low-resistance product of 50 to 5 Ω/□. 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, an inorganic salt such as iron (III) chloride may be added to the hole injection/transport material to form a layer.

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 this end, 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, and 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, heterocyclic compounds such as benzofuran derivatives, thiophene derivatives, oxadiazole derivatives, and porphyrin derivatives, and in polymer-based monomers, such as polysilanes. 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. 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) -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 ability 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, perfluorophenylene 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 preferable, 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.

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.

합성예Synthesis example

The synthesis of the above compound was performed as follows.

[Synthesis Example 1]

10 g (53.99 mmol) of 3-(λ ² -azaneyl)-N-phenylpyrazin-2-amine, 2 in a 1000 ml round bottom flask ^. -(3-bromophenoxy)-9-(pyridin-2-yl)-9H-carbazole (2-(3-bromophenoxy)-9-(pyridin-2-yl)-9H-carbazole) 20.4 g ( 49.13 mmol), 0.54 g (1.48 mmol) of Pd(allyl)Cl ₂ , 4.38 g (12.42 mmol) of cBRIDP, and 11.78 g (122.56 mmol) of NaOtBu were added. 324 mL of toluene was added as a solvent and stirred at 90°C. When the reaction was completed, the temperature was cooled to room temperature. Water was added to the reaction solution, stirred, and the organic layer and water layer were separated. The organic layer was filtered with silica gel and concentrated. <Formula 1-1> 20.5 g (72.93%) was obtained.

15 g (28.81 mmol) of <Formula 1-1> and 230 ml of triethyl orthoformate were added to a round bottom flask and stirred. Afterwards, 1.26 ml (34.58 mmol) of HCl (37%) was added, and it was stirred at 90°C for one day. When the reaction was completed, the product was filtered and washed with heptane to obtain 12 g (73.45%) of <Formula 1-2>.

10 g (17.64 mmol) of <Formula 1-2> and 2.45 g (10.58 mmol) of Ag ₂ O were added to a 1000 ml round bottom flask. 230 mL of 1,2-dichloroethane was added as a solvent and stirred for 2 days. After evaporating the solvent, the product was dissolved in 230 mL of o-dichlorobenzene, and 7.13 g (10.58 mmol) of Pt(COD)Cl ₂ was added to a 100 mL Schlenk flask, and stirred at reflux for 24 hours. did. The solvent was evaporated, adsorbed on silica, and purified by column to obtain 7.5 g of <Compound 1> (59.55%).

[Synthesis Example 45]

In a 1000 ml round bottom flask, 3-(λ ² -azanyl)-6-(tert-butyl)-N-phenylpyrazin-2-amine (3-(λ ² -azaneyl)-6-(tert-butyl)- N-phenylpyrazin-2-amine) 10 g (41.44 mmol), 2-(3-bromophenoxy)-9-(isoquinolin-3-yl)-9H-carbazole (2-(3-bromophenoxy)- 9-(isoquinolin-3-yl)-9H-carbazole) 17.5 g (37.71 mmol), Pd(allyl)Cl ₂ 0.42 g (1.14 mmol), cBRIDP 3.36 g (9.53 mmol) and NaOtBu 9.04 g (94.07 mmol) It was synthesized in the same manner as <Formula 1-1>, and 18.2 g (68.76%) of <Formula 2-1> was obtained.

15 g (23.93 mmol) of <Formula 2-1> and 191 ml of triethyl orthoformate were added to a round bottom plusk and stirred. After that, 1.05 ml (28.72 mmol) of HCl (37%) was added, and 11.5 g (71.38%) of <Formula 2-2> was obtained by synthesis in the same manner as <Formula 1-2>.

10 g (14.85 mmol) of <Formula 2-2> and 2.07 g (8.91 mmol) of Ag ₂ O were added to the round bottom flask. 193 mL of 1,2-dichloroethane was added as a solvent and stirred for 2 days. After evaporating the solvent, the product was dissolved in 193 mL of o-dichlorobenzene, and 6.05 g (16.04 mmol) of Pt(COD)Cl ₂ was added to a 100 mL Schlenk flask, and the product was dissolved in 193 mL of o-dichlorobenzene. > 7.2 g (58.41%) of <Compound 45> was obtained by synthesizing in the same manner as above.

[Synthesis Example 183]

3-(λ ² -azaneyl)-N,5,6-triphenylpyrazin-2-amine) in a 1000ml round bottom flask ^. 10 g (29.64 mmol), 2-(3-(3-bromophenoxy)phenoxy)pyridine (2-(3-(3-bromophenoxy)phenoxy)pyridine) 9.23 g (26.97 mmol), Pd(allyl) 0.30 g (0.815 mmol) of Cl ₂ , 2.40 g (6.82 mmol) of cBRIDP, and 6.47 g (67.28 mmol) of NaOtBu were synthesized in the same manner as <Formula 1-1> above to obtain 11.9 g (66.95%) of <Formula 3-1> got it

11 g (18.34 mmol) of <Formula 3-1> and 147 ml of triethyl orthoformate were added to a round bottom plusk and stirred. After that, 0.80 ml (22.01 mmol) of HCl (37%) was added, and 8.6 g (72.56%) of <Formula 3-2> was obtained by synthesis in the same manner as <Formula 1-2>.

8 g (11.88 mmol) of <Formula 3-2> and 1.65 g (7.13 mmol) of Ag ₂ O were added to the round bottom flask. 154 mL of 1,2-dichloroethane was added as a solvent and stirred for 2 days. After evaporating the solvent, the product was dissolved in 154 mL of o-dichlorobenzene, and 4.80 g (12.83 mmol) of Pt(COD)Cl ₂ was added to a 100 mL Schlenk flask, and the product was dissolved in 154 mL of o-dichlorobenzene. > was synthesized in the same manner as <Compound 183> 5.6 g (56.79%) was obtained.

Example 1

A glass substrate (made by Corning) with 15 Ω/cm (1200 Å) ITO as an anode was cut into 50 mm It was irradiated with ultraviolet rays for several minutes, cleaned by exposure to ozone, and installed in a vacuum evaporation device.

2-TNATA was vacuum deposited on the anode to form a hole injection layer with a thickness of 600 Å, and 4,4'-bis[N-(1-naphthyl)-N-phenylaminobiphenyl ( Hereinafter, NPB) was vacuum deposited to form a hole transport layer with a thickness of 300 Å.

Compound 1 (first compound), compound HOST A (second compound), and compound HOST B (third compound) were vacuum deposited on the hole transport layer to form a light emitting layer with a thickness of 400 Å. Here, the content of compound D6 was 10 wt% per total weight (100 wt%) of the emitting layer, and the weight ratio of compound host (HOST) A and compound host (HOST) B was adjusted to 3:7.

Compound ETH2 was vacuum deposited on the emitting layer to form a hole blocking layer with a thickness of 50 Å, Alq ₃ was vacuum deposited on the hole blocking layer to form an electron transport layer with a thickness of 300 Å, and then LiF was vacuum deposited on the electron transport layer. An organic light-emitting device was manufactured by depositing an electron injection layer with a thickness of 10 Å, and then vacuum-depositing Al to form a cathode with a thickness of 3,000 Å.

Examples 2 to 8 and Comparative Example A

An organic light-emitting device was manufactured using the same method as Example 1, except that the compounds listed in Table 1 below were used as the first, second, and third compounds when forming the light-emitting layer.

The specific types of the first compound, second compound, and third compound used in forming the light emitting layer are as follows:

No.No.	도펀트dopant	호스트host		구동 전압 (V)Driving Voltage (V)	(EQE) %(EQE) %	색변환 효 율 (cd/A/y)Color conversion effect rate (cd/A/y)	수명 (T95) (Hr)life span (T95) (Hr)
No.No.	제1화합물first compound	제2화합물Second compound	제3화합물Third compound	구동 전압 (V)Driving Voltage (V)	(EQE) %(EQE) %	색변환 효 율 (cd/A/y)Color conversion effect rate (cd/A/y)	수명 (T95) (Hr)life span (T95) (Hr)
비교예AComparative example A	화합물ACompound A	Host AHost A	Host BHost B	5.35.3	21.521.5	109109	5050
실시예1Example 1	1One	Host AHost A	Host BHost B	5.35.3	23.523.5	126.2126.2	78.278.2
실시예2Example 2	33	Host AHost A	Host BHost B	5.35.3	22.722.7	123.2123.2	80.180.1
실시예3Example 3	77	Host AHost A	Host BHost B	5.35.3	22.922.9	129.2129.2	68.668.6
실시예4Example 4	1111	Host AHost A	Host BHost B	5.45.4	22.122.1	125.4125.4	69.969.9
실시예5Example 5	1919	Host AHost A	Host BHost B	5.35.3	22.322.3	126.2126.2	71.171.1
실시예6Example 6	3535	Host AHost A	Host BHost B	5.15.1	22.222.2	118.9118.9	72.272.2
실시예7Example 7	129129	Host AHost A	Host BHost B	5.35.3	22.422.4	120.1120.1	73.373.3
실시예8Example 8	183183	Host AHost A	Host BHost B	5.45.4	22.222.2	119.3119.3	68.968.9

According to Table 1, compared to Comparative Example A, the organic light emitting device using the compound of the present invention as a dopant shows an equivalent level of driving voltage, has excellent EQE and color conversion efficiency, and exhibits long life characteristics. did.

Claims

Compound represented by Formula 1:

[Formula 1]

here,

m, n and o are the same or different from each other and are each independently an integer from 0 to 10,

p is an integer from 0 to 2,

M is beryllium (Be), magnesium (Mg), aluminum (Al), calcium (Ca), titanium (Ti), manganese (Mn), cobalt (Co), copper (Cu), zinc (Zn), gallium (Ga) ), germanium (Ge), zirconium (Zr), ruthenium (Ru), rhodium (Rh), palladium (Pd), silver (Ag), rhenium (Re), platinum (Pt), or gold (Au),

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

X 1 to X 7 are the same or different from each other and are each independently N or C(R 5 ),

X 8 is N(R 6 ) or C(R 7 )(R 8 ),

Y 1 and Y 2 are the same or different from each other, and each independently represents a single bond, a double bond, N(R 9 ), B(R 10 ), P(R 11 ), Si(R 12 )(R 13 ), Ge (R 14 )(R 15 ), S, Se, O, C(=O), C(=S), S(=O), S(=O) 2 , substituted or unsubstituted C 1 to C 20 selected from the group consisting of an alkylene group, a substituted or unsubstituted C 2 to C 30 alkenylene group, and a substituted or unsubstituted C 2 to C 20 alkynylene group,

R 1 to R 15 are the same or different from each other, and each independently represents hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted C 1 to C 4 alkylthio group, or a substituted or unsubstituted C 1 to C 30 alkyl group, substituted or unsubstituted C 3 to C 20 cycloalkyl group, substituted or unsubstituted C 2 to C 30 alkenyl group, substituted or unsubstituted C 2 to C 30 alkynyl group, substituted or Unsubstituted C 7 to C 30 aralkyl group, substituted or unsubstituted C 6 to C 30 aryl group, substituted or unsubstituted C 1 to C 30 heteroaryl group, substituted or unsubstituted C 6 to C 30 carbon atoms C 30 heteroarylalkyl group, substituted or unsubstituted C 1 to C 30 alkoxy group, substituted or unsubstituted C 1 to C 30 alkylamino group, substituted or unsubstituted C 6 to C 30 arylamino group, substituted Or an unsubstituted C 7 to C 30 aralkylamino group, a substituted or unsubstituted C 1 to C 30 heteroarylamino group, a substituted or unsubstituted C 1 to C 30 alkylsilyl group, or a substituted or unsubstituted C It is selected from the group consisting of 6 to C 30 arylsilyl groups and substituted or unsubstituted C 6 to C 30 aryloxy groups, and may be combined with adjacent groups to form a substituted or unsubstituted ring.
According to paragraph 1,

The compound represented by Formula 1 is a compound represented by Formula 2:

[Formula 2]

here,

n, m, o, p, M, A ring, B ring, C ring, X 1 to X 6 , X 8 , X 9 , Y 1 , Y 2 and R 1 to R 4 are as defined in paragraph 1 ,

X 10 is C.
According to paragraph 1,

The compound represented by Formula 1 is a compound represented by Formula 3 or Formula 4:

[Formula 3]

[Formula 4]

here,

m, o, p, M , A ring , C ring , X 1 to

Z is selected from the group consisting of N, P, P=O, C(R 18 ), Si(R 19 ) and Ge(R 20 );

X 11 to X 13 are the same or different from each other, and are each independently N or C(R 21 ),

R 16 to R 21 are the same or different from each other, and each independently represents hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted C 1 to C 4 alkylthio group, or a substituted or unsubstituted C 1 to C 30 alkyl group, substituted or unsubstituted C 3 to C 20 cycloalkyl group, substituted or unsubstituted C 2 to C 30 alkenyl group, substituted or unsubstituted C 2 to C 30 alkynyl group, substituted or Unsubstituted C 7 to C 30 aralkyl group, substituted or unsubstituted C 6 to C 30 aryl group, substituted or unsubstituted C 1 to C 30 heteroaryl group, substituted or unsubstituted C 6 to C 30 carbon atoms C 30 heteroarylalkyl group, substituted or unsubstituted C 1 to C 30 alkoxy group, substituted or unsubstituted C 1 to C 30 alkylamino group, substituted or unsubstituted C 6 to C 30 arylamino group, substituted Or an unsubstituted C 7 to C 30 aralkylamino group, a substituted or unsubstituted C 1 to C 30 heteroarylamino group, a substituted or unsubstituted C 1 to C 30 alkylsilyl group, or a substituted or unsubstituted C It is selected from the group consisting of 6 to C 30 arylsilyl groups and substituted or unsubstituted C 6 to C 30 aryloxy groups, and may be combined with adjacent groups to form a substituted or unsubstituted ring.
According to paragraph 1,

The A ring is a compound selected from the group consisting of the following formulas 5 to 9:

[Formula 5]

[Formula 6]

[Formula 7]

[Formula 8]

[Formula 9]

here,

* refers to the part combined with M,

*' refers to the combined part,

s is an integer from 0 to 4,

t and v are the same or different from each other and are each independently an integer from 0 to 6,

u is an integer from 0 to 7,

X15 is N(R 28 ) or C(R 29 )(R 30 ),

R 22 to R 30 are the same or different from each other, and each independently represents hydrogen, a cyano group, a nitro group, a halogen group, a hydroxy group, a substituted or unsubstituted C 1 to C 4 alkylthio group, or a substituted or unsubstituted C 1 to C 30 alkyl group, substituted or unsubstituted C 3 to C 20 cycloalkyl group, substituted or unsubstituted C 2 to C 30 alkenyl group, substituted or unsubstituted C 2 to C 30 alkynyl group, substituted or Unsubstituted C 7 to C 30 aralkyl group, substituted or unsubstituted C 6 to C 30 aryl group, substituted or unsubstituted C 1 to C 30 heteroaryl group, substituted or unsubstituted C 6 to C 30 carbon atoms C 30 heteroarylalkyl group, substituted or unsubstituted C 1 to C 30 alkoxy group, substituted or unsubstituted C 1 to C 30 alkylamino group, substituted or unsubstituted C 6 to C 30 arylamino group, substituted Or an unsubstituted C 7 to C 30 aralkylamino group, a substituted or unsubstituted C 1 to C 30 heteroarylamino group, a substituted or unsubstituted C 1 to C 30 alkylsilyl group, or a substituted or unsubstituted C It is selected from the group consisting of 6 to C 30 arylsilyl groups and substituted or unsubstituted C 6 to C 30 aryloxy groups, and may be combined with adjacent groups to form a substituted or unsubstituted ring.
According to paragraph 1,

Wherein M is platinum (Pt).
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 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 is a group consisting of triarylamine, carbazole derivatives, indolocarbazole derivatives, indenocarbazole derivatives, azacarbazole, silane, boron, triazine, dibenzofuran, dibenzothiophene derivatives, and mixtures thereof. An organic electroluminescent device comprising two or more host materials selected from: