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WO2015084021A1 - Novel organic electroluminescent compounds and organic electroluminescent device comprising the same - Google Patents

Novel organic electroluminescent compounds and organic electroluminescent device comprising the same Download PDF

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Publication number
WO2015084021A1
WO2015084021A1 PCT/KR2014/011698 KR2014011698W WO2015084021A1 WO 2015084021 A1 WO2015084021 A1 WO 2015084021A1 KR 2014011698 W KR2014011698 W KR 2014011698W WO 2015084021 A1 WO2015084021 A1 WO 2015084021A1
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Prior art keywords
group
substituted
unsubstituted
alkyl
aryl
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Inventor
Kyung-Joo Lee
Chi-Sik Kim
Seon-Woo Lee
Su-Hyun Lee
Jeong-Eun YANG
Young-Kwang Kim
Hyo-Jung Lee
Young-Jun Cho
Kyoung-Jin Park
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DuPont Specialty Materials Korea Ltd
DuPont Electronic Materials International LLC
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Rohm and Haas Electronic Materials Korea Ltd
Rohm and Haas Electronic Materials LLC
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Priority to CN201480063398.1A priority Critical patent/CN105745200B/en
Priority to JP2016532083A priority patent/JP6599860B2/en
Publication of WO2015084021A1 publication Critical patent/WO2015084021A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
    • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
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    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/10—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing aromatic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
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    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/615—Polycyclic condensed aromatic hydrocarbons, e.g. anthracene
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
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    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/60—Organic compounds having low molecular weight
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • H10K85/6572—Polycyclic condensed heteroaromatic hydrocarbons comprising only nitrogen in the heteroaromatic polycondensed ring system, e.g. phenanthroline or carbazole
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
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    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers

Definitions

  • the present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device comprising the same.
  • An electroluminescent (EL) device is a self-light-emitting device with the advantage of providing a wider viewing angle, a greater contrast ratio, and a faster response time.
  • An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as materials for forming a light-emitting layer (see Appl. Phys. Lett. 51, 913, 1987).
  • the organic EL device generally comprises an anode, a cathode, and an organic layer formed between the two electrodes and emits light when holes injected from an anode and electrons injected from a cathode form the excited state by their recombination and then the excited state is returned to the ground state.
  • the organic layer of the organic EL device may be composed of a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), a light-emitting layer (EML), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), etc.; the materials used in the organic layer can be classified into a hole injection material, a hole transport material, an electron blocking material, a light-emitting material, a hole blocking material, an electron transport material, an electron injection material, etc.
  • HIL hole injection layer
  • HTL hole transport layer
  • EBL electron blocking layer
  • HBL hole blocking layer
  • HBL hole blocking layer
  • ETL electron transport layer
  • EIL electron injection layer
  • the most important factor determining luminescent efficiency in the organic EL device is the light-emitting material.
  • the light-emitting material is required to have the following features: high quantum efficiency, high movement degree of an electron and a hole, formability of a uniform light-emitting material layer, and stability.
  • a mixed system of a dopant/host material can be used as the light-emitting material to improve color purity, luminescent efficiency, and stability. If the dopant/host material system is used, the selection of host materials is important since host materials greatly influence the efficiency and performance of a light-emitting device. In conventional technique, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known phosphorescent host material.
  • CBP 4,4’-N,N’-dicarbazol-biphenyl
  • the present invention can minimize crystallization by heat during and after vapor deposition at high temperature by increasing thermal stability of the materials.
  • glass transition temperature should be increased in order to increase thermal stability.
  • Tg glass transition temperature
  • many substituents should be bonded.
  • the temperature of vapor deposition excessively increases and the materials degrade and get damaged during vapor deposition when many substituents are bonded.
  • a suitable Tg should be maintained by introduction of the suitable number of substituents and low vapor deposition temperature should be retained despite high molecular weight.
  • the present invention solves the above problems by introducing a carbazole group into the 9-position of a fluorene structure.
  • the materials of the present invention have high molecular weight, they have lower vapor deposition temperature than the carbazole derivatives having similar molecular weight.
  • the materials of the present invention have a high Tg.
  • This feature results from the substitution of a carbazole group at the 9-position of a fluorene structure thereby increasing steric hindrance of the fluorene structure.
  • the higher steric hindrance the lesser interaction between molecules and the lower vapor deposition temperature.
  • Korean Patent Nos. 10-0957288, 10-0948700, and 10-0955993 disclose the compounds wherein a nitrogen-containing heterocyclic group is bonded to a carbazole group, the compounds wherein a nitrogen-containing heterocyclic group is bonded to an arylcarbazole or carbazolylalkylene group, and specific structures of indolocarbazole derivatives, respectively, as host materials in a light-emitting layer.
  • the organic EL devices comprising the compounds recited in the above publications still do not satisfy power efficiency, luminescent efficiency, lifespan, etc.
  • the present inventors have tried to find organic electroluminescent compounds which can provide the organic EL device with properties superior to the compounds recited in the above publications and have found materials having high Tg and low temperature of vapor deposition via the introduction of a carbazole group at the 9-position of a fluorene structure, and thus can provide the organic EL device with high luminescent efficiency and excellent properties.
  • the object of the present invention is to provide organic electroluminescent compounds having high luminescent efficiency and to provide an organic EL device comprising the organic electroluminescent compounds and having long driving lifespan, and improved power efficiency and current efficiency.
  • a 1 represents a substituted or unsubstituted 5- to 30-membered heteroaryl group
  • L 1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group;
  • R 1 represents a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkylamino group, a substituted or unsubstituted (C6-C30)arylamino group, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino group;
  • R 2 represents hydrogen, deuterium, a halogen, a cyano group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C1-C30)alkylsilyl group, a substituted or unsubstituted (C6-C30)arylsilyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl group, a substituted or unsubstituted (C1-C30)alkylamino group, a substituted or un
  • R 2 forms a benzocarbazole by fusion to a carbazole ring
  • R 3 represents hydrogen, deuterium, a halogen, a cyano group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C1-C30)alkylsilyl group, a substituted or unsubstituted (C6-C30)arylsilyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl group, a substituted or unsubstituted (C1-C30)alkylamino group, a substituted or un
  • X represents O, S, CR 11 R 12 , NR 13 , or SiR 13 R 14 ;
  • R 4 , R 5 and R 6 each independently represent hydrogen, deuterium, a halogen, a cyano group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C1-C30)alkylsilyl group, a substituted or unsubstituted (C6-C30)arylsilyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl group, a substituted or unsubstituted (C1-C30)alkylamin
  • R 11 to R 14 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
  • a, c, d and e each independently represent an integer of 1 to 4; where a, c, d or e is an integer of 2 or more, each R 2 , R 4 , R 5 or R 6 is the same or different;
  • b represents an integer of 1 to 3; where b is an integer of 2 or more, each R 3 is the same or different;
  • n an integer of 0 or 1;
  • n an integer of 1 or 2;
  • the organic electroluminescent compounds according to the present invention have high luminescent efficiency compared with conventional material, and thus the organic EL device comprising the compounds as a light-emitting host material has long driving lifespan and improved power efficiency thereby reducing consumption power.
  • the present invention relates to an organic electroluminescent compound represented by formula 1, an organic electroluminescent material comprising the organic electroluminescent compound, and an organic EL device comprising the material.
  • (C1-C30)alkyl(ene) is meant to be a linear or branched alkyl(ene) having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.
  • (C2-C30)alkenyl is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.
  • (C2-C30)alkynyl is a linear or branched alkynyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc.
  • (C3-C30)cycloalkyl is a mono- or polycyclic hydrocarbon having 3 to 30 carbon atoms, in which the number of carbon atoms is preferably 3 to 20, more preferably 3 to 7, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • (C6-C30)aryl(ene) is a monocyclic or fused ring derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, in which the number of carbon atoms is preferably 6 to 20, more preferably 6 to 15, and includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc.
  • substituted in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e., a substituent.
  • the compound of formula 1 is represented by the following formula 3, 4, or 5:
  • a 1 , L 1 , R 1 to R 5 , a, b, c, d, m and n are as defined in formula 1.
  • a 1 represents pyridine, pyrimidine, triazine, pyrazine, quinoline, quinazoline, quinoxaline, or naphthyridine
  • L 1 represents a single bond or a (C6-C20)arylene group
  • R 1 represents a (C1-C20)alkyl group, a (C6-C20)aryl group, or a 5- to 20-membered heteroaryl group
  • R 2 represents hydrogen, deuterium, a (C6-C20)aryl group, a 5- to 20-membered heteroaryl group, a (C6-C20)arylamino group, or formula 2, or forms a benzocarbazole by fusion to a carbazole ring
  • R 3 , R 4 , R 5 and R 6 each independently represent hydrogen or a (C1-C20)alkyl group
  • R 11 to R 14 each independently represent a (C1-C20)alkyl group, a (C
  • the compound of formula 1 can be selected from the group consisting of the following compounds:
  • organic electroluminescent compounds according to the present invention can be prepared by known methods to one skilled in the art, and can be prepared, for example, according to the following reaction scheme 1:
  • a 1 , L 1 , R 1 to R 5 , a, b, c, d, m and n are as defined in formula 1 and Hal represents a halogen.
  • the present invention further provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
  • the material can be comprised of the organic electroluminescent compound of the present invention alone, or can further include conventional materials generally included in organic electroluminescent materials.
  • the organic electroluminescent device may comprise a first electrode, a second electrode, and at least one organic layer between the first and second electrodes, wherein the organic layer comprises at least one organic electroluminescent compound of formula 1.
  • the organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, an electron injection layer, an interlayer, and a hole blocking layer.
  • the organic electroluminescent compound of formula 1 of the present invention can be included as a host material in the light-emitting layer.
  • the light-emitting layer may further include at least one dopant and, if necessary, may comprise other compounds, in addition to the organic electroluminescent compound of formula 1 of the present invention, as a second host material.
  • the present invention further provides materials for preparing an organic EL device.
  • the materials comprise the first and second host materials.
  • the first host material includes the organic electroluminescent compound of the present invention.
  • the first host material and the second host material may be in the range of 1:99 to 99:1 in a weight ratio.
  • the second host material can be any of the known phosphorescent hosts and preferably is selected from the group consisting of the compounds of the following formulae 6 to 10 in view of luminescent efficiency:
  • X represents O or S
  • R 21 to R 24 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- or 30-membered heteroaryl group, or R 25 R 26 R 27 Si-; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C5-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
  • R 25 to R 27 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group;
  • L 4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- or 30-membered heteroarylene group;
  • M represents a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- or 30-membered heteroaryl group;
  • Y 1 and Y 2 each independently represent -O-, -S-, -N(R 31 )- or -C(R 32 )(R 33 )-; and Y 1 and Y 2 are not simultaneously present;
  • R 31 to R 33 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- or 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C5-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur; and R 32 and R 33 may be the same or different;
  • h and i each independently represent an integer of 1 to 3;
  • j, k, l and m each independently represent an integer of 0 to 4.
  • each (Cz-L 4 ), each (Cz), each R 21 , each R 22 , each R 23 or each R 24 is the same or different.
  • the second host material includes the following:
  • TPS represents triphenylsilyl
  • the dopants are preferably one or more phosphorescent dopants.
  • the phosphorescent dopant material applied to the organic electroluminescent device of the present invention is not specifically limited, but preferably may be selected from complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), more preferably ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
  • the dopant used in the organic electroluminescent device of the present invention may be selected from the group consisting of the compounds represented by the following formulae 11 to 13:
  • L is selected from the following structures:
  • R 100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group
  • R 101 to R 109 and R 111 to R 123 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s), a substituted or unsubstituted (C3-C30)cycloalkyl group, a cyano group, or a substituted or unsubstituted (C1-C30)alkoxy group
  • R 120 to R 123 are linked to an adjacent substituent(s) to form a fused ring, for example, quinoline
  • R 124 to R 127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or
  • the dopant material includes the following:
  • the organic layer of the organic electroluminescent device of the present invention comprises the organic electroluminescent compounds of formula 1 and may further include at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
  • the organic layer may further comprise, in addition to the organic electroluminescent compounds of formula 1, at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4 th period, transition metals of the 5 th period, lanthanides, and organic metals of d-transition elements of the Periodic Table, or at least one complex compound comprising the metal.
  • the organic electroluminescent device of the present invention may emit white light by further comprising at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound, or a green electroluminescent compound, besides the organic electroluminescent compound of the present invention; and may further include a yellow or orange light-emitting layer, if necessary.
  • a surface layer selected from a chalcogenide layer, a metal halide layer and a metal oxide layer may be placed on an inner surface(s) of one or both electrode(s).
  • a chalcogenide (including oxides) layer of silicon or aluminum is placed on an anode surface of a light-emitting medium layer, and a metal halide layer or metal oxide layer is placed on a cathode surface of an electroluminescent medium layer.
  • the surface layer provides operating stability for the organic electroluminescent device.
  • the chalcogenide includes SiO X (1 ⁇ X ⁇ 2), AlO X (1 ⁇ X ⁇ 1.5), SiON, SiAlON, etc.;
  • the metal halide includes LiF, MgF 2 , CaF 2 , a rare earth metal fluoride, etc.; and the metal oxide includes Cs 2 O, Li 2 O, MgO, SrO, BaO, CaO, etc.
  • a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant may be placed on at least one surface of a pair of electrodes.
  • the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to a light-emitting medium.
  • the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to a light-emitting medium.
  • the oxidative dopant includes various Lewis acids and acceptor compounds; and the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof.
  • a reductive dopant layer may be employed as a charge-generating layer to prepare an organic electroluminescent device having two or more light-emitting layers and emitting white light.
  • dry film-forming methods such as vacuum deposition, sputtering, plasma, ion plating methods, etc.
  • wet film-forming methods such as spin coating, dip coating, flow coating methods, etc.
  • a thin film is formed by dissolving or dispersing the material constituting each layer in suitable solvents, such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • suitable solvents such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • the solvents are not specifically limited as long as the material constituting each layer is soluble or dispersible in the solvents, which do not cause any problems in forming a layer.
  • An organic light-emitting diode (OLED) device using the organic electroluminescent compound of the present invention was produced as follows: A transparent electrode indium tin oxide (ITO) thin film (15 ⁇ /sq) on a glass substrate for an OLED device (Samsung Corning, Republic of Korea) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol, and distilled water, sequentially, and was then stored in isopropanol. Next, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • ITO indium tin oxide
  • N 1 ,N 1’ -([1,1’-biphenyl]-4,4’-diyl)bis(N 1 -(naphthalene-1-yl)-N 4 ,N 4 -diphenylbenzene-1,4-diamine) was introduced into a cell of the vacuum vapor depositing apparatus, and the pressure in the chamber of the apparatus was then controlled to 10 -6 torr. Thereafter, an electric current was applied to the cell to evaporate the introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate.
  • N,N’-di(4-biphenyl)-N,N’-di(4-biphenyl)-4,4’-diaminobiphenyl was introduced into another cell of the vacuum vapor depositing apparatus, and an electric current was applied to the cell to evaporate the introduced material, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer.
  • Compound H-34 was introduced as a host into one cell of the vacuum vapor depositing apparatus, and compound D-1 as a dopant was introduced into another cell.
  • the two materials were evaporated at different rates and the dopant was deposited in a doping amount of 15 wt%, based on the total weight of the host and dopant, to form a light-emitting layer having a thickness of 30 nm on the hole transport layer.
  • 2-(4-(9,10-di(naphthalene-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidiazole was then introduced into one cell, and lithium quinolate was introduced into another cell.
  • the two materials were evaporated at the same rates and were respectively deposited in a doping amount of 50 wt% to form an electron transport layer having a thickness of 30 nm on the light-emitting layer.
  • an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer.
  • All the materials used for producing the OLED device were purified by vacuum sublimation at 10-6 torr prior to use.
  • the produced OLED device showed green emission having a current density of 3.32 mA/cm 2 and a luminance of 1310 cd/m 2 at 2.5 V.
  • An OLED device was produced in the same manner as in Device Example 1, except that compound H-57 was used as a host in a light-emitting material.
  • the produced OLED device showed green emission having a current density of 7.26 mA/cm 2 and a luminance of 2840 cd/m 2 at 2.6 V.
  • An OLED device was produced in the same manner as in Device Example 1, except that compound H-90 was used as a host in a light-emitting material.
  • the produced OLED device showed green emission having a current density of 9.40 mA/cm 2 and a luminance of 3910 cd/m 2 at 2.7 V.
  • An OLED device was produced in the same manner as in Device Example 1, except that compound H-15 was used as a host in a light-emitting material.
  • the produced OLED device showed green emission having a current density of 2.45 mA/cm 2 and a luminance of 890 cd/m 2 at 2.6 V.
  • Comparative Example 1 Production of an OLED device by using
  • An OLED device was produced in the same manner as in Device Example 1, except that Compound 1 was used as a host and compound D-86 was used as a dopant in a light-emitting material.
  • the produced OLED device showed green emission having a current density of 5.20 mA/cm 2 and a luminance of 1020 cd/m 2 at 4.3 V.
  • the organic electroluminescent compound of the present invention provides more excellent luminescent property than conventional light-emitting materials. Furthermore, the organic electroluminescent device using the organic electroluminescent compound of the present invention as a light-emitting host material provides good luminescent property and reduces the driving voltage, thereby enhancing power efficiency and improving consumption power.

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Abstract

The present invention relates to a novel organic electroluminescent compound and an organic electroluminescent device comprising the same. The organic electroluminescent compound according to the present invention can be used in a light-emitting layer and has excellent luminescent efficiency; and an organic electroluminescent device comprising the organic electroluminescent compounds of the present invention has long life span, and improved current efficiency and power efficiency.

Description

NOVEL ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present invention relates to novel organic electroluminescent compounds and an organic electroluminescent device comprising the same.
An electroluminescent (EL) device is a self-light-emitting device with the advantage of providing a wider viewing angle, a greater contrast ratio, and a faster response time. An organic EL device was first developed by Eastman Kodak, by using small aromatic diamine molecules and aluminum complexes as materials for forming a light-emitting layer (see Appl. Phys. Lett. 51, 913, 1987).
The organic EL device generally comprises an anode, a cathode, and an organic layer formed between the two electrodes and emits light when holes injected from an anode and electrons injected from a cathode form the excited state by their recombination and then the excited state is returned to the ground state. The organic layer of the organic EL device may be composed of a hole injection layer (HIL), a hole transport layer (HTL), an electron blocking layer (EBL), a light-emitting layer (EML), a hole blocking layer (HBL), an electron transport layer (ETL), an electron injection layer (EIL), etc.; the materials used in the organic layer can be classified into a hole injection material, a hole transport material, an electron blocking material, a light-emitting material, a hole blocking material, an electron transport material, an electron injection material, etc.
The most important factor determining luminescent efficiency in the organic EL device is the light-emitting material. The light-emitting material is required to have the following features: high quantum efficiency, high movement degree of an electron and a hole, formability of a uniform light-emitting material layer, and stability. A mixed system of a dopant/host material can be used as the light-emitting material to improve color purity, luminescent efficiency, and stability. If the dopant/host material system is used, the selection of host materials is important since host materials greatly influence the efficiency and performance of a light-emitting device. In conventional technique, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known phosphorescent host material. Pioneer (Japan) et al., currently developed a high performance organic EL device by employing bathocuproine (BCP), aluminum(III) bis(2-methyl-8-quinolinato)(4-phenylphenolate) (BAlq), etc., which were used in a hole blocking layer, as host materials.
Although these phosphorescent host materials provide good light-emitting characteristics, they have the following disadvantages: (1) Due to their low glass transition temperatures and poor thermal stability, their degradation may occur during a high-temperature deposition process in a vacuum. (2) The power efficiency of an organic EL device is given by [(π/voltage) × current efficiency], and the power efficiency is inversely proportional to voltage. An organic EL device comprising phosphorescent host materials provides higher current efficiency (cd/A) and has a higher driving voltage than one comprising fluorescent host materials. Thus, the organic EL device using conventional phosphorescent host materials has no advantage in terms of power efficiency (lm/W). (3) Furthermore, the operating lifespan and luminescent efficiency of the organic EL device are not satisfactory.
The present invention can minimize crystallization by heat during and after vapor deposition at high temperature by increasing thermal stability of the materials.
Generally, glass transition temperature (Tg) should be increased in order to increase thermal stability. In order to increase Tg, many substituents should be bonded. However, the temperature of vapor deposition excessively increases and the materials degrade and get damaged during vapor deposition when many substituents are bonded. Thus, a suitable Tg should be maintained by introduction of the suitable number of substituents and low vapor deposition temperature should be retained despite high molecular weight. The present invention solves the above problems by introducing a carbazole group into the 9-position of a fluorene structure. Although the materials of the present invention have high molecular weight, they have lower vapor deposition temperature than the carbazole derivatives having similar molecular weight. Furthermore, the materials of the present invention have a high Tg. This feature results from the substitution of a carbazole group at the 9-position of a fluorene structure thereby increasing steric hindrance of the fluorene structure. The higher steric hindrance, the lesser interaction between molecules and the lower vapor deposition temperature.
Thus, in order to embody excellent properties of the organic EL device, the materials constituting the organic layers in the device, in particular the host or dopant, should be suitably selected. Meanwhile, Korean Patent Nos. 10-0957288, 10-0948700, and 10-0955993 disclose the compounds wherein a nitrogen-containing heterocyclic group is bonded to a carbazole group, the compounds wherein a nitrogen-containing heterocyclic group is bonded to an arylcarbazole or carbazolylalkylene group, and specific structures of indolocarbazole derivatives, respectively, as host materials in a light-emitting layer. However, the organic EL devices comprising the compounds recited in the above publications still do not satisfy power efficiency, luminescent efficiency, lifespan, etc. Thus, the present inventors have tried to find organic electroluminescent compounds which can provide the organic EL device with properties superior to the compounds recited in the above publications and have found materials having high Tg and low temperature of vapor deposition via the introduction of a carbazole group at the 9-position of a fluorene structure, and thus can provide the organic EL device with high luminescent efficiency and excellent properties.
The object of the present invention is to provide organic electroluminescent compounds having high luminescent efficiency and to provide an organic EL device comprising the organic electroluminescent compounds and having long driving lifespan, and improved power efficiency and current efficiency.
The present inventors found that the above objective can be achieved by a compound represented by the following formula 1:
Figure PCTKR2014011698-appb-I000001
wherein
A1 represents a substituted or unsubstituted 5- to 30-membered heteroaryl group;
L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group;
R1 represents a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkylamino group, a substituted or unsubstituted (C6-C30)arylamino group, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino group;
R2 represents hydrogen, deuterium, a halogen, a cyano group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C1-C30)alkylsilyl group, a substituted or unsubstituted (C6-C30)arylsilyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl group, a substituted or unsubstituted (C1-C30)alkylamino group, a substituted or unsubstituted (C6-C30)arylamino group, a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino group, or the following formula 2:
Figure PCTKR2014011698-appb-I000002
R2 forms a benzocarbazole by fusion to a carbazole ring;
R3 represents hydrogen, deuterium, a halogen, a cyano group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C1-C30)alkylsilyl group, a substituted or unsubstituted (C6-C30)arylsilyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl group, a substituted or unsubstituted (C1-C30)alkylamino group, a substituted or unsubstituted (C6-C30)arylamino group, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino group;
X represents O, S, CR11R12, NR13, or SiR13R14;
R4, R5 and R6 each independently represent hydrogen, deuterium, a halogen, a cyano group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C1-C30)alkylsilyl group, a substituted or unsubstituted (C6-C30)arylsilyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl group, a substituted or unsubstituted (C1-C30)alkylamino group, a substituted or unsubstituted (C6-C30)arylamino group, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
R11 to R14 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
a, c, d and e each independently represent an integer of 1 to 4; where a, c, d or e is an integer of 2 or more, each R2, R4, R5 or R6 is the same or different;
b represents an integer of 1 to 3; where b is an integer of 2 or more, each R3 is the same or different;
n represents an integer of 0 or 1;
m represents an integer of 1 or 2; and
the heteroaryl(ene) group contains at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
The organic electroluminescent compounds according to the present invention have high luminescent efficiency compared with conventional material, and thus the organic EL device comprising the compounds as a light-emitting host material has long driving lifespan and improved power efficiency thereby reducing consumption power.
Hereinafter, the present invention will be described in detail. However, the following description is intended to explain the invention, and is not meant in any way to restrict the scope of the invention.
The present invention relates to an organic electroluminescent compound represented by formula 1, an organic electroluminescent material comprising the organic electroluminescent compound, and an organic EL device comprising the material.
Herein, “(C1-C30)alkyl(ene)” is meant to be a linear or branched alkyl(ene) having 1 to 30 carbon atoms, in which the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. “(C2-C30)alkenyl” is meant to be a linear or branched alkenyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc. “(C2-C30)alkynyl” is a linear or branched alkynyl having 2 to 30 carbon atoms, in which the number of carbon atoms is preferably 2 to 20, more preferably 2 to 10, and includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc. “(C3-C30)cycloalkyl” is a mono- or polycyclic hydrocarbon having 3 to 30 carbon atoms, in which the number of carbon atoms is preferably 3 to 20, more preferably 3 to 7, and includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. “3- to 7-membered heterocycloalkyl” is a cycloalkyl having at least one heteroatom selected from B, N, O, S, P(=O), Si and P, preferably O, S and N, and 3 to 7, preferably 5 to 7 ring backbone atoms, and includes tetrahydrofuran, pyrrolidine, thiolan, tetrahydropyran, etc. “(C6-C30)aryl(ene)” is a monocyclic or fused ring derived from an aromatic hydrocarbon having 6 to 30 carbon atoms, in which the number of carbon atoms is preferably 6 to 20, more preferably 6 to 15, and includes phenyl, biphenyl, terphenyl, naphthyl, fluorenyl, phenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, etc. “3- to 30-membered heteroaryl(ene)” is an aryl group having at least one, preferably 1 to 4 heteroatom selected from the group consisting of B, N, O, S, P(=O), Si and P, and 3 to 30 ring backbone atoms; is a monocyclic ring, or a fused ring condensed with at least one benzene ring; has preferably 3 to 20, more preferably 3 to 15 ring backbone atoms; may be partially saturated; may be one formed by linking at least one heteroaryl or aryl group to a heteroaryl group via a single bond(s); and includes a monocyclic ring-type heteroaryl including furyl, thiophenyl, pyrrolyl, imidazolyl, pyrazolyl, thiazolyl, thiadiazolyl, isothiazolyl, isoxazolyl, oxazolyl, oxadiazolyl, triazinyl, tetrazinyl, triazolyl, tetrazolyl, furazanyl, pyridyl, pyrazinyl, pyrimidinyl, pyridazinyl, etc., and a fused ring-type heteroaryl including benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzoimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, etc. “Halogen” includes F, Cl, Br and I.
Herein, “substituted” in the expression “substituted or unsubstituted” means that a hydrogen atom in a certain functional group is replaced with another atom or group, i.e., a substituent. Substituents of the substituted (C1-C30)alkyl group, the substituted (C1-C30)alkoxy group, the substituted (C3-C30)cycloalkyl group, the substituted (C6-C30)aryl(ene) group, the substituted 5- to 30-membered heteroaryl(ene) group, and the substituted (C6-C30)aryl(C1-C30)alky group in A1, L1, R1 to R6 and R11 to R14 of formula 1 are each independently at least one selected from the group consisting of deuterium; a halogen; a cyano group; a carboxyl group; a nitro group; a hydroxyl group; a (C1-C30)alkyl group; a halo(C1-C30)alkyl group; a (C2-C30)alkenyl group; a (C2-C30)alkynyl group; a (C1-C30)alkoxy group; a (C1-C30)alkylthio group; a (C3-C30)cycloalkyl group; a (C3-C30)cycloalkenyl group; a 3- to 7-membered heterocycloalkyl group; a (C6-C30)aryloxy group; a (C6-C30)arylthio group; a 3- to 30-membered heteroaryl group which is unsubstituted or substituted with a (C6-C30)aryl group; a (C6-C30)aryl group which is unsubstituted or substituted with a 3- to 30-membered heteroaryl group; a tri(C1-C30)alkylsilyl group; a tri(C6-C30)arylsilyl group; a di(C1-C30)alkyl(C6-C30)arylsilyl group; a (C1-C30)alkyldi(C6-C30)arylsilyl group; an amino group; a mono- or di(C1-C30)alkylamino group; a mono- or di(C6-C30)arylamino group; a (C1-C30)alkyl(C6-C30)arylamino group; a (C1-C30)alkylcarbonyl group; a (C1-C30)alkoxycarbonyl group; a (C6-C30)arylcarbonyl group; a di(C6-C30)arylboronyl group; a di(C1-C30)alkylboronyl group; a (C1-C30)alkyl(C6-C30)arylboronyl group; a (C6-C30)aryl(C1-C30)alkyl group; and a (C1-C30)alkyl(C6-C30)aryl group.
The compound of formula 1 is represented by the following formula 3, 4, or 5:
Figure PCTKR2014011698-appb-I000003
wherein
A1, L1, R1 to R5, a, b, c, d, m and n are as defined in formula 1.
In the compound of formula 1, preferably, A1 represents pyridine, pyrimidine, triazine, pyrazine, quinoline, quinazoline, quinoxaline, or naphthyridine; L1 represents a single bond or a (C6-C20)arylene group; R1 represents a (C1-C20)alkyl group, a (C6-C20)aryl group, or a 5- to 20-membered heteroaryl group; R2 represents hydrogen, deuterium, a (C6-C20)aryl group, a 5- to 20-membered heteroaryl group, a (C6-C20)arylamino group, or formula 2, or forms a benzocarbazole by fusion to a carbazole ring; R3, R4, R5 and R6 each independently represent hydrogen or a (C1-C20)alkyl group; and R11 to R14 each independently represent a (C1-C20)alkyl group, a (C6-C20)aryl group, or a 5- to 20-membered heteroaryl group.
The compound of formula 1 can be selected from the group consisting of the following compounds:
Figure PCTKR2014011698-appb-I000004
Figure PCTKR2014011698-appb-I000005
Figure PCTKR2014011698-appb-I000006
Figure PCTKR2014011698-appb-I000007
Figure PCTKR2014011698-appb-I000008
Figure PCTKR2014011698-appb-I000009
Figure PCTKR2014011698-appb-I000010
Figure PCTKR2014011698-appb-I000011
Figure PCTKR2014011698-appb-I000012
Figure PCTKR2014011698-appb-I000013
Figure PCTKR2014011698-appb-I000014
Figure PCTKR2014011698-appb-I000015
Figure PCTKR2014011698-appb-I000016
Figure PCTKR2014011698-appb-I000017
Figure PCTKR2014011698-appb-I000018
Figure PCTKR2014011698-appb-I000019
Figure PCTKR2014011698-appb-I000020
Figure PCTKR2014011698-appb-I000021
Figure PCTKR2014011698-appb-I000022
Figure PCTKR2014011698-appb-I000023
Figure PCTKR2014011698-appb-I000024
Figure PCTKR2014011698-appb-I000025
The organic electroluminescent compounds according to the present invention can be prepared by known methods to one skilled in the art, and can be prepared, for example, according to the following reaction scheme 1:
Reaction scheme 1
Figure PCTKR2014011698-appb-I000026
wherein
A1, L1, R1 to R5, a, b, c, d, m and n are as defined in formula 1 and Hal represents a halogen.
The present invention further provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material. The material can be comprised of the organic electroluminescent compound of the present invention alone, or can further include conventional materials generally included in organic electroluminescent materials.
The organic electroluminescent device according to the present invention may comprise a first electrode, a second electrode, and at least one organic layer between the first and second electrodes, wherein the organic layer comprises at least one organic electroluminescent compound of formula 1.
One of the first electrode and the second electrode can be an anode and the other can be a cathode. The organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from the group consisting of a hole injection layer, a hole transport layer, an electron blocking layer, an electron transport layer, an electron injection layer, an interlayer, and a hole blocking layer.
The organic electroluminescent compound of formula 1 of the present invention can be included as a host material in the light-emitting layer. Preferably, the light-emitting layer may further include at least one dopant and, if necessary, may comprise other compounds, in addition to the organic electroluminescent compound of formula 1 of the present invention, as a second host material.
The present invention further provides materials for preparing an organic EL device. The materials comprise the first and second host materials. The first host material includes the organic electroluminescent compound of the present invention. The first host material and the second host material may be in the range of 1:99 to 99:1 in a weight ratio.
The second host material can be any of the known phosphorescent hosts and preferably is selected from the group consisting of the compounds of the following formulae 6 to 10 in view of luminescent efficiency:
Figure PCTKR2014011698-appb-I000027
Figure PCTKR2014011698-appb-I000028
Figure PCTKR2014011698-appb-I000029
Figure PCTKR2014011698-appb-I000030
Figure PCTKR2014011698-appb-I000031
wherein
Cz represents the following structure:
Figure PCTKR2014011698-appb-I000032
X represents O or S;
R21 to R24 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- or 30-membered heteroaryl group, or R25R26R27Si-; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C5-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
R25 to R27 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group;
L4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- or 30-membered heteroarylene group;
M represents a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- or 30-membered heteroaryl group;
Y1 and Y2 each independently represent -O-, -S-, -N(R31)- or -C(R32)(R33)-; and Y1 and Y2 are not simultaneously present;
R31 to R33 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- or 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C5-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur; and R32 and R33 may be the same or different;
h and i each independently represent an integer of 1 to 3;
j, k, l and m each independently represent an integer of 0 to 4;
where h, i, j, k, l or m is an integer of 2 or more, each (Cz-L4), each (Cz), each R21, each R22, each R23 or each R24 is the same or different.
Specifically, the second host material includes the following:
Figure PCTKR2014011698-appb-I000033
Figure PCTKR2014011698-appb-I000034
Figure PCTKR2014011698-appb-I000035
Figure PCTKR2014011698-appb-I000036
Figure PCTKR2014011698-appb-I000037
Figure PCTKR2014011698-appb-I000038
Figure PCTKR2014011698-appb-I000039
Figure PCTKR2014011698-appb-I000040
Figure PCTKR2014011698-appb-I000041
Figure PCTKR2014011698-appb-I000042
Figure PCTKR2014011698-appb-I000043
Figure PCTKR2014011698-appb-I000044
Figure PCTKR2014011698-appb-I000045
wherein TPS represents triphenylsilyl.
The dopants are preferably one or more phosphorescent dopants. The phosphorescent dopant material applied to the organic electroluminescent device of the present invention is not specifically limited, but preferably may be selected from complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), more preferably ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu), and platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
The dopant used in the organic electroluminescent device of the present invention may be selected from the group consisting of the compounds represented by the following formulae 11 to 13:
Figure PCTKR2014011698-appb-I000046
wherein
L is selected from the following structures:
Figure PCTKR2014011698-appb-I000047
R100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C3-C30)cycloalkyl group; R101 to R109 and R111 to R123 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s), a substituted or unsubstituted (C3-C30)cycloalkyl group, a cyano group, or a substituted or unsubstituted (C1-C30)alkoxy group; R120 to R123 are linked to an adjacent substituent(s) to form a fused ring, for example, quinoline; R124 to R127 each independently represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl group, or a substituted or unsubstituted (C6-C30)aryl group; when R124 to R127 are aryl groups, they are linked to an adjacent substituent(s) to form a fused ring, for example, fluorene; R201 to R211 each independently represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl group unsubstituted or substituted with halogen(s), or a substituted or unsubstituted (C3-C30)cycloalkyl group; f and g each independently represent an integer of 1 to 3; where f or g is an integer of 2 or more, each R100 may be the same or different; and n represents an integer of 1 to 3.
The dopant material includes the following:
Figure PCTKR2014011698-appb-I000048
Figure PCTKR2014011698-appb-I000049
Figure PCTKR2014011698-appb-I000050
Figure PCTKR2014011698-appb-I000051
Figure PCTKR2014011698-appb-I000052
Figure PCTKR2014011698-appb-I000053
Figure PCTKR2014011698-appb-I000054
Figure PCTKR2014011698-appb-I000055
Figure PCTKR2014011698-appb-I000056
Figure PCTKR2014011698-appb-I000057
Figure PCTKR2014011698-appb-I000058
Figure PCTKR2014011698-appb-I000059
Figure PCTKR2014011698-appb-I000060
Figure PCTKR2014011698-appb-I000061
Figure PCTKR2014011698-appb-I000062
Figure PCTKR2014011698-appb-I000063
Figure PCTKR2014011698-appb-I000064
Figure PCTKR2014011698-appb-I000065
Figure PCTKR2014011698-appb-I000066
Figure PCTKR2014011698-appb-I000067
Figure PCTKR2014011698-appb-I000068
Figure PCTKR2014011698-appb-I000069
Figure PCTKR2014011698-appb-I000070
Figure PCTKR2014011698-appb-I000071
Figure PCTKR2014011698-appb-I000072
Figure PCTKR2014011698-appb-I000073
The organic layer of the organic electroluminescent device of the present invention comprises the organic electroluminescent compounds of formula 1 and may further include at least one compound selected from the group consisting of arylamine-based compounds and styrylarylamine-based compounds.
In the organic electroluminescent device of the present invention, the organic layer may further comprise, in addition to the organic electroluminescent compounds of formula 1, at least one metal selected from the group consisting of metals of Group 1, metals of Group 2, transition metals of the 4th period, transition metals of the 5th period, lanthanides, and organic metals of d-transition elements of the Periodic Table, or at least one complex compound comprising the metal.
In addition, the organic electroluminescent device of the present invention may emit white light by further comprising at least one light-emitting layer which comprises a blue electroluminescent compound, a red electroluminescent compound, or a green electroluminescent compound, besides the organic electroluminescent compound of the present invention; and may further include a yellow or orange light-emitting layer, if necessary.
Preferably, in the organic electroluminescent device of the present invention, at least one layer (hereinafter, "a surface layer”) selected from a chalcogenide layer, a metal halide layer and a metal oxide layer may be placed on an inner surface(s) of one or both electrode(s). Specifically, it is preferred that a chalcogenide (including oxides) layer of silicon or aluminum is placed on an anode surface of a light-emitting medium layer, and a metal halide layer or metal oxide layer is placed on a cathode surface of an electroluminescent medium layer. The surface layer provides operating stability for the organic electroluminescent device. Preferably, the chalcogenide includes SiOX(1≤X≤2), AlOX(1≤X≤1.5), SiON, SiAlON, etc.; the metal halide includes LiF, MgF2, CaF2, a rare earth metal fluoride, etc.; and the metal oxide includes Cs2O, Li2O, MgO, SrO, BaO, CaO, etc.
Preferably, in the organic electroluminescent device of the present invention, a mixed region of an electron transport compound and a reductive dopant, or a mixed region of a hole transport compound and an oxidative dopant may be placed on at least one surface of a pair of electrodes. In this case, the electron transport compound is reduced to an anion, and thus it becomes easier to inject and transport electrons from the mixed region to a light-emitting medium. Further, the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to a light-emitting medium. Preferably, the oxidative dopant includes various Lewis acids and acceptor compounds; and the reductive dopant includes alkali metals, alkali metal compounds, alkaline earth metals, rare-earth metals, and mixtures thereof. A reductive dopant layer may be employed as a charge-generating layer to prepare an organic electroluminescent device having two or more light-emitting layers and emitting white light.
In order to form each layer constituting the organic electroluminescent device of the present invention, dry film-forming methods, such as vacuum deposition, sputtering, plasma, ion plating methods, etc., or wet film-forming methods, such as spin coating, dip coating, flow coating methods, etc., can be used.
When using a wet film-forming method, a thin film is formed by dissolving or dispersing the material constituting each layer in suitable solvents, such as ethanol, chloroform, tetrahydrofuran, dioxane, etc. The solvents are not specifically limited as long as the material constituting each layer is soluble or dispersible in the solvents, which do not cause any problems in forming a layer.
Hereinafter, the organic electroluminescent compound of the present invention, the preparation method of the compound, and the luminescent properties of the device comprising the compound will be explained in detail with reference to the following examples:
Example 1: Preparation of compound H-34
Figure PCTKR2014011698-appb-I000074
Preparation of compound 1-2
2-Bromobiphenyl (50.0 g, 214.0 mmol) and tetrahydrofuran (THF) (1.0 L) in a 3 L round-bottom flask (RBF) were cooled to -78 °C and 2.5M n-butyl lithium (103.0 mL, 257.0 mmol) was added thereto. After 2 hrs, (4-bromophenyl)(phenyl)methanon (56.0 g, 214.0 mmol) was added to the flask. After 17 hrs, the mixture was extracted with methylene chloride (MC) and H2O, and the MC layer was dried over MgSO4. The MC layer was concentrated to obtain compound 1-1.
Compound 1-1, hydrochloric acid (100.0 mL), and acetic acid (1.0 L) in a 3 L RBF were stirred under reflux. After 14 hrs, the resulting solid was filtered, the filtered solid was dissolved in chloroform (CHCl3), and applied to column chromatography to obtain compound 1-2 (35.0 g, 42 %).
Preparation of compound 1-3
Compound 1-2 (35.0 g, 89.0 mmol), bis(pinacolato)diborane (27.0 g, 106.0 mmol), bis(triphenylphosphine)palladium(II) dichloride (Pd(PPh3)2Cl2) (3.1 g, 4.45 mmol), potassium acetate (KOAc) (22.0 g, 222.0 mmol), and 1,4-dioxane (445.0 mL) in a 1 L RBF were stirred under reflux. After 3 hrs, the mixture was extracted with dichloromethane (DCM) and H2O, and the DCM layer was dried over MgSO4 and filtered. The resulting solid was dissolved in CHCl3 and applied to column chromatography to obtain compound 1-3 (22.0 g, 56 %).
Preparation of compound 1-4
Compound 1-3 (22.0 g, 50.0 mmol), 2-bromonitrobenzene (12.0 g, 60.0 mmol), tetrakis(triphenylphosphine)palladium(O) (Pd(PPh3)4) (1.7 g, 1.5 mmol), K2CO3 (13.7 g, 99.4 mmol), toluene (100.0 mL), ethanol (EtOH) (25.0 mL), and H2O (25.0 L) in a 500 mL RBF were stirred under reflux. After 5 hrs, the mixture was extracted with DCM and H2O, and the DCM layer was dried over MgSO4 and filtered. The resulting solid was dissolved in CHCl3 and applied to column chromatography to obtain compound 1-4 (15.0 g, 70 %).
Preparation of compound 1-5
Compound 1-4 (15.0 g, 35.0 mmol), triethylphosphite (P(OEt)3) (100.0 mL), and 1,2-dichlorobenzene (1,2-DCB) (50.0 mL) in a 500 mL RBF were stirred under reflux. After 13 hrs, the solvent was distilled, and the residue was dissolved in CHCl3 and applied to column chromatography to obtain compound 1-5 (8.42 g, 59 %).
Preparation of compound 1-6
Compound 1-5 (8.4 g, 21.0 mmol), 1-bromo-3-iodobenzene (8.7 g, 31.0 mmol), CuI (2.0 g, 10.3 mmol), ethylenediamine (1.4 mL, 21.0 mmol), K3PO4 (13.0 g, 62.0 mmol), and toluene (103.0 mL) in a 500 mL RBF were stirred under reflux for 23 hrs. After completing the reaction, the mixture was cooled to room temperature and extracted with DCM and H2O, and the DCM layer was dried over MgSO4. The DCM layer was concentrated under reduced pressure and the resulting solution was applied to column chromatography to obtain compound 1-6 (9.5 g, 94 %).
Preparation of compound 1-7
Compound 1-6 (9.5 g, 19.5 mmol), bis(pinacolato)diborane (6.4 g, 25.0 mmol), Pd(PPh3)2Cl2)(684.0 mg, 0.97 mmol), KOAc (4.8 g, 49.0 mmol), and 1,4-dioxane (196.0 mL) in a 500 mL RBF were stirred under reflux. After 6 hrs, the mixture was extracted with DCM and H2O, and the DCM layer was dried over MgSO4 and filtered. The resulting solid was dissolved in CHCl3 and applied to column chromatography to obtain compound 1-7 (8.0 g, 69 %).
Preparation of compound H-34
Compound 1-7 (8.0 g, 13.0 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (4.2 g, 15.7 mmol), Pd(PPh3)4 (454.0 mg, 0.39 mmol), K2CO3 (3.6 g, 26.0 mmol), toluene (30.0 mL), EtOH (7.0 mL), and H2O (7.0 mL) in a 250 mL RBF were stirred under reflux. After 3 hrs, the mixture was extracted with DCM and H2O, and the DCM layer was dried over MgSO4 and filtered. The resulting solid was dissolved in CHCl3 and applied to column chromatography to obtain compound H-34 (3.95 g, 42 %).
mp 288 °C, UV 290 nm (in toluene), PL 430 nm (in toluene), MS/EIMS 714.28
Example 2: Preparation of compound H-57
Figure PCTKR2014011698-appb-I000075
Preparation of compound 2-1
Compound 1-3 (35.0 g, 78.0 mmol), 2,5-dibromonitrobenzene (26.2 g, 93.0 mmol), Pd(PPh3)4 (3.6 g, 3.1 mmol), Na2CO3 (20.6 g, 195.0 mmol), toluene (400.0 mL), EtOH (50.0 mL), and H2O (100.0 mL) in a 2 L RBF were stirred overnight under 130 °C. The reaction mixture was worked-up with ethyl acetate (EA) and H2O, the moisture was removed with MgSO4, and the residue was distilled under reduced pressure. The crude product was applied to column chromatography with MC:hexane (Hx) to obtain compound 2-1 (30.0 g, 75 %) in a solid form.
Preparation of compound 2-2
Compound 2-1 (30.0 g, 57.8 mmol), P(OEt)3 (200.0 mL) and 1,2-DCB (200.0 mL) in a 1 L RBF were stirred under 150 °C for 2 hrs. The reaction mixture was distilled to obtain solid. The crude product was applied to column chromatography with MC:Hx to obtain compound 2-2 (19.0 g, 68 %) as a white solid.
Preparation of compound 2-3
Compound 2-2 (5.7 g, 47.0 mmol), Pd(PPh3)4 (1.8 g, 1.5 mmol), K2CO3 (13.5 g, 97.0 mmol), toluene (200.0 mL), EtOH (50.0 mL), and H2O (50.0 mL) in a 500 mL RBF were stirred under 120 °C for 2.5 hrs. The reaction mixture was worked-up with EA and H2O, the moisture was removed with MgSO4, and the residue was distilled under reduced pressure. The crude product was applied to column chromatography with MC:Hx to obtain compound 2-3 (16.0 g, 84 %) as a white solid.
Preparation of compound H-57
Compound 2-3 (10.0 g, 20.6 mmol), 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine (9.6 g, 24.8 mmol), palladium(II) acetate (Pd(OAc)2) (232.0 mg, 1.0 mmol), 2-dicyclohexylphosphino-2’,-6’-dimethoxybiphenyl (s-phos) (850.0 mg, 2.0 mmol), sodium tert-butoxide (NaOtBu) (5.0 g, 51.6 mmol), and o-xylene (200.0 mL) in a 500 mL RBF were stirred under 180 °C for 2 hrs. The reaction mixture was worked-up with EA and H2O, the moisture was removed with MgSO4, and the residue was distilled under reduced pressure. The crude product was applied to column chromatography with MC:Hx to obtain compound H-57 (7.3 g, 45 %) as a white solid.
mp 312 °C, UV 344 nm (in toluene), PL 427 nm (in toluene), MS/EIMS 791
Example 3: Preparation of compound H-90
Figure PCTKR2014011698-appb-I000076
Preparation of compound 3-1
9-fluorenone (20.0 g, 111.0 mmol) was dissolved in THF (554.0 mL) in a flask and phenylmagnesium bromide (36.9 mL) was slowly added thereto at 0 °C. The mixture was stirred at room temperature for 24 hrs. After completing the reaction, the organic layer was extracted with EA and dried by removing the remaining moisture with MgSO4. The layer was separated by column chromatography to obtain compound 3-1 (20.0 g, 70 %).
Preparation of compound 3-2
2-bromo-9H-carbazole (20.0 g, 81.2 mmol), phenylboronic acid (11.9 g, 97.5 mmol), Pd(PPh3)4 (4.7 g, 4.06 mmol), 2M K2CO3 (121.0 mL), toluene (250.0 mL), and EtOH (121.0 mL) in a flask were stirred under reflux for 5 hrs. After completing the reaction, the organic layer was extracted with EA and dried by removing the remaining moisture with MgSO4. The layer was separated by column chromatography to obtain compound 3-2 (17.0 g, 86 %).
Preparation of compound 3-3
Compound 3-2 (17.0 g, 70.0 mmol), 1-iodo-3-bromobenzene (17.7 mL, 140.0 mmol), CuI (6.6 g, 35.0 mmol), K3PO4 (44.5 g, 210.0 mmol), ethylenediamine (EDA) (4.7 mL, 70.0 mmol), and toluene (350.0 mL) were dissolved in a flask and refluxed at 120 °C for 5 hrs. After completing the reaction, the organic layer was extracted with EA and dried by removing the remaining moisture with MgSO4. The layer was separated by column chromatography to obtain compound 3-3 (27.0 g, 97 %).
Preparation of compound 3-4
Compound 3-3 (27.0 g, 67.7 mmol) and compound 3-1 (17.5 g, 67.7 mmol) were dissolved in DCM (522.0 mL) in a flask. After adding P2O5 (0.04 mL, 1.35 mmol) in methanesulfonic acid (MSA), the mixture was stirred for 10 minutes. After completing the reaction, NaHCO3 (aq) was added and the organic layer was extracted with DCM. The organic layer was dried by removing the remaining moisture with MgSO4 and separated by column chromatography to obtain compound 3-4 (40.0 g, 95 %).
Preparation of compound 3-5
Compound 3-4 (15.0 g, 23.4 mmol), 2-(3-bromophenyl)-4,6-diphenyl-1,3,5-triazine (6.6 g, 25.74 mmol), palladium(II) chloride (PdCl2(PPh3)4) (659.0 mg, 0.94 mmol), and KOAc (10.0 g, 102.9 mmol) were dissolved in 1,4-dioxane (156.0 mL) in a flask. The mixture was stirred at 120 °C for 4 hrs. After completing the reaction, the organic layer was extracted with EA and dried by removing the remaining moisture with MgSO4. The organic layer was separated via column chromatography to obtain compound 3-5 (10.6 g, 66 %).
Preparation of compound H-90
Compound 3-5 (10.6 g, 15.4 mmol), 2-chloro-4,6-diphenyl-1,3,5-triazine (3.8 g, 14.0 mmol), Pd(PPh3)4 (820.0 mg, 0.77 mmol), 2M K2CO3 (60.0 mL), EtOH (60.0 mL), and toluene (180.0 mL) in a flask were stirred at 120 °C for 5 hrs. After completing the reaction, the organic layer was extracted with EA and dried by removing the remaining moisture with MgSO4. By recrystallizing with EA and MeOH, compound H-90 (4.0 g, 32.7 %) was obtained.
mp 256 °C, UV 324 nm (in toluene), PL 439 nm (in toluene), MS/EIMS 790.95
Device Example 1: Production of an OLED device by using the organic
electroluminescent compound according to the present invention
An organic light-emitting diode (OLED) device using the organic electroluminescent compound of the present invention was produced as follows: A transparent electrode indium tin oxide (ITO) thin film (15 Ω/sq) on a glass substrate for an OLED device (Samsung Corning, Republic of Korea) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol, and distilled water, sequentially, and was then stored in isopropanol. Next, the ITO substrate was mounted on a substrate holder of a vacuum vapor depositing apparatus. N1,N1’-([1,1’-biphenyl]-4,4’-diyl)bis(N1-(naphthalene-1-yl)-N4,N4-diphenylbenzene-1,4-diamine) was introduced into a cell of the vacuum vapor depositing apparatus, and the pressure in the chamber of the apparatus was then controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the introduced material, thereby forming a hole injection layer having a thickness of 60 nm on the ITO substrate. Next, N,N’-di(4-biphenyl)-N,N’-di(4-biphenyl)-4,4’-diaminobiphenyl was introduced into another cell of the vacuum vapor depositing apparatus, and an electric current was applied to the cell to evaporate the introduced material, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Compound H-34 was introduced as a host into one cell of the vacuum vapor depositing apparatus, and compound D-1 as a dopant was introduced into another cell. The two materials were evaporated at different rates and the dopant was deposited in a doping amount of 15 wt%, based on the total weight of the host and dopant, to form a light-emitting layer having a thickness of 30 nm on the hole transport layer. 2-(4-(9,10-di(naphthalene-2-yl)anthracene-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidiazole was then introduced into one cell, and lithium quinolate was introduced into another cell. The two materials were evaporated at the same rates and were respectively deposited in a doping amount of 50 wt% to form an electron transport layer having a thickness of 30 nm on the light-emitting layer. Next, after depositing lithium quinolate as an electron injection layer having a thickness of 2 nm on the electron transport layer, an Al cathode having a thickness of 150 nm was deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED device was produced. All the materials used for producing the OLED device were purified by vacuum sublimation at 10-6 torr prior to use.
The produced OLED device showed green emission having a current density of 3.32 mA/cm2 and a luminance of 1310 cd/m2 at 2.5 V.
Device Example 2: Production of an OLED device by using the organic
electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except that compound H-57 was used as a host in a light-emitting material.
The produced OLED device showed green emission having a current density of 7.26 mA/cm2 and a luminance of 2840 cd/m2 at 2.6 V.
Device Example 3: Production of an OLED device by using the organic
electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except that compound H-90 was used as a host in a light-emitting material.
The produced OLED device showed green emission having a current density of 9.40 mA/cm2 and a luminance of 3910 cd/m2 at 2.7 V.
Device Example 4: Production of an OLED device by using the organic
electroluminescent compound according to the present invention
An OLED device was produced in the same manner as in Device Example 1, except that compound H-15 was used as a host in a light-emitting material.
The produced OLED device showed green emission having a current density of 2.45 mA/cm2 and a luminance of 890 cd/m2 at 2.6 V.
Comparative Example 1: Production of an OLED device by using
conventional light-emitting materials
An OLED device was produced in the same manner as in Device Example 1, except that Compound 1 was used as a host and compound D-86 was used as a dopant in a light-emitting material.
The produced OLED device showed green emission having a current density of 5.20 mA/cm2 and a luminance of 1020 cd/m2 at 4.3 V.
Figure PCTKR2014011698-appb-I000077
The organic electroluminescent compound of the present invention provides more excellent luminescent property than conventional light-emitting materials. Furthermore, the organic electroluminescent device using the organic electroluminescent compound of the present invention as a light-emitting host material provides good luminescent property and reduces the driving voltage, thereby enhancing power efficiency and improving consumption power.

Claims (6)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2014011698-appb-I000078
    wherein
    A1 represents a substituted or unsubstituted 5- to 30-membered heteroaryl group;
    L1 represents a single bond, a substituted or unsubstituted (C6-C30)arylene group, or a substituted or unsubstituted 5- to 30-membered heteroarylene group;
    R1 represents a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkylamino group, a substituted or unsubstituted (C6-C30)arylamino group, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino group;
    R2 represents hydrogen, deuterium, a halogen, a cyano group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C1-C30)alkylsilyl group, a substituted or unsubstituted (C6-C30)arylsilyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl group, a substituted or unsubstituted (C1-C30)alkylamino group, a substituted or unsubstituted (C6-C30)arylamino group, a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino group, or the following formula 2:
    Figure PCTKR2014011698-appb-I000079
    R2 forms a benzocarbazole by fusion to a carbazole ring;
    R3 represents hydrogen, deuterium, a halogen, a cyano group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C1-C30)alkylsilyl group, a substituted or unsubstituted (C6-C30)arylsilyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl group, a substituted or unsubstituted (C1-C30)alkylamino group, a substituted or unsubstituted (C6-C30)arylamino group, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino group;
    X represents O, S, CR11R12, NR13, or SiR13R14;
    R4, R5 and R6 each independently represent hydrogen, deuterium, a halogen, a cyano group, a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, a substituted or unsubstituted 5- to 30-membered heteroaryl group, a substituted or unsubstituted (C3-C30)cycloalkyl group, a substituted or unsubstituted (C1-C30)alkoxy group, a substituted or unsubstituted (C1-C30)alkylsilyl group, a substituted or unsubstituted (C6-C30)arylsilyl group, a substituted or unsubstituted (C6-C30)aryl(C1-C30)alkylsilyl group, a substituted or unsubstituted (C1-C30)alkylamino group, a substituted or unsubstituted (C6-C30)arylamino group, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
    R11 to R14 each independently represent a substituted or unsubstituted (C1-C30)alkyl group, a substituted or unsubstituted (C6-C30)aryl group, or a substituted or unsubstituted 5- to 30-membered heteroaryl group; or are linked to an adjacent substituent(s) to form a mono- or polycyclic (C3-C30) alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen and sulfur;
    a, c, d and e each independently represent an integer of 1 to 4; where a, c, d or e is an integer of 2 or more, each R2, R4, R5 or R6 is the same or different;
    b represents an integer of 1 to 3; where b is an integer of 2 or more, each R3 is the same or different;
    n represents an integer of 0 or 1;
    m represents an integer of 1 or 2; and
    the heteroaryl(ene) group contains at least one hetero atom selected from B, N, O, S, P(=O), Si and P.
  2. The organic electroluminescent compound according to claim 1, wherein the compound of formula 1 is represented by the following formula 3, 4, or 5:
    Figure PCTKR2014011698-appb-I000080
    wherein
    A1, L1, R1 to R5, a, b, c, d, m and n are as defined in claim 1.
  3. The organic electroluminescent compound according to claim 1, wherein A1 represents pyridine, pyrimidine, triazine, pyrazine, quinoline, quinazoline, quinoxaline, or naphthyridine; L1 represents a single bond or a (C6-C20)arylene group; R1 represents a (C1-C20)alkyl group, a (C6-C20)aryl group, or a 5- to 20-membered heteroaryl group; R2 represents hydrogen, deuterium, a (C6-C20)aryl group, a 5- to 20-membered heteroaryl group, a (C6-C20)arylamino group, or formula 2, or forms a benzocarbazole by fusion to a carbazole ring; R3, R4, R5 and R6 each independently represent hydrogen or a (C1-C20)alkyl group; and R11 to R14 each independently represent a (C1-C20)alkyl group, a (C6-C20)aryl group, or a 5- to 20-membered heteroaryl group.
  4. The organic electroluminescent compound according to claim 1, wherein the substituents of the substituted (C1-C30)alkyl group, the substituted (C1-C30)alkoxy group, the substituted (C3-C30)cycloalkyl group, the substituted (C6-C30)aryl(ene) group, the substituted 5- to 30-membered heteroaryl(ene) group, and the substituted (C6-C30)aryl(C1-C30)alky group in A1, L1, R1 to R6 and R11 to R14 of formula 1 are each independently at least one selected from the group consisting of deuterium; a halogen; a cyano group; a carboxyl group; a nitro group; a hydroxyl group; a (C1-C30)alkyl group; a halo(C1-C30)alkyl group; a (C2-C30)alkenyl group; a (C2-C30)alkynyl group; a (C1-C30)alkoxy group; a (C1-C30)alkylthio group; a (C3-C30)cycloalkyl group; a (C3-C30)cycloalkenyl group; a 3- to 7-membered heterocycloalkyl group; a (C6-C30)aryloxy group; a (C6-C30)arylthio group; a 3- to 30-membered heteroaryl group unsubstituted or substituted with a (C6-C30)aryl group; a (C6-C30)aryl group unsubstituted or substituted with a 3- to 30-membered heteroaryl group; a tri(C1-C30)alkylsilyl group; a tri(C6-C30)arylsilyl group; a di(C1-C30)alkyl(C6-C30)arylsilyl group; a (C1-C30)alkyldi(C6-C30)arylsilyl group; an amino group; a mono- or di(C1-C30)alkylamino group; a mono- or di(C6-C30)arylamino group; a (C1-C30)alkyl(C6-C30)arylamino group; a (C1-C30)alkylcarbonyl group; a (C1-C30)alkoxycarbonyl group; a (C6-C30)arylcarbonyl group; a di(C6-C30)arylboronyl group; a di(C1-C30)alkylboronyl group; a (C1-C30)alkyl(C6-C30)arylboronyl group; a (C6-C30)aryl(C1-C30)alkyl group; and a (C1-C30)alkyl(C6-C30)aryl group.
  5. The organic electroluminescent compound according to claim 1, wherein the compound of formula 1 is selected from the group consisting of the following compounds:
    Figure PCTKR2014011698-appb-I000081
    Figure PCTKR2014011698-appb-I000082
    Figure PCTKR2014011698-appb-I000084
    Figure PCTKR2014011698-appb-I000085
    Figure PCTKR2014011698-appb-I000086
    Figure PCTKR2014011698-appb-I000087
    Figure PCTKR2014011698-appb-I000088
    Figure PCTKR2014011698-appb-I000089
    Figure PCTKR2014011698-appb-I000090
    Figure PCTKR2014011698-appb-I000091
    Figure PCTKR2014011698-appb-I000092
    Figure PCTKR2014011698-appb-I000093
    Figure PCTKR2014011698-appb-I000094
    Figure PCTKR2014011698-appb-I000095
    Figure PCTKR2014011698-appb-I000096
    Figure PCTKR2014011698-appb-I000097
    Figure PCTKR2014011698-appb-I000098
    Figure PCTKR2014011698-appb-I000099
    Figure PCTKR2014011698-appb-I000100
    Figure PCTKR2014011698-appb-I000101
    Figure PCTKR2014011698-appb-I000102
  6. An organic electroluminescent device comprising the organic electroluminescent compound according to claim 1.
PCT/KR2014/011698 2013-12-04 2014-12-02 Novel organic electroluminescent compounds and organic electroluminescent device comprising the same Ceased WO2015084021A1 (en)

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