WO2015093814A1 - Organic electroluminescent compounds and organic electroluminescent device comprising the same - Google Patents

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

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Publication number
WO2015093814A1
WO2015093814A1 PCT/KR2014/012388 KR2014012388W WO2015093814A1 WO 2015093814 A1 WO2015093814 A1 WO 2015093814A1 KR 2014012388 W KR2014012388 W KR 2014012388W WO 2015093814 A1 WO2015093814 A1 WO 2015093814A1
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substituted
unsubstituted
membered
alkyl
organic electroluminescent
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PCT/KR2014/012388
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French (fr)
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Mi-Ja Lee
Nam-Kyun Kim
Chi-Sik Kim
Young-Jun Cho
Kyung-Joo Lee
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Rohm And Haas Electronic Materials Korea Ltd.
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Publication of WO2015093814A1 publication Critical patent/WO2015093814A1/en

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • 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
    • C07D495/00—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms
    • C07D495/02—Heterocyclic compounds containing in the condensed system at least one hetero ring having sulfur atoms as the only ring hetero atoms in which the condensed system contains two hetero rings
    • C07D495/04—Ortho-condensed systems
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
    • H05B33/00—Electroluminescent light sources
    • H05B33/12—Light sources with substantially two-dimensional radiating surfaces
    • H05B33/20—Light sources with substantially two-dimensional radiating surfaces characterised by the chemical or physical composition or the arrangement of the material in which the electroluminescent material is embedded
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/654—Aromatic compounds comprising a hetero atom comprising only nitrogen as heteroatom
    • 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
    • H10K85/649—Aromatic compounds comprising a hetero atom
    • H10K85/657—Polycyclic condensed heteroaromatic hydrocarbons
    • 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
    • H10K85/649—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
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K2101/00—Properties of the organic materials covered by group H10K85/00
    • H10K2101/10—Triplet emission
    • 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
    • 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 disclosure relates to organic electroluminescent compounds and organic electroluminescent device comprising the same.
  • An electroluminescent (EL) device is a self-light-emitting device which has advantages in that it provides 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 to form a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
  • the most important factor determining luminous efficiency in the organic EL device is light-emitting materials.
  • fluorescent materials have been widely used as light-emitting material.
  • phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, phosphorescent light-emitting materials have been widely researched.
  • Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C-3’)iridium(acetylacetonate) ((acac)Ir(btp) 2 ), tris(2-phenylpyridine)iridium (Ir(ppy) 3 ) and bis(4,6-difluorophenylpyridinato-N,C2)picolinato iridium (Firpic) as red-, green- and blue-emitting materials, respectively.
  • CBP 4,4’-N,N’-dicarbazol-biphenyl
  • BCP bathocuproine
  • BAlq aluminum(III) bis(2-methyl-8-quinolinate)(4-phenylphenolate)
  • Korean Patent Application Laid-open No. 10-2013-0073700 discloses a compound having a backbone fused with two carbazoles, as a compound for an organic EL device. However, it fails to disclose an organic electroluminescent compound having a backbone fused with carbazole and dibenzothiophene.
  • the objective of the present disclosure is to provide (1) an organic electroluminescent compound, which can produce an organic electroluminescent device having long lifespan, low driving voltage, and excellent current and power efficiencies, and (2) an organic electroluminescent device comprising the organic electroluminescent compound.
  • A represents the following formula 2a or 2b:
  • L 1 represents a single bond, a substituted or unsubstituted (3- to 30-membered) heteroarylene, or a substituted or unsubstituted (C6-C30)arylene;
  • Ring E represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
  • X 1 to X 3 each independently, represent -N- or -CR 6 -;
  • R 1 to R 6 each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyl
  • a and b each independently, represent an integer of 1 to 4; where a or b represents an integer of 2 or more, each of R 1 or R 2 may be the same or different;
  • c, d and e each independently, represent an integer of 1 to 2; and where c, d or e represents 2, each of R 3 , R 4 or R 5 may be the same or different.
  • the organic electroluminescent compound of the present disclosure can provide an organic electroluminescent device showing long lifespan, low driving voltage, and excellence in current and power efficiencies.
  • the present disclosure provides the organic electroluminescent compound of formula 1 above, an organic electroluminescent material comprising the organic electroluminescent compound, and an organic electroluminescent device comprising the organic electroluminescent compound.
  • alkyl includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc.
  • Alkenyl includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc.
  • Alkynyl includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc.
  • Cycloalkyl includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc.
  • aryl(ene) indicates a monocyclic or fused ring derived from an aromatic hydrocarbon, and includes spiro compounds in which two rings are linked at one atom.
  • the examples of the aryl include phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, spirobifluorenyl, 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.
  • Ring E represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; and preferably, a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered)heteroaryl; and more preferably, a substituted or unsubstituted benzene ring, or a substituted or unsubstituted pyridine ring.
  • ring E may represent a benzene ring.
  • L 1 represents a single bond, a substituted or unsubstituted (3- to 30-membered)heteroarylene, or a substituted or unsubstituted (C6-C30)arylene; and preferably, a single bond, a substituted or unsubstituted (5- to 21-membered)heteroarylene, or a substituted or unsubstituted (C6-C21)arylene; and more preferably, a single bond, or a substituted or unsubstituted (C6-C18)arylene.
  • L 1 may represent a single bond, or phenyl.
  • X 1 to X 3 each independently, represent -N- or -CR 6 -; and preferably, zero to two of X 1 to X 3 represents -N-, and the remainder(s) represents -CR 6 -.
  • A represents formula 2a
  • X 1 to X 3 may represent -CR 6 -; or X 1 may represent -N-, and X 2 and X 3 may represent -CR 6 -; or X 1 and X 3 may represent -N-, and X 2 may represent -CR 6 -.
  • one of X 1 to X 3 may represent -N-, and the reminders may represent -CR 6 -, specifically; and more specifically, one of X 1 and X 2 may represent -N-, and the reminders may represent -CR 6 -.
  • R 1 to R 6 each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyl
  • R 1 and R 2 each independently, represent hydrogen, a halogen, a substituted or unsubstituted (C1-C10)alkyl, a substituted or unsubstituted (C5-C18)cycloalkyl, a substituted or unsubstituted (C6-C18)aryl, a substituted or unsubstituted tri(C6-C18)arylsilyl, or a substituted or unsubstituted di(C6-C18)arylamino, and may be fused with an adjacent substituent(s) to form a substituted or unsubstituted (5- to 18-membered) monocyclic aromatic ring;
  • R 3 represents hydrogen, a substituted or unsubstituted (C6-C18)aryl, or a substituted or unsubstituted (5- to 18-membered)heteroaryl;
  • R 4 and R 5 each independently, represent hydrogen, or a substituted or unsubstitute
  • R 1 and R 2 each independently, may represent hydrogen, a halogen, a (C1-C4)alkyl, cyclohexyl, phenyl, triphenylsilyl, or diphenylamino, and may be fused with an adjacent substituent(s) to form a benzene ring;
  • R 3 may represent hydrogen, phenyl, biphenyl, naphthyl, dibenzothiophenyl, dibenzofuranyl, 9-phenyl-9H-carbazolyl, or 9,9-dimethyl-9H-fluorenyl;
  • R 4 and R 5 each independently, may represent hydrogen or phenyl; and R 6 may represent hydrogen.
  • a and b each independently, represent an integer of 1 to 4; and preferably, 1 or 2; and more preferably 1; and where a or b represents 2 or more, each of R 1 or R 2 may be the same or different.
  • c, d and e each independently, represent an integer of 1 or 2; and preferably, c represents 1 or 2; d and e represent 1; and where c, d or e represents 2, each of R 3 , R 4 or R 5 may be the same or different.
  • ring E represents a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered)heteroaryl;
  • L 1 represents a single bond, a substituted or unsubstituted (5- to 21-membered)heteroarylene, or a substituted or unsubstituted (C6-C21)arylene;
  • zero to two of X 1 to X 3 represents -N-, and the remainder(s) represents -CR 6 -;
  • R 1 to R 6 each independently, represent hydrogen, a halogen, a cyano, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C5-C21)cycloalkyl, a substituted or unsubstituted (C6-C21)aryl, a substituted or unsubstituted (5- to 21
  • the compound of formula 1 may be represented by the following formula 3:
  • L 1 , X 1 , X 3 , R 1 to R 5 , and a to e are as defined in formula 1.
  • X 1 to X 3 each independently, represent -N- or -CH-;
  • R 3 represents hydrogen, a substituted or unsubstituted (C6-C18)aryl, or a substituted or unsubstituted (5- to 18-membered)heteroaryl;
  • c represents an integer of 1 or 2. Where c represents 2, each of R 3 may be the same or different.
  • the compound of formula 1 may be represented by the following formula 4:
  • R 3 represents a substituted or unsubstituted (C6-C18)aryl, or a substituted or unsubstituted (5- to 18-membered)heteroaryl; and c represents 1.
  • organic electroluminescent compound of the present disclosure includes the following, but is not limited thereto:
  • organic electroluminescent compounds of the present disclosure can be prepared by a synthetic method known to one skilled in the art. For example, they can be prepared according to the following reaction scheme 1.
  • the present disclosure provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
  • the material may consist of the organic electroluminescent compound of the present disclosure. Otherwise, the material may further comprise a conventional compound(s) which has been comprised for an organic electroluminescent material, in addition to the compound of the present disclosure.
  • the organic electroluminescent device of the present disclosure may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes.
  • the organic layer may comprise at least one compound of formula 1.
  • the organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, an electron buffer layer, and an electron blocking layer.
  • the organic electroluminescent compound of the present disclosure may be comprised in the light-emitting layer.
  • the organic electroluminescent compound of the present disclosure may be comprised as a host material.
  • the light-emitting layer may further comprise at least one dopant, and if necessary, a compound other than the organic electroluminescent compound of formula 1 may be comprised additionally as a second host material.
  • the second host material may be from any of the known phosphorescent host materials. Specifically, the material selected from the group consisting of the compounds of formulae 5 to 9 below is preferable as the second host material in view of luminous 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, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5- to 30-membered)heteroaryl, or R 25 R 26 R 27 Si-;
  • R 25 to R 27 each independently, represent a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl;
  • L 4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene;
  • M represents a substituted or unsubstituted (C6-C30)aryl, or
  • the second host material includes the following:
  • TPS represents triphenylsilyl
  • the dopant is preferably at least one phosphorescent dopant.
  • the phosphorescent dopant material for the organic electroluminescent device of the present disclosure is not limited, but may be preferably selected from metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) or platinum (Pt), more preferably selected from ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) or platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
  • the dopant for the organic electroluminescent device of the present disclosure includes compounds represented by the following formulae 10 to 12.
  • L is selected from the following structures:
  • R 100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl;
  • R 101 to R 109 and R 111 to R 123 each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen, a substituted or unsubstituted (C3-C30)cycloalkyl, a cyano, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (C1-C30)alkoxy;
  • R 106 to R 109 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a substituted or unsubstituted fluorene, a substituted or unsubstituted
  • the dopant material includes the following:
  • a material for preparing an organic electroluminescent device comprises the compound of the present disclosure.
  • the material may be a material for preparing a light-emitting layer or an electron transport layer of an organic electroluminescent device.
  • the compound of the present disclosure may be comprised as a host material.
  • the material may further comprise a second host material, in which the weight ratio of the first host material to the second host material may be in the range of 1:99 to 99:1.
  • the compound of the present disclosure may be comprised as an electron transport material.
  • the material may be in a form of mixture or composition.
  • the organic electroluminescent device of the present disclosure may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes, wherein the organic layer may comprise the material for the organic electroluminescent device of the present disclosure.
  • the organic electroluminescent device of the present disclosure may further comprise, in addition to the compound of formula 1, 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 compound 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 the d-transition elements of the Periodic Table, or at least one complex compound comprising the metal.
  • the organic layer may further comprise one or more additional light-emitting layers and a charge generating layer.
  • the organic electroluminescent device of the present disclosure 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 known in the field, besides the compound of the present disclosure. If necessary, it may further comprise a yellow light-emitting layer or an orange light-emitting layer.
  • a surface layer may be placed on an inner surface(s) of one or both electrode(s), selected from a chalcogenide layer, a metal halide layer and a metal oxide layer.
  • a chalcogenide (includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer
  • a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer.
  • 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 an electroluminescent 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 the electroluminescent medium.
  • the oxidative dopant includes various Lewis acids and acceptor compounds
  • 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 electroluminescent device having two or more light-emitting layers and emitting white light.
  • dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as ink jet printing, nozzle printing, slot coating, spin coating, dip coating, and flow coating methods can be used.
  • a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc.
  • the solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
  • OLED comprising the organic electroluminescent compounds of the present disclosure was produced as follows.
  • a transparent electrode indium tin oxide (ITO) thin film (15 ⁇ /sq) on a glass substrate for an organic light-emitting diode (OLED) (Samsung Corning) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol, and distilled water, sequentially, and was then stored in isopropanol.
  • the ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus.
  • N 1 ,N 1’ -([1,1’-biphenyl]-4,4’-diyl)bis(N 1 -(naphthalen-1-yl)-N 4 ,N 4 -diphenylbenzene-1,4-diamine) was introduced into a cell of said vacuum vapor depositing apparatus, and the pressure in the chamber of said apparatus was then controlled to 10 -6 torr. Thereafter, an electric current was applied to the cell to evaporate the above 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 then introduced into another cell of said vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer.
  • compound H-15 of the present disclosure was introduced into one cell of the vacuum vapor depositing apparatus, as a host, and compound D-87 was introduced into another cell as a dopant.
  • the two materials were evaporated at different rates so that the dopant was deposited in a doping amount of 4 wt% based on the total amount 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(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[ d ]imidazole was then introduced into one cell, and lithium quinolate was introduced into another cell.
  • the two materials were evaporated at the same rate so that they 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 then deposited by another vacuum vapor deposition apparatus on the electron injection layer.
  • All the materials used for producing the OLED were those purified by vacuum sublimation at 10 -6 torr.
  • the produced OLED showed red emission having a luminance of 920 cd/m 2 and a current density of 7.9 mA/cm 2 at a driving voltage of 3.6 V.
  • the time period for the luminance to decrease to 90% at 5000 nits was 70 hours or more.
  • OLED was produced in the same manner as in Device Example 1, except for using the compound shown below as a host and compound D-87 as a dopant to form a light-emitting layer.
  • the produced OLED showed red emission having a luminance of 900 cd/m 2 and a current density of 8.9 mA/cm 2 at a driving voltage of 3.6 V.
  • the time period for the luminance to decrease to 90% at 5000 nits was 40 hours or more.
  • an organic electroluminescent device can show long lifespan and excellent luminous and power efficiencies by using the organic electroluminescent compound of the present disclosure.

Abstract

The present invention relates to an organic electroluminescent compound and an organic electroluminescent device comprising the same. Using the organic electroluminescent compound according to the present invention, an organic electroluminescent device can have long lifespan and low driving voltage to enhance current and power efficiencies.

Description

ORGANIC ELECTROLUMINESCENT COMPOUNDS AND ORGANIC ELECTROLUMINESCENT DEVICE COMPRISING THE SAME
The present disclosure relates to organic electroluminescent compounds and organic electroluminescent device comprising the same.
An electroluminescent (EL) device is a self-light-emitting device which has advantages in that it provides 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 to form a light-emitting layer [Appl. Phys. Lett. 51, 913, 1987].
The most important factor determining luminous efficiency in the organic EL device is light-emitting materials. Until now, fluorescent materials have been widely used as light-emitting material. However, in view of electroluminescent mechanisms, since phosphorescent materials theoretically enhance luminous efficiency by four (4) times compared to fluorescent materials, phosphorescent light-emitting materials have been widely researched. Iridium(III) complexes have been widely known as phosphorescent materials, including bis(2-(2’-benzothienyl)-pyridinato-N,C-3’)iridium(acetylacetonate) ((acac)Ir(btp)2), tris(2-phenylpyridine)iridium (Ir(ppy)3) and bis(4,6-difluorophenylpyridinato-N,C2)picolinato iridium (Firpic) as red-, green- and blue-emitting materials, respectively.
At present, 4,4’-N,N’-dicarbazol-biphenyl (CBP) is the most widely known host material for phosphorescent materials. Recently, Pioneer (Japan) et al., developed a high performance organic EL device using bathocuproine (BCP) and aluminum(III) bis(2-methyl-8-quinolinate)(4-phenylphenolate) (BAlq), etc., as host materials, which were known as hole blocking materials.
Although these materials provide good luminous characteristics, they have the following disadvantages: (1) Due to their low glass transition temperature and poor thermal stability, their degradation may occur during a high-temperature deposition process in a vacuum. (2) The power efficiency of the organic EL device is given by [(π/voltage) × current efficiency], and the power efficiency is inversely proportional to the voltage. Although the organic EL device comprising phosphorescent host materials provides higher current efficiency (cd/A) than one comprising fluorescent materials, a significantly high driving voltage is necessary. Thus, there is no merit in terms of power efficiency (lm/W). (3) Furthermore, the operational lifespan of the organic EL device is short, and luminous efficiency is still necessary to improve.
Korean Patent Application Laid-open No. 10-2013-0073700 discloses a compound having a backbone fused with two carbazoles, as a compound for an organic EL device. However, it fails to disclose an organic electroluminescent compound having a backbone fused with carbazole and dibenzothiophene.
The objective of the present disclosure is to provide (1) an organic electroluminescent compound, which can produce an organic electroluminescent device having long lifespan, low driving voltage, and excellent current and power efficiencies, and (2) an organic electroluminescent device comprising the organic electroluminescent compound.
The present inventors found that the above objective can be achieved by an organic electroluminescent compound represented by the following formula 1:
Figure PCTKR2014012388-appb-I000001
wherein
A represents the following formula 2a or 2b:
Figure PCTKR2014012388-appb-I000002
Figure PCTKR2014012388-appb-I000003
* represents a bonding site;
L1 represents a single bond, a substituted or unsubstituted (3- to 30-membered) heteroarylene, or a substituted or unsubstituted (C6-C30)arylene;
Ring E represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
X1 to X3, each independently, represent -N- or -CR6-;
R1 to R6, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di-(C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or R1, R2 and R6, each independently, may be fused with an adjacent substituent(s) to form a substituted or unsubstituted (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
the heteroaryl(ene) and heterocycloalkyl, each independently, contain at least one hetero atom selected from B, N, O, S, P(=O), Si and P;
a and b, each independently, represent an integer of 1 to 4; where a or b represents an integer of 2 or more, each of R1 or R2 may be the same or different;
c, d and e, each independently, represent an integer of 1 to 2; and where c, d or e represents 2, each of R3, R4 or R5 may be the same or different.
The organic electroluminescent compound of the present disclosure can provide an organic electroluminescent device showing long lifespan, low driving voltage, and excellence in current and power efficiencies.
Hereinafter, the present disclosure 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 disclosure provides the organic electroluminescent compound of formula 1 above, an organic electroluminescent material comprising the organic electroluminescent compound, and an organic electroluminescent device comprising the organic electroluminescent compound.
The details of the organic electroluminescent compound of formula 1 are as follows.
Herein, “alkyl” includes methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, etc. “Alkenyl” includes vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 2-methylbut-2-enyl, etc. “Alkynyl” includes ethynyl, 1-propynyl, 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methylpent-2-ynyl, etc. “Cycloalkyl” includes cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, etc. “(3- to 7-membered)heterocycloalkyl” indicates a cycloalkyl having 3 to 7 ring backbone atoms including at least one hetero atom selected from B, N, O, S, P(=O), Si, and P, preferably O, S, and N, and includes tetrahydrofuran, pyrrolidine, thiolan, tetrahydropyran, etc. Furthermore, “aryl(ene)” indicates a monocyclic or fused ring derived from an aromatic hydrocarbon, and includes spiro compounds in which two rings are linked at one atom. The examples of the aryl include phenyl, biphenyl, terphenyl, naphthyl, binaphthyl, phenylnaphthyl, naphthylphenyl, fluorenyl, phenylfluorenyl, benzofluorenyl, dibenzofluorenyl, phenanthrenyl, phenylphenanthrenyl, anthracenyl, indenyl, triphenylenyl, pyrenyl, tetracenyl, perylenyl, chrysenyl, naphthacenyl, fluoranthenyl, spirobifluorenyl, etc. “(3- to 30-membered)heteroaryl(ene)” indicates an aryl group having 3 to 30 ring backbone atoms including at least one, preferably 1 to 4, hetero atom selected from the group consisting of B, N, O, S, P(=O), Si, and P; may be a monocyclic ring, or a fused ring condensed with at least one benzene ring; 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 such as 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 such as benzofuranyl, benzothiophenyl, isobenzofuranyl, dibenzofuranyl, dibenzothiophenyl, benzimidazolyl, benzothiazolyl, benzoisothiazolyl, benzoisoxazolyl, benzoxazolyl, isoindolyl, indolyl, indazolyl, benzothiadiazolyl, quinolyl, isoquinolyl, cinnolinyl, quinazolinyl, quinoxalinyl, carbazolyl, phenoxazinyl, phenanthridinyl, benzodioxolyl, dihydroacridinyl, etc. Furthermore, “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. The substituents of the substituted (C1-C30)alkyl, the substituted (C3-C30)cycloalkyl, the substituted (C3-C30)cycloalkenyl, the substituted (3- to 7-membered)heterocycloalkyl, the substituted (C6-C30)aryl(ene), the substituted (3- to 30-membered)heteroaryl(ene), the substituted (C6-C30)arylamino and the substituted (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring in L1 and R1 to R6, each independently, are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a (C1-C30)alkyl, a halo(C1-C30)alkyl, a (C2-C30)alkenyl, a (C2-C30)alkynyl, a (C1-C30)alkoxy, a (C1-C30)alkylthio, a (C3-C30)cycloalkyl, a (C3-C30)cycloalkenyl, a (3- to 7-membered)heterocycloalkyl, a (C6-C30)aryloxy, a (C6-C30)arylthio, a (3- to 30-membered)heteroaryl unsubstituted or substituted with a (C6-C30)aryl, a (C6-C30)aryl unsubstituted or substituted with a (3- to 30-membered)heteroaryl, a tri(C1-C30)alkylsilyl, a tri(C6-C30)arylsilyl, a di(C1-C30)alkyl(C6-C30)arylsilyl, a (C1-C30)alkyldi(C6-C30)arylsilyl, an amino, a mono- or di-(C1-C30)alkylamino, a mono- or di-(C6-C30)arylamino, a (C1-C30)alkyl(C6-C30)arylamino, a (C1-C30)alkylcarbonyl, a (C1-C30)alkoxycarbonyl, a (C6-C30)arylcarbonyl, a di(C6-C30)arylboronyl, a di(C1-C30)alkylboronyl, a (C1-C30)alkyl(C6-C30)arylboronyl, a (C6-C30)aryl(C1-C30)alkyl and a (C1-C30)alkyl(C6-C30)aryl; and preferably, each independently, are at least one selected from the group consisting of a cyano, a halogen, a (C1-C10)alkyl, a (C3-C12)cycloalkyl, a (C5-C18)aryl, a (5- to 18-membered)heteroaryl, a tri(C6-C30)arylsilyl, a di(C6-C12)arylamino, and a (C1-C10)alkyl(C5-C18)aryl.
Ring E represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl; and preferably, a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered)heteroaryl; and more preferably, a substituted or unsubstituted benzene ring, or a substituted or unsubstituted pyridine ring. Specifically, ring E may represent a benzene ring.
L1 represents a single bond, a substituted or unsubstituted (3- to 30-membered)heteroarylene, or a substituted or unsubstituted (C6-C30)arylene; and preferably, a single bond, a substituted or unsubstituted (5- to 21-membered)heteroarylene, or a substituted or unsubstituted (C6-C21)arylene; and more preferably, a single bond, or a substituted or unsubstituted (C6-C18)arylene. Specifically, L1 may represent a single bond, or phenyl.
X1 to X3, each independently, represent -N- or -CR6-; and preferably, zero to two of X1 to X3 represents -N-, and the remainder(s) represents -CR6-. Specifically, where A represents formula 2a, X1 to X3 may represent -CR6-; or X1 may represent -N-, and X2 and X3 may represent -CR6-; or X1 and X3 may represent -N-, and X2 may represent -CR6-. In addition, where A represents formula 2b, one of X1 to X3 may represent -N-, and the reminders may represent -CR6-, specifically; and more specifically, one of X1 and X2 may represent -N-, and the reminders may represent -CR6-.
R1 to R6, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di-(C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or R1, R2 and R6, each independently, may be fused with an adjacent substituent(s) to form a substituted or unsubstituted (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur; and preferably, R1 to R6, each independently, represent hydrogen, a halogen, a cyano, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C5-C21)cycloalkyl, a substituted or unsubstituted (C6-C21)aryl, a substituted or unsubstituted (5- to 21-membered)heteroaryl, a substituted or unsubstituted tri(C6-C21)arylsilyl, a substituted or unsubstituted (C1-C20)alkyldi(C6-C21)arylsilyl, a substituted or unsubstituted mono- or di-(C6-C21)arylamino, or a substituted or unsubstituted (C1-C20)alkyl(C6-C21)arylamino; or R1, R2 and R6, each independently, may be fused with an adjacent substituent(s) to form a substituted or unsubstituted (5- to 21-membered), mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with one or two hetero atom(s) selected from nitrogen, oxygen, and sulfur. More preferably, R1 and R2, each independently, represent hydrogen, a halogen, a substituted or unsubstituted (C1-C10)alkyl, a substituted or unsubstituted (C5-C18)cycloalkyl, a substituted or unsubstituted (C6-C18)aryl, a substituted or unsubstituted tri(C6-C18)arylsilyl, or a substituted or unsubstituted di(C6-C18)arylamino, and may be fused with an adjacent substituent(s) to form a substituted or unsubstituted (5- to 18-membered) monocyclic aromatic ring; R3 represents hydrogen, a substituted or unsubstituted (C6-C18)aryl, or a substituted or unsubstituted (5- to 18-membered)heteroaryl; R4 and R5, each independently, represent hydrogen, or a substituted or unsubstituted (C6-C18)aryl; and R6 represents hydrogen or a (C1-C6)alkyl. Specifically, R1 and R2, each independently, may represent hydrogen, a halogen, a (C1-C4)alkyl, cyclohexyl, phenyl, triphenylsilyl, or diphenylamino, and may be fused with an adjacent substituent(s) to form a benzene ring; R3 may represent hydrogen, phenyl, biphenyl, naphthyl, dibenzothiophenyl, dibenzofuranyl, 9-phenyl-9H-carbazolyl, or 9,9-dimethyl-9H-fluorenyl; R4 and R5, each independently, may represent hydrogen or phenyl; and R6 may represent hydrogen.
a and b, each independently, represent an integer of 1 to 4; and preferably, 1 or 2; and more preferably 1; and where a or b represents 2 or more, each of R1 or R2 may be the same or different.
c, d and e, each independently, represent an integer of 1 or 2; and preferably, c represents 1 or 2; d and e represent 1; and where c, d or e represents 2, each of R3, R4 or R5 may be the same or different.
According to one aspect of the present disclosure, ring E represents a substituted or unsubstituted (C6-C21)aryl, or a substituted or unsubstituted (5- to 21-membered)heteroaryl; L1 represents a single bond, a substituted or unsubstituted (5- to 21-membered)heteroarylene, or a substituted or unsubstituted (C6-C21)arylene; zero to two of X1 to X3 represents -N-, and the remainder(s) represents -CR6-; R1 to R6, each independently, represent hydrogen, a halogen, a cyano, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C5-C21)cycloalkyl, a substituted or unsubstituted (C6-C21)aryl, a substituted or unsubstituted (5- to 21-membered)heteroaryl, a substituted or unsubstituted tri(C6-C21)arylsilyl, a substituted or unsubstituted (C1-C20)alkyldi(C6-C21)arylsilyl, a substituted or unsubstituted mono- or di-(C6-C21)arylamino, or a substituted or unsubstituted (C1-C20)alkyl(C6-C21)arylamino; or R1, R2 and R6, each independently, may be fused with an adjacent substituent(s) to form a substituted or unsubstituted (5- to 21-membered), mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with one or two hetero atom(s) selected from nitrogen, oxygen, and sulfur; the heteroaryl(ene) contains one or two hetero atom(s) selected from N, O, and S; a and b, each independently, represent 1 or 2, where a or b represents 2, each of R1 or R2 may be the same or different; and c represents 1 or 2, d and e represent 1, and where c represents 2, each of R3 may be the same or different.
According to another aspect of the present disclosure, the compound of formula 1 may be represented by the following formula 3:
Figure PCTKR2014012388-appb-I000004
wherein L1, X1, X3, R1 to R5, and a to e are as defined in formula 1. Preferably, X1 to X3, each independently, represent -N- or -CH-; R3 represents hydrogen, a substituted or unsubstituted (C6-C18)aryl, or a substituted or unsubstituted (5- to 18-membered)heteroaryl; and c represents an integer of 1 or 2. Where c represents 2, each of R3 may be the same or different.
According to another aspect of the present disclosure, the compound of formula 1 may be represented by the following formula 4:
Figure PCTKR2014012388-appb-I000005
wherein L1, R1 to R5, and a to e are as defined in formula 1. Preferably, R3 represents a substituted or unsubstituted (C6-C18)aryl, or a substituted or unsubstituted (5- to 18-membered)heteroaryl; and c represents 1.
More specifically, the organic electroluminescent compound of the present disclosure includes the following, but is not limited thereto:
Figure PCTKR2014012388-appb-I000006
Figure PCTKR2014012388-appb-I000007
Figure PCTKR2014012388-appb-I000008
Figure PCTKR2014012388-appb-I000009
Figure PCTKR2014012388-appb-I000010
Figure PCTKR2014012388-appb-I000011
Figure PCTKR2014012388-appb-I000012
Figure PCTKR2014012388-appb-I000013
Figure PCTKR2014012388-appb-I000014
Figure PCTKR2014012388-appb-I000015
Figure PCTKR2014012388-appb-I000016
The organic electroluminescent compounds of the present disclosure can be prepared by a synthetic method known to one skilled in the art. For example, they can be prepared according to the following reaction scheme 1.
[Reaction Scheme 1]
Figure PCTKR2014012388-appb-I000017
Furthermore, the present disclosure provides an organic electroluminescent material comprising the organic electroluminescent compound of formula 1, and an organic electroluminescent device comprising the material.
The material may consist of the organic electroluminescent compound of the present disclosure. Otherwise, the material may further comprise a conventional compound(s) which has been comprised for an organic electroluminescent material, in addition to the compound of the present disclosure.
The organic electroluminescent device of the present disclosure may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes. The organic layer may comprise at least one compound of formula 1.
One of the first and second electrodes may be an anode, and the other may be a cathode. The organic layer may comprise a light-emitting layer, and may further comprise at least one layer selected from a hole injection layer, a hole transport layer, an electron transport layer, an electron injection layer, an interlayer, a hole blocking layer, an electron buffer layer, and an electron blocking layer.
The organic electroluminescent compound of the present disclosure may be comprised in the light-emitting layer. When used in the light-emitting layer, the organic electroluminescent compound of the present disclosure may be comprised as a host material. Preferably, the light-emitting layer may further comprise at least one dopant, and if necessary, a compound other than the organic electroluminescent compound of formula 1 may be comprised additionally as a second host material.
The second host material may be from any of the known phosphorescent host materials. Specifically, the material selected from the group consisting of the compounds of formulae 5 to 9 below is preferable as the second host material in view of luminous efficiency.
Figure PCTKR2014012388-appb-I000018
Figure PCTKR2014012388-appb-I000019
Figure PCTKR2014012388-appb-I000020
Figure PCTKR2014012388-appb-I000021
Figure PCTKR2014012388-appb-I000022
wherein, Cz represents the following structure:
Figure PCTKR2014012388-appb-I000023
X' represents -O- or -S-; R21 to R24, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (5- to 30-membered)heteroaryl, or R25R26R27Si-; R25 to R27, each independently, represent a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; L4 represents a single bond, a substituted or unsubstituted (C6-C30)arylene, or a substituted or unsubstituted (5- to 30-membered)heteroarylene; M represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl; Z1 and Z2, each independently, represent -O-, -S-, -N(R31)- or -C(R32)(R33)-, provided that Z1 and Z2 do not simultaneously exist; R31 to R33, each independently, represent a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (5- to 30-membered)heteroaryl, 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 p, each independently, represent an integer of 0 to 4; and where h, i, j, k, l, or p is an integer of 2 or more, each of (Cz-L4), each of (Cz), each of R21, each of R22, each of R23, or each of R24 may be the same or different.
Specifically, the second host material includes the following:
Figure PCTKR2014012388-appb-I000024
Figure PCTKR2014012388-appb-I000025
Figure PCTKR2014012388-appb-I000026
Figure PCTKR2014012388-appb-I000027
Figure PCTKR2014012388-appb-I000028
Figure PCTKR2014012388-appb-I000029
Figure PCTKR2014012388-appb-I000030
Figure PCTKR2014012388-appb-I000031
Figure PCTKR2014012388-appb-I000032
Figure PCTKR2014012388-appb-I000033
Figure PCTKR2014012388-appb-I000034
Figure PCTKR2014012388-appb-I000035
Figure PCTKR2014012388-appb-I000036
Figure PCTKR2014012388-appb-I000037
Figure PCTKR2014012388-appb-I000038
Figure PCTKR2014012388-appb-I000039
Figure PCTKR2014012388-appb-I000040
(Wherein, TPS represents triphenylsilyl.)
The dopant is preferably at least one phosphorescent dopant. The phosphorescent dopant material for the organic electroluminescent device of the present disclosure is not limited, but may be preferably selected from metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) or platinum (Pt), more preferably selected from ortho-metallated complex compounds of iridium (Ir), osmium (Os), copper (Cu) or platinum (Pt), and even more preferably ortho-metallated iridium complex compounds.
The dopant for the organic electroluminescent device of the present disclosure includes compounds represented by the following formulae 10 to 12.
Figure PCTKR2014012388-appb-I000041
wherein L is selected from the following structures:
Figure PCTKR2014012388-appb-I000042
R100 represents hydrogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C3-C30)cycloalkyl; R101 to R109 and R111 to R123, each independently, represent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen, a substituted or unsubstituted (C3-C30)cycloalkyl, a cyano, a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (C1-C30)alkoxy; R106 to R109 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a substituted or unsubstituted fluorene, a substituted or unsubstituted dibenzothiophene, or a substituted or unsubstituted dibenzofuran; R120 to R123 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a substituted or unsubstituted quinoline; R124 to R127, each independently, represent hydrogen, deuterium, a halogen, a substituted or unsubstituted (C1-C30)alkyl, or a substituted or unsubstituted (C6-C30)aryl; R124 to R127 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a substituted or unsubstituted fluorene, a substituted or unsubstituted dibenzothiophene, or a substituted or unsubstituted dibenzofuran; R201 to R211, each independently, repesent hydrogen, deuterium, a halogen, a (C1-C30)alkyl unsubstituted or substituted with a halogen, a substituted or unsubstituted (C3-C30)cycloalkyl, or a substituted or unsubstituted (C6-C30)aryl, and R208 to R211 may be linked to an adjacent substituent(s) to form a substituted or unsubstituted fused ring, for example, a substituted or unsubstituted fluorene, a substituted or unsubstituted dibenzothiophene, or a substituted or unsubstituted dibenzofuran; f and g, each independently, represent an integer of 1 to 3; where f or g is an integer of 2 or more, each of R100 may be the same or different; and n represents an integer of 1 to 3.
Specifically, the dopant material includes the following:
Figure PCTKR2014012388-appb-I000043
Figure PCTKR2014012388-appb-I000044
Figure PCTKR2014012388-appb-I000045
Figure PCTKR2014012388-appb-I000046
Figure PCTKR2014012388-appb-I000047
Figure PCTKR2014012388-appb-I000048
Figure PCTKR2014012388-appb-I000049
Figure PCTKR2014012388-appb-I000050
Figure PCTKR2014012388-appb-I000051
Figure PCTKR2014012388-appb-I000052
Figure PCTKR2014012388-appb-I000053
Figure PCTKR2014012388-appb-I000054
Figure PCTKR2014012388-appb-I000055
Figure PCTKR2014012388-appb-I000056
Figure PCTKR2014012388-appb-I000057
Figure PCTKR2014012388-appb-I000058
Figure PCTKR2014012388-appb-I000059
Figure PCTKR2014012388-appb-I000060
Figure PCTKR2014012388-appb-I000061
Figure PCTKR2014012388-appb-I000062
Figure PCTKR2014012388-appb-I000063
According to an additional aspect of the present disclosure, a material for preparing an organic electroluminescent device is provided. The material comprises the compound of the present disclosure. The material may be a material for preparing a light-emitting layer or an electron transport layer of an organic electroluminescent device. When the compound of the present disclosure is comprised in the material for preparing a light-emitting layer of an organic electroluminescent device, the compound of the present disclosure may be comprised as a host material. When the compound of the present disclosure is comprised as a host material, the material may further comprise a second host material, in which the weight ratio of the first host material to the second host material may be in the range of 1:99 to 99:1. When the compound of the present disclosure is comprised in the material for preparing an electron transport layer of an organic electroluminescent device, the compound of the present disclosure may be comprised as an electron transport material. The material may be in a form of mixture or composition.
The organic electroluminescent device of the present disclosure may comprise a first electrode, a second electrode, and at least one organic layer disposed between the first and second electrodes, wherein the organic layer may comprise the material for the organic electroluminescent device of the present disclosure.
The organic electroluminescent device of the present disclosure may further comprise, in addition to the compound of formula 1, 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 disclosure, the organic layer may further comprise, in addition to the compound 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 the d-transition elements of the Periodic Table, or at least one complex compound comprising the metal. The organic layer may further comprise one or more additional light-emitting layers and a charge generating layer.
In addition, the organic electroluminescent device of the present disclosure 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 known in the field, besides the compound of the present disclosure. If necessary, it may further comprise a yellow light-emitting layer or an orange light-emitting layer.
In the organic electroluminescent device of the present disclosure, preferably, at least one layer (hereinafter, "a surface layer”) may be placed on an inner surface(s) of one or both electrode(s), selected from a chalcogenide layer, a metal halide layer and a metal oxide layer. Specifically, a chalcogenide (includes oxides) layer of silicon or aluminum is preferably placed on an anode surface of an electroluminescent medium layer, and a metal halide layer or a metal oxide layer is preferably placed on a cathode surface of an electroluminescent medium layer. Such a surface layer provides operation 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.
In the organic electroluminescent device of the present disclosure, 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 an electroluminescent medium. Furthermore, the hole transport compound is oxidized to a cation, and thus it becomes easier to inject and transport holes from the mixed region to the electroluminescent 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 electroluminescent device having two or more light-emitting layers and emitting white light.
In order to form each layer of the organic electroluminescent device of the present disclosure, dry film-forming methods such as vacuum evaporation, sputtering, plasma and ion plating methods, or wet film-forming methods such as ink jet printing, nozzle printing, slot coating, spin coating, dip coating, and flow coating methods can be used.
When using a wet film-forming method, a thin film can be formed by dissolving or diffusing materials forming each layer into any suitable solvent such as ethanol, chloroform, tetrahydrofuran, dioxane, etc. The solvent can be any solvent where the materials forming each layer can be dissolved or diffused, and where there are no problems in film-formation capability.
Hereinafter, the compound of the present disclosure, the preparation method of the compound, and the luminescent properties of the device will be explained in detail with reference to the following examples.
Example 1: Preparation of compound H-1
Figure PCTKR2014012388-appb-I000064
Figure PCTKR2014012388-appb-I000065
Preparation of compound 2
After dissolving compound 1 (25 g, 87.42 mmol), 2-methylthioboronic acid (14.7 g, 87.42 mmol), and tetrakis(triphenylphosphine)palladium(O) (Pd(pph3)4) (5 g, 4.37 mmol) in 2 M Na2CO3 (100 mL), toluene (430 mL), and ethanol (100 mL), the mixture was under reflux for 4 hours at 120°C. After completing the reaction, an organic layer was extracted with ethyl acetate. The obtained organic layer was dried with magnesium sulfate to remove the residual moisture therefrom, and the remaining product was purified by column chromatography to obtain compound 2 (20 g, 70 %).
Preparation of compound 3
After dissolving compound 2 (20 g, 60.74 mmol), bis(pinacolato)diboran (18.5 g, 72.89 mmol), bis(triphenylphosphine)palladium(II)dichloride (PbCl2(pph3)2) (1.7 g, 2.43 mmol), and potassium acetate (15 g, 151 mmol) in tetrahydrofuran (THF) (300 mL), the mixture was under reflux for 10 hours at 100°C. After completing the reaction, an organic layer was extracted with ethyl acetate. The obtained organic layer was dried with magnesium sulfate to remove the residual moisture therefrom, and the remaining product was purified by column chromatography to obtain compound 3 (19.5 g, 85 %).
Preparation of compound 4
After dissolving compound 3 (19.5 g, 51.81 mmol), 2-bromonitrobenzene (11.5 g, 56.99 mmol), and Pd(pph3)4 (3 g, 2.59 mmol) in 2 M Na2CO3 (70 mL), toluene (260 mL), and ethanol (70 mL), the mixture was under reflux for 4 hours at 120°C. After completing the reaction, an organic layer was extracted with ethyl acetate. The obtained organic layer was dried with magnesium sulfate to remove the residual moisture therefrom, and the remaining product was purified by column chromatography to obtain compound 4 (19.1 g, 95 %).
Preparation of compound 5
After dissolving compound 4 (19 g, 51.1 mmol) in THF (300 mL) and acetic acid (150 mL), hydrogen peroxide (35 %) (13.1 mL) was added slowly and dropwise thereto, and the mixture was then under reflux for 10 hours at room temperature. After completing the reaction, the mixture was concentrated and an organic layer was extracted with dichloromethane and purified water. The obtained organic layer was dried with magnesium sulfate to remove the residual moisture therefrom, and concentrated. Thereafter, the next reaction was conducted immediately.
Preparation of compound 6
After dissolving crude compound 5 (18 g) in trifluoromethanesulfonic acid (63 mL), the mixture was under reflux for 2 days at room temperature, the mixture was added slowly and dropwise to a solution of pyridine (90mL)/purified water (700mL), and heated. Thereafter, the mixture was under reflux for 4 hours at 120°C. After completing the reaction, an organic layer was extracted with dichloromethane, and the remaining product was purified by column chromatography to obtain compound 6 (13 g, 78.8 %).
Preparation of compound 7
After dissolving compound 6 (13 g, 36.57 mmol) and triphenylphosphine (24 g, 91.44 mmol) in dichlorobenzene (180 mL), the mixture was under reflux for 12 hours at 195°C. After completing the reaction, dichlorobenzene was removed by distillation, and the remaining product was purified by column chromatography to obtain compound 7 (5.6 g, 47 %).
Preparation of compound H-1
After dissolving compound 7 (2.6 g, 9.65 mmol) and compound 10 (3 g, 11.57 mmol) in dimethylformamide (DMF) (50 mL), NaH (1.2 g, 28.9 mmol, 60% in mineral oil) was added thereto, and the mixture was then under reflux for 12 hours at room temperature. Thereafter, methanol and purified water were added thereto. The produced solid was filtered under reduced pressure, and the remaining product was purified by column chromatography to obtain compound H-1 (2.2 g, 45 %).
UV: 338 nm, PL: 493 nm, mp: 286 °C,
MS/EIMS: 555 (measured value), 554.6 (calculated value)
Example 2: Preparation of compound H-15
Figure PCTKR2014012388-appb-I000066
After dissolving compound 7 (3 g, 9.28 mmol) and compound 8 (2.67 g, 11.13 mmol) in dimethylformamide (DMF) (100 mL), NaH (1.1 g, 27.83 mmol, 60% in mineral oil) was added thereto. The mixture was then under reflux for 12 hours at room temperature. Thereafter, methanol and purified water were added thereto. The produced solid was filtered under reduced pressure, and the remaining product was purified by column chromatography to obtain compound H-15 (2.2 g, 45 %).
UV: 324 nm, PL: 503 nm, mp: 324 °C,
MS/EIMS: 528 (measured value), 527 (calculated value)
[Device Example 1] OLED using the compound of the present disclosure
OLED comprising the organic electroluminescent compounds of the present disclosure was produced as follows. A transparent electrode indium tin oxide (ITO) thin film (15 Ω/sq) on a glass substrate for an organic light-emitting diode (OLED) (Samsung Corning) was subjected to an ultrasonic washing with trichloroethylene, acetone, ethanol, and distilled water, sequentially, and was then stored in isopropanol. The ITO substrate was then mounted on a substrate holder of a vacuum vapor depositing apparatus. N1,N1’-([1,1’-biphenyl]-4,4’-diyl)bis(N1-(naphthalen-1-yl)-N4,N4-diphenylbenzene-1,4-diamine) was introduced into a cell of said vacuum vapor depositing apparatus, and the pressure in the chamber of said apparatus was then controlled to 10-6 torr. Thereafter, an electric current was applied to the cell to evaporate the above 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 then introduced into another cell of said vacuum vapor depositing apparatus, and evaporated by applying electric current to the cell, thereby forming a hole transport layer having a thickness of 20 nm on the hole injection layer. Thereafter, compound H-15 of the present disclosure was introduced into one cell of the vacuum vapor depositing apparatus, as a host, and compound D-87 was introduced into another cell as a dopant. The two materials were evaporated at different rates so that the dopant was deposited in a doping amount of 4 wt% based on the total amount 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(naphthalen-2-yl)anthracen-2-yl)phenyl)-1-phenyl-1H-benzo[d]imidazole was then introduced into one cell, and lithium quinolate was introduced into another cell. The two materials were evaporated at the same rate so that they 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. 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 then deposited by another vacuum vapor deposition apparatus on the electron injection layer. Thus, an OLED was produced. All the materials used for producing the OLED were those purified by vacuum sublimation at 10-6 torr.
The produced OLED showed red emission having a luminance of 920 cd/m2 and a current density of 7.9 mA/cm2 at a driving voltage of 3.6 V. The time period for the luminance to decrease to 90% at 5000 nits was 70 hours or more.
[Comparative Device Example 1] OLED using conventional compounds
OLED was produced in the same manner as in Device Example 1, except for using the compound shown below as a host and compound D-87 as a dopant to form a light-emitting layer.
The produced OLED showed red emission having a luminance of 900 cd/m2 and a current density of 8.9 mA/cm2 at a driving voltage of 3.6 V. The time period for the luminance to decrease to 90% at 5000 nits was 40 hours or more.
Figure PCTKR2014012388-appb-I000067
From the above device examples, it is confirmed that an organic electroluminescent device can show long lifespan and excellent luminous and power efficiencies by using the organic electroluminescent compound of the present disclosure.

Claims (7)

  1. An organic electroluminescent compound represented by the following formula 1:
    Figure PCTKR2014012388-appb-I000068
    wherein
    A represents the following formula 2a or 2b:
    Figure PCTKR2014012388-appb-I000069
    Figure PCTKR2014012388-appb-I000070
    * represents a bonding site;
    L1 represents a single bond, a substituted or unsubstituted (3- to 30-membered) heteroarylene, or a substituted or unsubstituted (C6-C30)arylene;
    ring E represents a substituted or unsubstituted (C6-C30)aryl, or a substituted or unsubstituted (3- to 30-membered)heteroaryl;
    X1 to X3, each independently, represent -N- or -CR6-;
    R1 to R6, each independently, represent hydrogen, deuterium, a halogen, a cyano, a substituted or unsubstituted (C1-C30)alkyl, a substituted or unsubstituted (C3-C30)cycloalkyl, a substituted or unsubstituted (C3-C30)cycloalkenyl, a substituted or unsubstituted (3- to 7-membered)heterocycloalkyl, a substituted or unsubstituted (C6-C30)aryl, a substituted or unsubstituted (3- to 30-membered)heteroaryl, a substituted or unsubstituted tri(C6-C30)arylsilyl, a substituted or unsubstituted di(C1-C30)alkyl(C6-C30)arylsilyl, a substituted or unsubstituted (C1-C30)alkyldi(C6-C30)arylsilyl, a substituted or unsubstituted mono- or di-(C6-C30)arylamino, or a substituted or unsubstituted (C1-C30)alkyl(C6-C30)arylamino; or R1, R2 and R6, each independently, may be fused with an adjacent substituent(s) to form a substituted or unsubstituted (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with at least one hetero atom selected from nitrogen, oxygen, and sulfur;
    the heteroaryl(ene) and heterocycloalkyl, each independently, contain at least one hetero atom selected from B, N, O, S, P(=O), Si and P;
    a and b, each independently, represent an integer of 1 to 4; where a or b represents an integer of 2 or more, each of R1 or R2 may be the same or different;
    c, d and e, each independently, represent an integer of 1 to 2; and where c, d or e represents 2, each of R3, R4 or R5 may be the same or different.
  2. The organic electroluminescent compound according to claim 1, wherein the substituents of the substituted (C1-C30)alkyl, the substituted (C3-C30)cycloalkyl, the substituted (C3-C30)cycloalkenyl, the substituted (3- to 7-membered)heterocycloalkyl, the substituted (C6-C30)aryl(ene), the substituted (3- to 30-membered)heteroaryl(ene), the substituted (C6-C30)arylamino and the substituted (3- to 30-membered), mono- or polycyclic, alicyclic or aromatic ring in L1 and R1 to R6, each independently, are at least one selected from the group consisting of deuterium, a halogen, a cyano, a carboxyl, a nitro, a hydroxyl, a (C1-C30)alkyl, a halo(C1-C30)alkyl, a (C2-C30)alkenyl, a (C2-C30)alkynyl, a (C1-C30)alkoxy, a (C1-C30)alkylthio, a (C3-C30)cycloalkyl, a (C3-C30)cycloalkenyl, a (3- to 7-membered)heterocycloalkyl, a (C6-C30)aryloxy, a (C6-C30)arylthio, a (3- to 30-membered)heteroaryl unsubstituted or substituted with a (C6-C30)aryl, a (C6-C30)aryl unsubstituted or substituted with a (3- to 30-membered)heteroaryl, a tri(C1-C30)alkylsilyl, a tri(C6-C30)arylsilyl, a di(C1-C30)alkyl(C6-C30)arylsilyl, a (C1-C30)alkyldi(C6-C30)arylsilyl, an amino, a mono- or di-(C1-C30)alkylamino, a mono- or di-(C6-C30)arylamino, a (C1-C30)alkyl(C6-C30)arylamino, a (C1-C30)alkylcarbonyl, a (C1-C30)alkoxycarbonyl, a (C6-C30)arylcarbonyl, a di(C6-C30)arylboronyl, a di(C1-C30)alkylboronyl, a (C1-C30)alkyl(C6-C30)arylboronyl, a (C6-C30)aryl(C1-C30)alkyl and a (C1-C30)alkyl(C6-C30)aryl.
  3. The organic electroluminescent compound according to claim 1, wherein
    ring E represents a substituted or unsubstituted (C6-C21)aryl or a substituted or unsubstituted (5- to 21-membered)heteroaryl;
    L1 represents a single bond, a substituted or unsubstituted (5- to 21-membered)heteroarylene, or a substituted or unsubstituted (C6-C21)arylene;
    zero to two of X1 to X3 represents -N-, and the remainder(s) represents -CR6-;
    R1 to R6, each independently, represent hydrogen, a halogen, a cyano, a substituted or unsubstituted (C1-C20)alkyl, a substituted or unsubstituted (C5-C21)cycloalkyl, a substituted or unsubstituted (C6-C21)aryl, a substituted or unsubstituted (5- to 21-membered)heteroaryl, a substituted or unsubstituted tri(C6-C21)arylsilyl, a substituted or unsubstituted (C1-C20)alkyldi(C6-C21)arylsilyl, a substituted or unsubstituted mono- or di-(C6-C21)arylamino, or a substituted or unsubstituted (C1-C20)alkyl(C6-C21)arylamino; or R1, R2 and R6, each independently, may be fused with an adjacent substituent(s) to form a substituted or unsubstituted (5- to 21-membered), mono- or polycyclic, alicyclic or aromatic ring whose carbon atom(s) may be replaced with one or two hetero atom(s) selected from nitrogen, oxygen, and sulfur;
    the heteroaryl(ene) contains one or two hetero atom(s) selected from N, O, and S;
    a and b, each independently, represent 1 or 2; where a or b represents 2, each of R1 or R2 may be the same or different;
    c represents 1 or 2; d and e represent 1; and where c represents 2, each of R3 may be the same or different.
  4. The organic electroluminescent compound according to claim 1, wherein the compound is represented by the following formula 3:
    Figure PCTKR2014012388-appb-I000071
    wherein
    L1, X1, X3, R1 to R5, and a to e are as defined in claim 1.
  5. The organic electroluminescent compound according to claim 1, wherein the compound is represented by the following formula 4:
    Figure PCTKR2014012388-appb-I000072
    wherein
    L1, R1 to R5, and a to e are as defined in claim 1.
  6. The organic electroluminescent compound according to claim 1, wherein the compound of formula 1 is selected from the group consisting of:
    Figure PCTKR2014012388-appb-I000073
    Figure PCTKR2014012388-appb-I000074
    Figure PCTKR2014012388-appb-I000075
    Figure PCTKR2014012388-appb-I000076
    Figure PCTKR2014012388-appb-I000077
    Figure PCTKR2014012388-appb-I000078
    Figure PCTKR2014012388-appb-I000079
    Figure PCTKR2014012388-appb-I000080
    Figure PCTKR2014012388-appb-I000081
    Figure PCTKR2014012388-appb-I000082
    Figure PCTKR2014012388-appb-I000083
  7. An organic electroluminescent device comprising the compound according to claim 1.
PCT/KR2014/012388 2013-12-16 2014-12-16 Organic electroluminescent compounds and organic electroluminescent device comprising the same WO2015093814A1 (en)

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